JPH09234378A - Catalyst for exhaust gas purification and its preparation - Google Patents
Catalyst for exhaust gas purification and its preparationInfo
- Publication number
- JPH09234378A JPH09234378A JP8046411A JP4641196A JPH09234378A JP H09234378 A JPH09234378 A JP H09234378A JP 8046411 A JP8046411 A JP 8046411A JP 4641196 A JP4641196 A JP 4641196A JP H09234378 A JPH09234378 A JP H09234378A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- carrier
- noble metal
- fsm
- porous body
- 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 55
- 238000000746 purification Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title 1
- 239000011148 porous material Substances 0.000 claims abstract description 104
- 239000007789 gas Substances 0.000 claims abstract description 69
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- 239000000377 silicon dioxide Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 28
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 55
- 238000000034 method Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002429 nitrogen sorption measurement Methods 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WZEYZMKZKQPXSX-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1.CC1=CC(C)=CC(C)=C1 WZEYZMKZKQPXSX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZVBWPVOCTORPLM-UHFFFAOYSA-N formylsilicon Chemical compound [Si]C=O ZVBWPVOCTORPLM-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、内燃機関などから
排出される排ガスを浄化する排ガス浄化用触媒及びその
製造方法に関し、詳しくはＮＯX 等の排ガスを浄化する
ための排ガス浄化用触媒及びその製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying catalyst for purifying exhaust gas discharged from an internal combustion engine or the like and a method for producing the same, and more specifically to an exhaust gas purifying catalyst for purifying exhaust gas such as NO x and the like. The present invention relates to a manufacturing method.
【０００２】[0002]
【従来の技術】内燃機関から排出される排ガス中には、
一酸化炭素（ＣＯ）、窒素酸化物（ＮＯX ）等の有害な
物質が含まれている。このうちＮＯX の浄化方法とし
て、触媒作用によって排気ガス中に同時に含まれる炭化
水素（ＨＣ）でＮＯX を還元し、無害な窒素分子
（Ｎ2 ）にする方法や、あるいは、排ガス中に炭化水素
を添加して、その炭化水素によりＮＯX を還元し浄化す
る方法がある。このような還元反応を促す触媒として
は、白金（Ｐｔ）、ロジウム（Ｒｈ）、パラジウム（Ｐ
ｄ）、イリジウム（Ｉｒ）等の貴金属が知られており、
こうした貴金属を担体に担持させて構成される排ガス浄
化用触媒が排ガスの浄化に使用されている。2. Description of the Related Art In exhaust gas discharged from an internal combustion engine,
It contains harmful substances such as carbon monoxide (CO) and nitrogen oxides (NO x ). Among them, as a method of purifying NO x, a method of reducing NO x with hydrocarbon (HC) simultaneously contained in the exhaust gas by a catalytic action to form harmless nitrogen molecules (N 2 ), or carbonization in exhaust gas There is a method in which hydrogen is added and NO x is reduced and purified by the hydrocarbon. As a catalyst for promoting such a reduction reaction, platinum (Pt), rhodium (Rh), palladium (P
d), noble metals such as iridium (Ir) are known,
Exhaust gas purifying catalysts which are formed by supporting such precious metals on a carrier are used for purifying exhaust gas.
【０００３】従来、このような貴金属を担体に担持させ
て構成される排ガス浄化用触媒の製造方法としては、ア
ルミナ、シリカゲル、ゼオライト、セピオライト等の高
比表面積担体に貴金属を含む塩の水溶液を接触させ、そ
の後、塩が分解するのに必要な温度で熱処理する方法が
とられていた。このうち、セピオライト担体にパラジウ
ムを担持した後、これらを炭化水素を含まない酸化雰囲
気において４００〜７００℃の温度で熱処理して排ガス
浄化用触媒を製造する方法（特開平６−３７６号公報）
や、アルミナ担体に白金を担持した後７００〜１０００
℃で熱処理する方法（特公昭６２−５６７８３号公報）
が提案されている。Conventionally, as a method for producing an exhaust gas purifying catalyst constituted by supporting such a noble metal on a carrier, an aqueous solution of a salt containing a noble metal is contacted with a carrier having a high specific surface area such as alumina, silica gel, zeolite or sepiolite. And then heat-treating at the temperature required for the salt to decompose. Of these, a method of supporting palladium on a sepiolite carrier and then heat-treating these in a hydrocarbon-free oxidizing atmosphere at a temperature of 400 to 700 ° C. to produce an exhaust gas purifying catalyst (JP-A-6-376)
Or 700 to 1000 after loading platinum on an alumina carrier
Method of heat treatment at ℃ (Japanese Patent Publication No. 62-56783)
Has been proposed.
