JP3508180B2 - Exhaust gas purification catalyst and method for producing the same - Google Patents
Exhaust gas purification catalyst and method for producing the sameInfo
- Publication number
- JP3508180B2 JP3508180B2 JP27176293A JP27176293A JP3508180B2 JP 3508180 B2 JP3508180 B2 JP 3508180B2 JP 27176293 A JP27176293 A JP 27176293A JP 27176293 A JP27176293 A JP 27176293A JP 3508180 B2 JP3508180 B2 JP 3508180B2
- Authority
- JP
- Japan
- Prior art keywords
- active species
- metal
- exhaust gas
- noble metal
- base material
- 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 40
- 238000000746 purification Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 229910000510 noble metal Inorganic materials 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052741 iridium Inorganic materials 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
- 238000005987 sulfurization reaction Methods 0.000 claims description 12
- 239000010970 precious metal Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052702 rhenium Inorganic materials 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 150000004760 silicates Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 description 17
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 13
- 239000010948 rhodium Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 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 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は排気ガス浄化用触媒及び
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.
【０００２】[0002]
【従来の技術】自動車用エンジンの三元触媒、酸化触
媒、酸素過剰雰囲気でのＮＯｘ浄化を図るＮＯｘ浄化用
触媒等の排気ガス浄化用触媒は、無機多孔質の母材に活
性種（触媒金属）を担持させて構成されている。Exhaust gas purifying catalysts such as three-way catalysts for automobile engines, oxidation catalysts, and NOx purifying catalysts for purifying NOx in an oxygen-rich atmosphere are used as active species (catalyst metal) in an inorganic porous base material. ) Is carried.
【０００３】上記母材への活性種の担持にあたっては、
母材に活性種の溶液を含浸させて乾燥させる含浸法、活
性種の溶液に粉末状の母材を分散させてなるスラリーを
蒸発乾固する蒸発乾固法、活性種をゼオライト等の金属
含有シリケート（多数の細孔を有する結晶質の多孔質
体）の陽イオンと交換させるイオン交換法など種々の方
法が採用されている。例えば、特開平４−２４３５４５
号公報には、ゼオライト母材に活性種としてのＰｔやＲ
ｈをイオン交換法によって担持させる方法が記載されて
いる。In carrying the active species on the base material,
Impregnation method in which base material is impregnated with a solution of active species and dried, evaporation dry method in which slurry of powdered base material dispersed in solution of active species is evaporated to dryness, active species containing metal such as zeolite Various methods such as an ion exchange method of exchanging with cations of silicate (a crystalline porous body having a large number of pores) have been adopted. For example, Japanese Patent Laid-Open No. 4-243545
In the publication, Pt and R as active species are added to the zeolite matrix.
A method of supporting h by an ion exchange method is described.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上述の如き触
媒を高温雰囲気下において長時間使用すると、母材に担
持されている活性種のシンタリングを生じる。その結
果、触媒活性が大きく低下し、以後は所期の浄化率を期
待することができなくなる。すなわち、本発明の課題は
上記活性種のシンタリングを防止することにある。However, when the above catalyst is used for a long time in a high temperature atmosphere, the active species carried on the base material are sintered. As a result, the catalytic activity is greatly reduced, and thereafter, the desired purification rate cannot be expected. That is, an object of the present invention is to prevent sintering of the active species.
【０００５】[0005]
【課題を解決するための手段及びその作用】本発明者
は、このような課題に対して、母材に活性種と共に金属
の硫化物もしくはリン化物を担持させると、該硫化物な
いしはリン化物が立体障害となって活性種のシンタリン
グを阻止することを見出だし、本発明を完成するに至っ
たものである。Means for Solving the Problems and Actions Thereof The present inventor responds to such problems by allowing a base material to carry a metal sulfide or phosphide together with active species, so that the sulfide or phosphide is formed. The present inventors have found that it causes steric hindrance and prevents the sintering of active species, thus completing the present invention.
【０００６】すなわち、請求項１に係る発明は、ミクロ
の細孔を有する結晶質の金属含有シリケートに、Ｐｔ、
Ｉｒ及びＲｈの貴金属活性種と、該貴金属活性種よりも
硫黄との親和力が強い Ｉｎ、Ｓｎ、Ｇｅ及びＲｅのうち
から選ばれる１種以上の金属とを担持させ、しかる後に
ＳＯ 2 雰囲気で加熱する硫化処理を行なうことにより、
上記貴金属活性種と、上記選択された金属の硫化物とが
上記金属含有シリケートに分散担持されていることを特
徴とする排気ガス浄化用触媒である。That is, the invention according to claim 1 is
To the crystalline metal-containing silicate having pores of Pt,
Noble metal active species of Ir and Rh and more than the noble metal active species
Of In, Sn, Ge and Re that have a strong affinity for sulfur
One or more metals selected from
By performing sulfurization treatment by heating in an SO 2 atmosphere,
The noble metal active species and the sulfide of the selected metal are
An exhaust gas purifying catalyst, wherein the catalyst is dispersed and carried on the metal-containing silicate .
【０００７】請求項２に係る発明は、ミクロの細孔を有
する結晶質の金属含有シリケートに、Ｐｔ、Ｉｒ及びＲ
ｈの貴金属活性種とＩｎとを担持させ、しかる後にリン
蒸気によるリン化処理を行なうことにより、上記貴金属
活性種と、上記Ｉｎのリン化物とが上記金属含有シリケ
ートに分散担持されていることを特徴とする排気ガス浄
化用触媒である。 The invention according to claim 2 has micropores.
To the crystalline metal-containing silicate
The precious metal active species of h and In are supported, and then phosphorus is added.
The above precious metals can be treated by steam phosphatization.
The active species and the In phosphide are the above-mentioned metal-containing liquor.
Exhaust gas cleaning
It is a chemical catalyst.
【０００８】上記請求項１，２の各触媒においては、活
性種のシンタリングが抑えられるが、これは活性種の間
に介在する金属硫化物もしくはＩｎのリン化物が立体障
害となって高温時における当該活性種の移動を阻止する
ためと考えられる。In the catalysts of claims 1 and 2, the sintering of the active species is suppressed, but this is because the metal sulfide or In phosphide intervening between the active species causes steric hindrance at high temperature. It is considered to prevent the migration of the active species.
【０００９】母材として金属含有シリケートを採用した
から、排気ガス中のＮＯｘの浄化率を高める上で有利に
なる。金属含有シリケートとしては、結晶の骨格をＡｌ
が構成するアルミノシリケート（所謂ゼオライト）の
他、結晶骨格構成金属としてＧａ、Ｃｅ、Ｍｎ、Ｔｂな
ど他の金属を単独でもしくはＡｌと共に用いたものであ
ってもよい。アルミノシリケートとしては、Ａ型、Ｘ
型、Ｙ型、モルデナイト、ＺＳＭ−５などいずれでも採
用することができる。 A metal-containing silicate is used as a base material.
Therefore, it is advantageous in increasing the purification rate of NOx in the exhaust gas.
Become. As the metal-containing silicate, the crystal skeleton is Al
Of aluminosilicate (so-called zeolite)
In addition, Ga, Ce, Mn, and Tb are used as the metal constituting the crystal skeleton.
Other metals alone or with Al
You may. As aluminosilicate, type A, X
Type, Y type, mordenite, ZSM-5, etc.
Can be used.
【００１０】また、上記活性種としてＰｔ、Ｉｒ及びＲ
ｈの貴金属活性種を採用したから、耐熱性を確保しなが
ら所期のＮＯｘ浄化を行なう上で有利である。 Further , Pt, Ir and R are used as the active species.
Since the precious metal active species of h is adopted, heat resistance must be secured.
It is advantageous in performing desired NOx purification.
【００１１】請求項３に係る発明は、無機多孔質の母材
にＰｔ、Ｉｒ及びＲｈの貴金属活性種を担持させた後
に、該貴金属活性種よりも硫黄との親和力が強いＩｎ、
Ｓｎ、Ｇｅ及びＲｅのうちから選ばれる１種以上の金属
を担持させ、しかる後に該金属の硫化処理をＳＯ 2 雰囲
気で行なうことを特徴とする排気ガス浄化用触媒の製造
方法である。 The invention according to claim 3 is an inorganic porous base material.
After supporting Pt, Ir and Rh precious metal active species on
In, which has a stronger affinity for sulfur than the noble metal active species,
One or more metals selected from Sn, Ge and Re
And then the sulfurization treatment of the metal is carried out in an SO 2 atmosphere.
Manufacture of an exhaust gas purifying catalyst characterized by being performed by air
Is the way.
【００１２】上記母材としては、ミクロの細孔有する結
晶質の金属含有シリケートを用いることが排気ガス中の
ＮＯｘの浄化率を高める上で好適であるが、γ−アルミ
ナなど他の無機多孔質材を用いることもできる。上記金
属含有シリケートとしては、結晶の骨格をＡｌが構成す
るアルミノシリケート（所謂ゼオライト）の他、結晶骨
格構成金属としてＧａ、Ｃｅ、Ｍｎ、Ｔｂなど他の金属
を単独でもしくはＡｌと共に用いたものであってもよ
い。アルミノシリケートとしては、Ａ型、Ｘ型、Ｙ型、
モルデナイト、ＺＳＭ−５などいずれでも採用すること
ができる。[0012] As the base material, although the use of a crystalline metal-containing silicate having pores of Mi black is preferable in increasing the purification rate of NOx in the exhaust gas, other inorganic porous such γ- alumina A quality material can also be used. As the metal-containing silicate, in addition to aluminosilicate (so-called zeolite) whose crystal skeleton is composed of Al, other metals such as Ga, Ce, Mn, and Tb are used alone or together with Al as crystal skeleton-constituting metals. It may be. As aluminosilicate, A type, X type, Y type,
Any of mordenite, ZSM-5 and the like can be adopted.