【０００４】しかし、酸素が多く含まれる排ガスにおい
ては、これらの方法によって製造された排ガス浄化用触
媒では、その排ガス中に含まれるＮＯX の浄化効率が低
い。However, in the exhaust gas containing a large amount of oxygen, the exhaust gas purifying catalyst produced by these methods has a low purification efficiency of NO x contained in the exhaust gas.
【０００５】[0005]
【発明が解決しようとする課題】そこで上記のような酸
素過剰下でのＮＯX の選択的還元反応等の排ガス浄化反
応に対し、十分な活性を有する排ガス浄化用触媒とし
て、層状シリカ多孔体あるいは層状シリカ−金属酸化物
多孔体よりなる担体に白金を担持し、３５０℃で熱処理
した後、炭化水素と空気とで構成され炭化水素に対する
空気の空燃比が１８以下である雰囲気中で５００℃以上
の温度で熱処理する方法（特開平６−６３４００号公
報）が開示されている。しかし、この方法で製造された
排ガス浄化用触媒は酸素過剰下にある排ガスにおいて高
いＮＯX の浄化作用を有するが、まだ十分とはいえな
い。なお、空燃比とは、空気の体積と気化したガソリン
の体積比をいう。Therefore, a layered silica porous material or a layered silica porous material is used as an exhaust gas purifying catalyst having sufficient activity for the exhaust gas purifying reaction such as the selective reduction reaction of NO X under the excessive oxygen as described above. Platinum is supported on a carrier composed of a layered silica-metal oxide porous body, heat-treated at 350 ° C., and then 500 ° C. or more in an atmosphere composed of hydrocarbon and air and having an air-fuel ratio of air to hydrocarbon of 18 or less. There is disclosed a method of heat treatment at the temperature (Japanese Patent Laid-Open No. 6-63400). However, although the exhaust gas-purifying catalyst produced by this method has a high NO X purification effect in the exhaust gas in the presence of excess oxygen, it cannot be said to be sufficient yet. The air-fuel ratio means the volume ratio of air to vaporized gasoline.
【０００６】本発明は、上記問題に鑑みてなされたもの
であり、内燃機関などから排出される排ガスを浄化し、
特に酸素過剰下において、さらに高いＮＯX の浄化作用
を有する排ガス浄化用触媒およびその製造方法を提供す
ることを目的とする。The present invention has been made in view of the above problems, and purifies exhaust gas discharged from an internal combustion engine or the like,
Particularly, it is an object of the present invention to provide an exhaust gas purifying catalyst having a higher NO X purifying effect in the presence of excess oxygen and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】本発明者は、従来技術に
よって製造された排ガス浄化用触媒においては担体上に
担持された貴金属は粒径が３０ｎｍ以上に粒成長してい
ること、そして特開平６−６３４００号公報に示されて
いる排ガス浄化用触媒においては貴金属が１０ｎｍ以上
の粒径に粒成長していないことに着眼し、貴金属の粒径
が１０〜３０ｎｍである時、酸素過剰下でのＮＯX の選
択的還元反応等の排ガス浄化反応に対して活性が高いこ
とを見出し、また、中心細孔直径が１〜１０ｎｍの範囲
内にあって、全細孔の６０％以上の細孔が該中心細孔直
径の±５ｎｍの範囲内の直径を有する担体を用いると、
貴金属の平均粒径が１０〜３０ｎｍの範囲内になるよう
に粒成長を制御できることを発見し、本発明に至ったの
である。DISCLOSURE OF THE INVENTION The inventors of the present invention have found that in the exhaust gas purifying catalyst produced by the prior art, the noble metal supported on the carrier is grown to have a particle size of 30 nm or more. In the exhaust gas purifying catalyst disclosed in Japanese Patent Laid-Open No. 6-63400, it is noted that the noble metal does not grow to a particle size of 10 nm or more, and when the particle size of the noble metal is 10 to 30 nm, it is under oxygen excess. Found to have high activity for exhaust gas purification reactions such as the selective reduction reaction of NO x , and having a central pore diameter in the range of 1 to 10 nm and 60% or more of all pores. Using a carrier having a diameter within the range of ± 5 nm of the central pore diameter,
The inventors have found that the grain growth can be controlled so that the average grain size of the noble metal is within the range of 10 to 30 nm, and have reached the present invention.