【００１３】このような製造方法においては、母材に対
してＩｎ等の金属よりも先に活性種を担持させるから、
該活性種の母材に対する担持性が他の金属により阻害さ
れることがなく、所期の量の貴金属を担持させることが
容易になる。そして、Ｉｎ、Ｓｎ、Ｇｅ及びＲｅは貴金
属よりも硫黄との親和力が強いから、硫化処理によって
貴金属のシンタリング防止に有効な上記Ｉｎ等の硫化物
が生成することになる。In such a manufacturing method, since the active species are supported on the base material before the metal such as In is supported,
The ability of the active species to be supported on the base material is not hindered by other metals, and it becomes easy to support the desired amount of the noble metal. Since In, Sn, Ge and Re have a stronger affinity for sulfur than noble metals, the above sulfides such as In that are effective in preventing sintering of noble metals are generated by the sulfurating treatment.
【００１４】上記硫化処理としては、上記貴金属活性種
及びＩｎ等の金属が担持された母材をＳＯ2濃度５０〜
２００ｐｐｍの雰囲気中で温度４００〜６００℃に加熱
することによって行なうことが好適である。ＳＯ2濃度
５０ｐｐｍ未満では上記Ｉｎ等の硫化が円滑に行なわれ
ず、また、２００ｐｐｍを越えるＳＯ2濃度では貴金属
が余分に被毒される懸念があるからである。一方、上記
温度４００℃未満では上記Ｉｎ等の硫化が円滑に行なわ
れず、また、６００℃を越える温度は母材の酸特性が変
化し好ましくない。In the sulfurization treatment, the base material on which the active metal of the noble metal and the metal such as In are carried is SO 2 concentration 50 to 50.
It is suitable to carry out by heating to a temperature of 400 to 600 ° C. in an atmosphere of 200 ppm. This is because if the SO 2 concentration is less than 50 ppm, the sulfuration of In or the like will not be carried out smoothly, and if the SO 2 concentration exceeds 200 ppm, the noble metal may be excessively poisoned. On the other hand, if the temperature is lower than 400 ° C., the sulfuration of In or the like is not carried out smoothly, and if the temperature exceeds 600 ° C., the acid characteristics of the base material change, which is not preferable.
【００１５】請求項４に係る発明は、無機多孔質の母材
に貴金属活性種を担持させた後に、この貴金属活性種が
担持された母材をＳＯ2雰囲気で加熱することによって
当該貴金属活性種の一部を貴金属硫化物に変えることを
特徴とする。According to a fourth aspect of the present invention , a noble metal active species is supported on an inorganic porous base material, and then the base material on which the noble metal active species is supported is heated in an SO 2 atmosphere. It is characterized in that a part of is converted into a noble metal sulfide.
【００１６】このような製造方法であれば、母材に対し
て、金属硫化物を構成する金属のみを単独で担持させる
必要がなく製造工程の簡素化が図れる。According to such a manufacturing method, it is not necessary to separately support only the metal forming the metal sulfide on the base material, and the manufacturing process can be simplified.
【００１７】当該方法における硫化処理としては、ＳＯ
2濃度を５０〜１００００ｐｐｍ程度として、４００〜
８００℃の加熱を行なうことが適当である。The sulfurizing treatment in this method is SO
2 From the concentration of 50 to 10,000 ppm, 400 to
It is appropriate to carry out heating at 800 ° C.
【００１８】[0018]
【発明の効果】従って、請求項１に係る発明によれば、
金属含有シリケートに担持されたＰｔ、Ｉｒ及びＲｈの
貴金属活性種によってＮＯｘ浄化率を高めながら、ＳＯ
2 雰囲気で加熱する硫化処理によって生成したＩｎ、Ｓ
ｎ、Ｇｅ又はＲｅの硫化物の立体障害効果によって、当
該貴金属活性種のシンタリングを防止することができ
る。Therefore, according to the invention of claim 1,
Of Pt, Ir and Rh supported on a metal-containing silicate
While increasing the NOx purification rate by the active species of precious metals, SO
In, S produced by sulfurization treatment by heating in 2 atmosphere
Depending on the steric hindrance effect of the sulfide of n, Ge or Re,
It is possible to prevent sintering of the noble metal active species.
【００１９】また、請求項２に係る発明によれば、金属
含有シリケートに担持されたＰｔ、Ｉｒ及びＲｈの貴金
属活性種によってＮＯｘ浄化率を高めながら、リン化処
理によって生成したＩｎのリン化物の立体障害効果によ
って、当該貴金属活性種のシンタリングを防止すること
ができる。 According to the invention of claim 2, the metal is
Noble gold of Pt, Ir and Rh supported on silicate containing
Phosphorus treatment while increasing NOx purification rate by genus active species
By the steric hindrance effect of In phosphide produced by
Prevent the sintering of the precious metal active species.