【０００８】すなわち、本発明は、多孔質の担体と、該
担体に担持された貴金属とよりなる排ガス浄化用触媒で
あって、該担体は、中心細孔直径が１〜１０ｎｍの範囲
内にあって、全細孔の６０％以上の細孔が該中心細孔直
径の±５ｎｍの範囲内の直径を有する多孔体であり、か
つ該貴金属は平均粒径が１０〜３０ｎｍの範囲内にある
金属粒子であることを特徴とする排ガス浄化用触媒であ
る。またもう一つの本発明は、中心細孔直径が１〜１０
ｎｍの範囲内にあって、全細孔の６０％以上の細孔が該
中心細孔直径の±５ｎｍの範囲内の直径を有する担体に
貴金属を担持させる担持工程と、貴金属が担持された該
担体を、酸素・燃料比が４以上である混合気体の雰囲
気、又は炭化水素を含まず酸素を含む雰囲気中で６００
〜１０００℃に加熱する加熱工程と、からなることを特
徴とする排ガス浄化用触媒の製造方法である。なお、酸
素・燃料比とは、酸素ガスの体積と気化したガソリンの
体積比をいう。That is, the present invention is an exhaust gas purifying catalyst comprising a porous carrier and a noble metal supported on the carrier, the carrier having a central pore diameter in the range of 1 to 10 nm. 60% or more of all the pores are porous bodies having a diameter within the range of ± 5 nm of the central pore diameter, and the noble metal is a metal having an average particle diameter within the range of 10 to 30 nm. It is an exhaust gas-purifying catalyst characterized by being particles. Another aspect of the present invention is that the central pore diameter is 1 to 10
nm, and 60% or more of all the pores have a supporting step of supporting the noble metal on a carrier having a diameter within the range of ± 5 nm of the central pore diameter. The carrier is 600 in an atmosphere of a mixed gas having an oxygen / fuel ratio of 4 or more or an atmosphere containing no hydrocarbon and containing oxygen.
A method for producing an exhaust gas-purifying catalyst, comprising: a heating step of heating to ˜1000 ° C. The oxygen / fuel ratio is the volume ratio of oxygen gas to vaporized gasoline.
【０００９】[0009]
【発明の実施の形態】担体としては、層状シリカ多孔体
あるいは層状シリカ−金属酸化物多孔体を使用すること
ができる。なお、層状シリカ多孔体とは、骨格がシリカ
よりなる層状物を原料として、この層状物を多孔体とし
たものである。また、層状シリカ−金属酸化物多孔体と
は、前記の層状シリカ多孔体にアルミニウム等の金属の
酸化物を担持したものである。この層状シリカ多孔体
は、例えば、以下の製造方法により製造することができ
る。BEST MODE FOR CARRYING OUT THE INVENTION As the carrier, a layered silica porous material or a layered silica-metal oxide porous material can be used. The layered silica porous material is a layered material having a skeleton made of silica as a raw material, and the layered material is a porous material. The layered silica-metal oxide porous body is the layered silica porous body carrying an oxide of a metal such as aluminum. This layered silica porous material can be manufactured, for example, by the following manufacturing method.