You can
【００２０】また、請求項３に係る発明によれば、無機
多孔質の母材にＰｔ、Ｉｒ及びＲｈの貴金属活性種を担
持させた後にＩｎ、Ｓｎ、Ｇｅ及びＲｅのうちから選ば
れる１種以上の金属を担持させ、しかる後に当該金属の
硫化処理を行なうようにしたから、上記貴金属活性種の
母材への担持性を阻害することなく、該貴金属活性種の
シンタリングに有効な硫化物を母材に分散担持させるこ
とができる。Further, according to the invention of claim 3, one kind selected from In, Sn, Ge and Re after supporting the noble metal active species of Pt, Ir and Rh on the inorganic porous base material. by supporting the above metal, it is so arranged perform sulfurization treatment of the metal and thereafter, without inhibiting the carrying property to the noble metal active species preform, effective sulfide sintering of the noble metal active species Can be dispersed and supported on the base material.
【００２１】また、請求項４に係る発明によれば、無機
多孔質の母材に貴金属活性種を担持させた後に、この貴
金属活性種が担持された母材をＳＯ2雰囲気で加熱する
ことによって当該貴金属活性種の一部を貴金属硫化物に
変えるようにしたから、母材への金属硫化物の分散担持
が容易になる。Further, according to the invention of claim 4, the noble metal active species are supported on the inorganic porous base material, and the base material on which the noble metal active species is supported is heated in an SO 2 atmosphere. Since a part of the noble metal active species is changed to the noble metal sulfide, it becomes easy to disperse and support the metal sulfide on the base material.
【００２２】[0022]
【実施例】以下、本発明の実施例を説明する。EXAMPLES Examples of the present invention will be described below.
【００２３】（実施例１）
−触媒材料の調製−
Ｐｔ、Ｉｒ及びＲｈが重量比で３０：１０：１となるよ
うに且つそれらの総量が触媒１リットル当たり６ｇとな
るように、２価白金アンミン結晶と三塩化イリジウムと
硝酸ロジウムとを秤量した。２価白金アンミン結晶と硝
酸ロジウムとについては水（イオン交換水）に溶解し、
三塩化イリジウムについてはエタノールに分散させ、し
かる後に両者を混合し、さらにその中にケイバン比７０
のＨ型ＺＳＭ−５粉末を加えた。そして、室温で２時間
撹拌した後、８０℃で３時間程加熱して液体分を蒸発さ
せ、さらに、１５０℃の恒温器で約６時間乾燥してＰ
ｔ、Ｉｒ及びＲｈがＺＳＭ−５に担持されてなる触媒粉
末を得た。(Example 1) -Preparation of catalyst material-Pt, Ir and Rh so that the weight ratio is 30: 10: 1 and the total amount thereof is 6 g per liter of the catalyst, divalent platinum. Ammine crystals, iridium trichloride and rhodium nitrate were weighed. Divalent platinum ammine crystals and rhodium nitrate are dissolved in water (ion-exchanged water),
Iridium trichloride was dispersed in ethanol, and then both were mixed, and the Caban ratio 70
H-form ZSM-5 powder was added. Then, after stirring at room temperature for 2 hours, it is heated at 80 ° C. for about 3 hours to evaporate the liquid content, and further dried in a thermostat at 150 ° C. for about 6 hours, and then P
A catalyst powder was obtained in which t, Ir and Rh were supported on ZSM-5.
【００２４】−ウォッシュコート−
上記触媒粉末をバインダ（水和アルミナ）と共に４００
セル／inch2のコーディエライト製ハニカム担体にウォ
ッシュコートした。-Washcoat- The above catalyst powder was mixed with a binder (hydrated alumina) 400
The cell / inch 2 cordierite honeycomb carrier was wash-coated.
【００２５】−硫化物の担持−
上記触媒粉末が担持されたハニカムをＩｎが触媒１リッ
トル当たり３ｇとなるように調製した硝酸インジウムＩ
ｎ(ＮＯ3)3・Ｈ2Ｏ溶液に浸漬した後、引上げて大気中
で５００℃×２時間の焼成を行なった。そして、当該ハ
ニカムをＳＯ2濃度１００ｐｐｍ（Ｎ2バランス）雰囲気
中で５００℃に２時間加熱することによってＩｎＳを生
成させた。-Support of Sulfide- Indium nitrate I prepared by adjusting the amount of In to be 3 g per liter of the catalyst supporting the above-mentioned catalyst powder.
After immersing in an n (NO 3 ) 3 · H 2 O solution, it was pulled up and fired in the atmosphere at 500 ° C. for 2 hours. Then, the honeycomb was heated at 500 ° C. for 2 hours in an atmosphere of SO 2 concentration of 100 ppm (N 2 balance) to generate InS.
【００２６】（実施例２〜１５）
実施例２〜４の各々は、実施例１におけるＩｎに代えて
Ｓｎ、Ｇｅ、Ｒｅを採用したものであり、他は実施例１
と同様にして排気ガス浄化用触媒を得た。Ｓｎについて
は酢酸第１スズＳｎ(ＣＨ3ＣＯＯ)2溶液を用い、Ｇｅに
ついては四塩化ゲルマニウムＧｅＣｌ4溶液を用い、ま
た、Ｒｅについては三塩化レニウムＲｅＣｌ3溶液を用
いた。この場合、実施例２ではＳｎＳ2が生成し、実施
例３ではＧｅＳ2が生成し、実施例４ではＲｅＳ2が生成
する。(Examples 2 to 15) In each of Examples 2 to 4, Sn, Ge, Re was adopted in place of In in Example 1, and other examples were adopted.
An exhaust gas purifying catalyst was obtained in the same manner as in. A stannous acetate Sn (CH 3 COO) 2 solution was used for Sn, a germanium tetrachloride GeCl 4 solution was used for Ge, and a rhenium trichloride ReCl 3 solution was used for Re. In this case, SnS 2 is generated in the second embodiment, GeS 2 is generated in the third embodiment, and ReS 2 is generated in the fourth embodiment.
【００２７】実施例５〜７の各々は、実施例１における
Ｉｎ量を３ｇ／ｌに代えてそれぞれ６ｇ／ｌ、９ｇ／
ｌ、１ｇ／ｌとしたものであり、他は実施例１と同様に
して排気ガス浄化用触媒を得た。In each of Examples 5 to 7, the amount of In in Example 1 was changed to 3 g / l, and 6 g / l and 9 g / l, respectively.
The exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that the amount was 1, 1 g / l.
【００２８】実施例８〜１０の各々は、実施例２におけ
るＳｎ量を３ｇ／ｌに代えてそれぞれ６ｇ／ｌ、９ｇ／
ｌ、１ｇ／ｌとしたものであり、他は実施例１と同様に
して排気ガス浄化用触媒を得た。In each of Examples 8 to 10, the amount of Sn in Example 2 was changed to 3 g / l, and 6 g / l and 9 g / l, respectively.
The exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that the amount was 1, 1 g / l.
【００２９】実施例１１〜１３の各々は、実施例１にお
ける硫化処理温度条件を５００℃×２時間に代えてそれ
ぞれ６００℃×２時間、７００℃×２時間、４００℃×
２時間としたものであり、他は実施例１と同様にして排
気ガス浄化用触媒を得た。In each of Examples 11 to 13, 600 ° C. × 2 hours, 700 ° C. × 2 hours, and 400 ° C. × were replaced with the sulfurization treatment temperature condition of Example 1 instead of 500 ° C. × 2 hours.
Exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that it was 2 hours.
【００３０】実施例１４，１５の各々は、実施例１にお
ける硫化処理のＳＯ2濃度を１００ｐｐｍに代えてそれ
ぞれ５０ｐｐｍ、２００ｐｐｍとしたものであり、他は
実施例１と同様にして排気ガス浄化用触媒を得た。In each of Examples 14 and 15, the SO 2 concentration of the sulfurating treatment in Example 1 was changed to 100 ppm to 50 ppm and 200 ppm, respectively. A catalyst was obtained.
【００３１】（実施例１６）
実施例１における硫化処理に代えてリン蒸気によるリン
化処理を行なったこと以外は実施例１と同様にして排気
ガス浄化用触媒を得た。(Example 16) An exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that the phosphorus treatment with phosphorus vapor was performed instead of the sulfurating treatment in Example 1.
【００３２】（比較例１）
硫化物の担持を行なわないこと以外は実施例１と同様に
して排気ガス浄化用触媒を得た（但し、触媒粉末ウォッ
シュコート後の焼成は行なった）。(Comparative Example 1) An exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that sulfide was not carried (however, the catalyst powder was washcoated and then calcined).
【００３３】（比較例２）
硫化処理を行なわないこと以外は実施例１と同様にして
排気ガス浄化用触媒を得た。すなわち、触媒粉末をウォ
ッシュコートしてなるハニカムをＩｎ溶液に浸漬し、引
上げてそのまま焼成処理を行なった。Comparative Example 2 An exhaust gas purifying catalyst was obtained in the same manner as in Example 1 except that the sulfurating treatment was not performed. That is, a honeycomb obtained by wash-coating the catalyst powder was immersed in the In solution, pulled up, and subjected to the firing treatment as it was.