【００１０】先ず、珪酸ソーダ等の珪酸塩を焼成してカ
ネマイト等の層状珪酸塩を形成する。この層状珪酸塩に
界面活性剤を添加し、この界面活性剤を層状珪酸塩の層
間に導入すると共に、界面活性剤が導入された部分以外
で隣合う層状珪酸塩どうしを結合させる。この結合は、
隣合う層状珪酸塩中のシラール（Ｓｉ−ＯＨ）どうしが
脱水縮合し、シロキサン結合（Ｓｉ−Ｏ−Ｓｉ）が形成
されることにより生じる。この結合により、全体として
３次元ハニカム状となる。この３次元ハニカム状の層状
珪酸塩を焼成することにより、導入された界面活性剤が
除去されて細孔が形成される。このとき、添加する界面
活性剤の大きさを変化させることにより、形成される細
孔の直径を調整することができる。First, a silicate such as sodium silicate is fired to form a layered silicate such as kanemite. A surfactant is added to the layered silicate to introduce the surfactant between the layers of the layered silicate, and to bond adjacent layered silicates other than the portion where the surfactant is introduced. This join
It occurs when silal (Si-OH) in adjacent layered silicates is dehydrated and condensed to form a siloxane bond (Si-O-Si). By this bonding, the whole becomes a three-dimensional honeycomb shape. By firing this three-dimensional honeycomb layered silicate, the introduced surfactant is removed and pores are formed. At this time, the diameter of the formed pores can be adjusted by changing the size of the added surfactant.
【００１１】貴金属はＰｔ、Ｒｈ、Ｐｄ、Ｉｒから選ば
れる少なくとも１種の貴金属であることが望ましい。な
お、貴金属にはＡｌ、Ｍｇ、Ｔｉから選ばれる少なくと
も１種の金属の酸化物が添加されることが望ましい。担
体に貴金属を担持させる方法としては、貴金属を含む溶
液中に担体を浸漬することにより担体中に貴金属を含む
溶液を含浸させ、加熱等により水分等の溶媒を蒸発させ
て担体中に貴金属を吸着させる方法が望ましい。このと
き貴金属は塩の形態で溶媒中に溶かすこともでき、貴金
属の塩は、該貴金属の塩の熱分解温度以上で加熱するこ
とによって分解し、単体金属として貴金属が担体に担持
される。なお、貴金属を含む溶液は酸性、中性、アルカ
リ性のいずれでもよい。また、溶液の溶媒を蒸発させる
ための加熱は１１０℃が望ましい。この方法によれば貴
金属の担持量を、貴金属を含む溶液の濃度の調整によっ
て行うことができ、貴金属の担持量を制御しやすいため
好ましい。The noble metal is preferably at least one noble metal selected from Pt, Rh, Pd and Ir. It is desirable that the noble metal be added with an oxide of at least one metal selected from Al, Mg, and Ti. As a method of supporting the noble metal on the carrier, the carrier is impregnated with the solution containing the noble metal by immersing the carrier in the solution containing the noble metal, and the solvent such as water is evaporated by heating or the like to adsorb the noble metal on the carrier. It is desirable to use the method. At this time, the noble metal can be dissolved in the solvent in the form of a salt, and the noble metal salt is decomposed by heating at a temperature not lower than the thermal decomposition temperature of the noble metal salt, and the noble metal is supported as a single metal on the carrier. The solution containing the noble metal may be acidic, neutral or alkaline. Further, the heating for evaporating the solvent of the solution is preferably 110 ° C. According to this method, the amount of the precious metal supported can be adjusted by adjusting the concentration of the solution containing the precious metal, and the amount of the precious metal supported can be easily controlled, which is preferable.