【００３４】（浄化テスト）
上記実施例１〜１６及び比較例１，２の各排気ガス浄化
用触媒を常圧固定床流通式反応装置に装着し、Ａ／Ｆ＝
２２相当のモデルガスを用いて、各々のフレッシュ状態
（触媒として未使用であり且つエージング処理なし）及
びエージング（触媒として未使用のものに８００℃×８
時間の熱処理を施した）後の各最高ＮＯｘ浄化率を測定
した。結果は表１乃至表３に示されている。(Purification test) The exhaust gas purifying catalysts of Examples 1 to 16 and Comparative Examples 1 and 2 were mounted in an atmospheric pressure fixed bed flow reactor, and A / F =
Using a model gas equivalent to 22, each fresh state (unused as a catalyst and without aging treatment) and aging (800 ° C. × 8 for an unused catalyst)
Each maximum NOx purification rate after the heat treatment for a time) was measured. The results are shown in Tables 1 to 3.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】[0037]
【表３】 [Table 3]
【００３８】（評価）
表１乃至表３によれば、実施例１〜１６はいずれも比較
例１よりもエージング後のＮＯｘ浄化率が高く、且つエ
ージングによるＮＯｘ浄化率の低下率が低い。この結果
から、上述の硫化物やリン化物の担持が活性種のシンタ
リング防止に有効であることがわかる。また、Ｉｎの含
浸担持後に硫化処理及びリン化処理を行なわなかった比
較例２の場合、フレッシュ時のＮＯｘ浄化率は高いもの
の、エージング後のＮＯｘ浄化率が大きく低下してお
り、このことから、硫化処理もしくはリン化処理の効果
が裏付けられる。(Evaluation) According to Tables 1 to 3, Examples 1 to 16 have a higher NOx purification rate after aging and a lower rate of reduction of NOx purification rate due to aging than Comparative Example 1. From this result, it is understood that the above-mentioned sulfide and phosphide support is effective in preventing sintering of active species. Further, in the case of Comparative Example 2 in which the sulfurization treatment and the phosphating treatment were not carried out after the impregnation and loading of In, the NOx purification rate at the time of freshness was high, but the NOx purification rate after aging was significantly reduced. The effect of the sulfurating treatment or the phosphating treatment is confirmed.
【００３９】そうして、表１の実施例１〜４をみると、
これらは硫化物の種類が互いに異なる例であるが、Ｉｎ
の硫化物を担持させた実施例１がフレッシュ状態及びエ
ージング後のいずれにおいて最も高いＮＯｘ浄化率を示
している。しかし、エージング後のＮＯｘ浄化率が最も
低い実施例４（Ｒｅの硫化物を担持）でも、そのＮＯｘ
浄化率の低下率は１７．９％であり、Ｉｎ、Ｓｎ、Ｇ
ｅ、Ｒｅのいずれの硫化物でも上記シンタリング防止に
高い効果があることがわかる。Then, looking at Examples 1 to 4 in Table 1,
These are examples of different kinds of sulfides.
Example 1 in which the above sulfide was supported shows the highest NOx purification rate both in the fresh state and after aging. However, even in Example 4 (carrying Re sulfide) having the lowest NOx purification rate after aging, the NOx purification rate
The reduction rate of the purification rate was 17.9%, and In, Sn, G
It can be seen that both sulfides of e and Re are highly effective in preventing the sintering.
【００４０】次に表２の実施例１，５〜７をみると、こ
れらはＩｎ量が互いに異なる例であるが、Ｉｎ量３ｇ／
ｌの実施例１及び６ｇ／ｌの実施例５が最も良い結果を
示しており、これにＩｎ量が最も少ない実施例７（１ｇ
／ｌ）、Ｉｎ量が最も多い実施例６（９ｇ／ｌ）が続い
ている。Ｓｎ量が互いに異なる実施例２，８〜１０でも
同様の傾向を示している。この結果から、硫化物とする
金属の量は１〜６ｇ／ｌとすることが好ましく、より好
ましいのは３〜６ｇ／ｌないしは６ｇ／ｌ前後であるこ
とがわかる。Next, looking at Examples 1 and 5 to 7 in Table 2, these are examples in which the In amounts are different from each other.
1 of Example 1 and 6 g / l of Example 5 showed the best results, with Example 7 (1 g
/ L), and Example 6 (9 g / l) having the highest In content follows. The same tendency is shown in Examples 2, 8 to 10 in which the amounts of Sn are different from each other. From this result, it is understood that the amount of the metal as the sulfide is preferably 1 to 6 g / l, more preferably 3 to 6 g / l or around 6 g / l.
【００４１】次に表３の実施例１，１１〜１３をみる
と、これらは硫化処理の温度条件が互いに異なる例であ
るが、同温度５００℃の実施例１が最も良い結果を示し
ており、これに６００℃の実施例１１、４００℃の実施
例１３、７００℃の実施例１２が続いている。この結果
から、当該温度は４００〜６００℃が好ましく、より好
ましいのは５００℃前後ないしは５００〜６００℃であ
ることがわかる。Next, looking at Examples 1 and 11 to 13 in Table 3, these are examples in which the temperature conditions of the sulfurization treatment are different from each other, and Example 1 at the same temperature of 500 ° C. shows the best result. This is followed by Example 11 at 600 ° C, Example 13 at 400 ° C, Example 12 at 700 ° C. From this result, it is understood that the temperature is preferably 400 to 600 ° C, more preferably about 500 ° C or 500 to 600 ° C.
【００４２】また、実施例１，１４，１５をみると、こ
れらはＳＯ2濃度が互いに異なる例であるが、同濃度が
１００ｐｐｍの実施例１が最も良い結果を示しており、
これに同濃度が５０ｐｐｍの実施例１４、２００ｐｐｍ
の実施例１５が続いている。この結果から、ＳＯ2濃度
は５０〜１００ｐｐｍないしは１００ｐｐｍ前後が好ま
しいことがわかる。Looking at Examples 1, 14 and 15, these are examples in which the SO 2 concentrations are different from each other, but Example 1 in which the concentration is 100 ppm shows the best results,
Example 14 with the same concentration of 50 ppm, 200 ppm
Example 15 of is followed. From this result, it is understood that the SO 2 concentration is preferably 50 to 100 ppm or around 100 ppm.
【００４３】さらに、実施例１６をみると、これはＩｎ
のリン化物を担持させた例であるが、そのフレッシュ時
及びエージング後の各ＮＯｘ浄化率は、硫化物を担持さ
せた実施例１と略同程度であり、このことから、リン化
物の担持が硫化物の担持と同様に活性種のシンタリング
防止に効を奏することがわかる。Further, looking at Example 16, this is In
In this example, the NOx purification rates at the time of fresh and after aging are almost the same as those in Example 1 in which sulfide was supported. It can be seen that it is effective in preventing sintering of active species as in the case of supporting sulfide.
【００４４】（実施例１７〜３０）
実施例１と同様の方法によってＰｔ、Ｉｒ及びＲｈがＺ
ＳＭ−５に担持されている触媒粉末を調製した。但し、
Ｐｔ：Ｉｒ：Ｒｈ＝３０：６：１であり、各貴金属活性
種の担持量はＰｔ＝２．８３ｗｔ％、Ｉｒ＝０．５６ｗ
ｔ％、Ｒｈ＝０．１０ｗｔ％である。そして、これを表
４に示すようにＳＯ2濃度５０ｐｐｍの雰囲気において
３００〜８５０℃の温度に加熱することによって各量の
硫黄を担持させた後に実施例１と同様のハニカム担体に
ウォッシュコートすることによって実施例１７〜２３の
各ハニカム触媒を得た。また、ＳＯ2濃度を１００００
ｐｐｍとして実施例１７〜２３と同様の処理を行なうこ
とにより、実施例２４〜３０の各ハニカム触媒を得た。(Examples 17 to 30) Pt, Ir and Rh were Z in the same manner as in Example 1.
A catalyst powder supported on SM-5 was prepared. However,
Pt: Ir: Rh = 30: 6: 1, the loading amount of each noble metal active species is Pt = 2.83 wt%, Ir = 0.56w
t% and Rh = 0.10 wt%. Then, as shown in Table 4, by heating to a temperature of 300 to 850 ° C. in an atmosphere having an SO 2 concentration of 50 ppm to carry each amount of sulfur, and then wash-coating the same honeycomb carrier as in Example 1. Thus, the honeycomb catalysts of Examples 17 to 23 were obtained. Also, the SO 2 concentration should be 10,000
The honeycomb catalysts of Examples 24 to 30 were obtained by performing the same treatment as in Examples 17 to 23 in ppm.
【００４５】そうして、各実施例のハニカム触媒に８０
０℃×８時間の大気中熱処理を施した後に、Ａ／Ｆ＝２
２相当のモデルガスを用いて最高ＮＯｘ浄化率を測定し
た。また、同時に比較例（ＳＯ2濃度零の雰囲気で５０
０℃に加熱）についても同様にして最高ＮＯｘ浄化率を
測定した。これらの結果は表４に示されている。Then, the honeycomb catalyst of each of the examples has 80
After heat treatment in air at 0 ° C. for 8 hours, A / F = 2
The maximum NOx purification rate was measured using 2 model gases. Also, 50 in an atmosphere of Comparative Example (SO 2 concentration zero simultaneously
The maximum NOx purification rate was similarly measured for (heated to 0 ° C.). The results are shown in Table 4.