【００１２】前記の様に担体に貴金属を担持した後、酸
素・燃料比が４以上である混合気体の雰囲気、又は炭化
水素を含まず酸素を含む雰囲気中で貴金属が担持された
担体を加熱することが望ましい。このとき、炭化水素を
含まず空気（酸素２０％含有）のみを含む雰囲気、すな
わち大気中で加熱することもでき、あるいはまた、酸素
が１００％含まれる雰囲気中で加熱することもできる。
こうした熱処理条件下において貴金属の粒成長が促進さ
れ、貴金属の平均粒径を１０〜３０ｎｍの範囲内とする
ことができる。これは、酸素の働きにより貴金属の結晶
粒間の結合を促進しているためであると考えられる。な
お、酸素・燃料比が４以下である混合気体の雰囲気、又
は酸素を含まない雰囲気中で加熱すると、貴金属の粒成
長が促進されず、貴金属の平均粒径を１０〜３０ｎｍの
範囲内とすることはできない。After supporting the noble metal on the carrier as described above, the carrier on which the noble metal is supported is heated in an atmosphere of a mixed gas having an oxygen / fuel ratio of 4 or more, or in an atmosphere containing no hydrocarbon and oxygen. Is desirable. At this time, heating can be performed in an atmosphere containing only air (containing 20% oxygen) without containing hydrocarbons, that is, in the atmosphere, or in an atmosphere containing 100% oxygen.
Under such heat treatment conditions, the grain growth of the noble metal is promoted, and the average grain size of the noble metal can be set within the range of 10 to 30 nm. It is considered that this is because the action of oxygen promotes the bond between the crystal grains of the noble metal. When heated in a mixed gas atmosphere having an oxygen / fuel ratio of 4 or less, or in an atmosphere containing no oxygen, the grain growth of the noble metal is not promoted and the average grain size of the noble metal is set within the range of 10 to 30 nm. It is not possible.
【００１３】[0013]
【作用】本発明の排ガス浄化用触媒によって、排ガス中
に含まれるＮＯX が排気ガス中に同時に含まれる炭化水
素（ＨＣ）で還元され、無害な窒素分子（Ｎ2 ）にな
る。また、本発明の排ガス浄化用触媒の製造方法によっ
て、酸素・燃料比が４以上である混合気体の雰囲気、又
は炭化水素を含まず酸素を含む雰囲気中では、中心細孔
直径が１〜１０ｎｍの範囲内にあって全細孔の６０％以
上の細孔が該中心細孔直径の±５ｎｍの範囲内の直径を
有する担体においては、貴金属が担体に担持された状態
で６００〜１０００℃で加熱することで平均粒径が１０
〜３０ｎｍの範囲内に粒径の成長を制御することができ
る。これは、酸素・燃料比が４以上である混合気体の雰
囲気、又は炭化水素を含まず酸素を含む雰囲気中では貴
金属の微粒子が部分的に酸化され、粒子径が成長しやす
い状態となり、また中心細孔直径が１〜１０ｎｍの範囲
内にあって中心細孔直径の±５ｎｍの範囲内にある直径
の細孔が全細孔の６０％以上ある担体においては、細孔
によって形成される担体表面の凹凸の周期が規則的とな
り、粒子径が制御されやすくなるためである。そして６
００〜１０００℃の加熱によって、担体に担持された貴
金属が粒成長する。このとき、貴金属が塩の形態で担体
に担持された場合も、塩の熱分解を経て単体貴金属の形
態で粒成長する。With the catalyst for purifying exhaust gas of the present invention, NO x contained in the exhaust gas is reduced by hydrocarbon (HC) contained in the exhaust gas at the same time to become harmless nitrogen molecules (N 2 ). Further, according to the method for producing an exhaust gas purifying catalyst of the present invention, in a mixed gas atmosphere having an oxygen / fuel ratio of 4 or more, or in an atmosphere containing oxygen without hydrocarbons, the central pore diameter is 1 to 10 nm. In a carrier in which 60% or more of all the pores have a diameter within ± 5 nm of the central pore diameter, heating at 600 to 1000 ° C. with the noble metal supported on the carrier is carried out. The average particle size is 10
Particle size growth can be controlled within the range of ~ 30 nm. This is because the noble metal fine particles are partially oxidized in an atmosphere of a mixed gas having an oxygen / fuel ratio of 4 or more, or in an atmosphere not containing a hydrocarbon and containing oxygen, and the particle diameter easily grows. In the case of a carrier having 60% or more of all the pores having a diameter within the range of 1 to 10 nm and a central pore diameter of ± 5 nm, the carrier surface formed by the pores. This is because the cycle of the unevenness becomes regular and the particle size is easily controlled. And 6
The noble metal supported on the carrier is grain-grown by heating at 0 to 1000 ° C. At this time, even when the noble metal is supported on the carrier in the form of a salt, the particles grow in the form of a simple noble metal through thermal decomposition of the salt.