【００４６】[0046]
【表４】 [Table 4]
【００４７】同表によれば、ＳＯ2濃度５０ｐｐｍ、１
００００ｐｐｍのいずれにおいても比較例よりも最高Ｎ
Ｏｘ浄化率が高くなっており、特に加熱温度４００〜８
００℃のときに、また硫黄量０．２〜０．４ｗｔ％のと
きにその効果が顕著になることがわかる。According to the table, SO 2 concentration of 50 ppm, 1
Highest N than any of the comparative examples at any of 0000 ppm
Ox purification rate is high, especially heating temperature 400 ~ 8
It can be seen that the effect becomes remarkable when the temperature is 00 ° C. and when the sulfur amount is 0.2 to 0.4 wt%.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高見 明秀 広島県安芸郡府中町新地３番１号 マツ ダ株式会社内 (72)発明者 京極 誠 広島県安芸郡府中町新地３番１号 マツ ダ株式会社内 (56)参考文献 特開 昭50−101291（ＪＰ，Ａ) 特開 平４−215848（ＪＰ，Ａ) 特開 昭54−78391（ＪＰ，Ａ) 特開 平４−171048（ＪＰ，Ａ) 特開 平１−135541（ＪＰ，Ａ) 特開 平６−262082（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 B01D 53/00 - 53/96 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihide Takami No. 3 Shinchi, Fuchu-cho, Aki-gun, Hiroshima Prefecture Mazda Co., Ltd. (72) Inventor Makoto Kyogoku No. 3 Shinchi, Fuchu-cho, Aki-gun, Hiroshima Prefecture Mazda Incorporated (56) Reference JP-A-50-101291 (JP, A) JP-A-4-215848 (JP, A) JP-A-54-78391 (JP, A) JP-A-4-171048 (JP, A) A) JP-A-1-135541 (JP, A) JP-A-6-262082 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) B01J 21/00 -38/74 B01D 53 / 00-53/96
Claims (4)
シリケートに、Ｐｔ、Ｉｒ及びＲｈの貴金属活性種と、
該貴金属活性種よりも硫黄との親和力が強いＩｎ、Ｓ
ｎ、Ｇｅ及びＲｅのうちから選ばれる１種以上の金属と
を担持させ、しかる後にＳＯ 2 雰囲気で加熱する硫化処
理を行なうことにより、上記貴金属活性種と、上記選択
された金属の硫化物とが上記金属含有シリケートに分散
担持されていることを特徴とする排気ガス浄化用触媒。1. A crystalline metal containing micropores
Silicates with Pt, Ir and Rh precious metal active species,
In, S having a stronger affinity with sulfur than the noble metal active species
One or more metals selected from n, Ge and Re
Sulfurization treatment in which is supported and then heated in an SO 2 atmosphere
The above noble metal active species and the above selection
An exhaust gas purifying catalyst, characterized in that the metal sulfide thus obtained is carried on the metal-containing silicate in a dispersed manner.
シリケートに、Ｐｔ、Ｉｒ及びＲｈの貴金属活性種とＩ
ｎとを担持させ、しかる後にリン蒸気によるリン化処理
を行なうことにより、上記貴金属活性種と、上記Ｉｎの
リン化物とが上記金属含有シリケートに分散担持されて
いることを特徴とする排気ガス浄化用触媒。2. A crystalline metal containing micropores
In silicate, Pt, Ir and Rh precious metal active species and I
n and then phosphorus treatment with phosphorus vapor
By carrying out the above-mentioned noble metal active species and In
The phosphide and the metal-containing silicate are dispersed and supported on the silicate.
Exhaust gas purifying catalyst, characterized in that there.
の貴金属活性種を担持させた後に、該貴金属活性種より
も硫黄との親和力が強いＩｎ、Ｓｎ、Ｇｅ及びＲｅのう
ちから選ばれる１種以上の金属を担持させ、しかる後に
該金属の硫化処理をＳＯ 2 雰囲気で行なうことを特徴と
する排気ガス浄化用触媒の製造方法。 3. Pt, Ir and Rh are added to an inorganic porous base material.
After supporting the noble metal active species of
Also has a strong affinity with sulfur such as In, Sn, Ge and Re
After supporting one or more metals selected from the following,
The sulfurization treatment of the metal is performed in an SO 2 atmosphere.
Exhaust gas purification catalyst manufacturing method.
させた後に、この貴金属活性種が担持された母材をＳＯ
2雰囲気で加熱することによって当該貴金属活性種の一
部を貴金属硫化物に変えることを特徴とする排気ガス浄
化用触媒の製造方法。4. An inorganic porous base material is loaded with a noble metal active species, and the base material loaded with the noble metal active species is subjected to SO.
(2) A method for producing an exhaust gas purifying catalyst, characterized in that a part of the precious metal active species is converted into a precious metal sulfide by heating in an atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27176293A JP3508180B2 (en) | 1993-07-08 | 1993-10-29 | Exhaust gas purification catalyst and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-168817 | 1993-07-08 | ||
| JP16881793 | 1993-07-08 | ||
| JP27176293A JP3508180B2 (en) | 1993-07-08 | 1993-10-29 | Exhaust gas purification catalyst and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0768177A JPH0768177A (en) | 1995-03-14 |
| JP3508180B2 true JP3508180B2 (en) | 2004-03-22 |
Family
ID=26492364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27176293A Expired - Fee Related JP3508180B2 (en) | 1993-07-08 | 1993-10-29 | Exhaust gas purification catalyst and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3508180B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60235607D1 (en) * | 2001-01-11 | 2010-04-22 | Ict Co Ltd | CATALYST FOR CLEANING NITROGEN OXIDES |
-
1993
- 1993-10-29 JP JP27176293A patent/JP3508180B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0768177A (en) | 1995-03-14 |
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