【００１４】[0014]
【実施例】以下、実施例により本発明を具体的に説明す
る。 （担体の形成）珪酸ソーダ粉末（ＳｉＯ2 ／Ｎａ2 Ｏ＝
２．００；日本化学工業製）を空気中において７００℃
で６時間焼成した。そして、得られた焼成珪酸ソーダ粉
末のうち５０ｇを粒径１ｍｍ以下に粉砕した後、５００
ｍｌの水に分散させ、室温で３時間攪拌した。その後、
ブフナーロートを用いて固形分を濾別し、層状珪酸塩の
一種であるカネマイト（ＮａＨＳｉ2 Ｏ5 ・３Ｈ2 Ｏ）
を得た。The present invention will be described below in detail with reference to examples. (Formation of Carrier) Sodium silicate powder (SiO 2 / Na 2 O =
2.00; manufactured by Nippon Kagaku Kogyo) in air at 700 ° C
It was baked for 6 hours. Then, 50 g of the obtained baked sodium silicate powder was pulverized to a particle size of 1 mm or less, and then 500
It was dispersed in ml of water and stirred at room temperature for 3 hours. afterwards,
Kanemite (NaHSi 2 O 5 · 3H 2 O), which is a type of layered silicate, is obtained by filtering off the solid content using a Buchner funnel.
I got
【００１５】次に、０．１モルのヘキサデシルトリメチ
ルアンモニウムクロライド（Ｃ16Ｈ 33Ｎ（ＣＨ3 ）3 Ｃ
ｌ）、あるいはドデシルトリメチルアンモニウムブロマ
イド（Ｃ12Ｈ25Ｎ（ＣＨ3 ）3 Ｂｒ）を１０００ｍｌの
水に溶解させることにより調整したアルキルトリメチル
アンモニウム（Ｃn Ｈ2n+1Ｎ+ （ＣＨ3 ）3 ）水溶液
に、乾燥せずに湿った状態のままの上記カネマイトを分
散させた。そして、これらの２種類の分散液をそれぞれ
２０００ｍｌ容器のフラスコに入れ、攪拌モーターで攪
拌しながらオイルバス中において７０℃で３時間加熱
し、２Ｎの塩酸水溶液を滴下して分散液のｐＨをゆっく
り８．５に調整してさらに攪拌しながら７０℃で３時間
加熱した。加熱後、分散液を室温まで冷却し、固形生成
物を濾別した。得られた固形生成物を１０００ｍｌのイ
オン交換水で合計５回洗浄した後、乾燥して粉末を得
た。これらの粉末を空気中で５５０℃中において６時間
焼成し、２種類の層状シリカ多孔体を得た。これらの多
孔体はアルキル鎖長がｎ＝１２のものをＦＳＭ−２３と
し、ｎ＝１６のものをＦＳＭ−２８とした。Next, 0.1 mol of hexadecyl trimethyl
Lumonium chloride (C16H 33N (CHThree)ThreeC
l), or dodecyl trimethyl ammonium bromide
Id (C12Htwenty fiveN (CHThree)ThreeBr) of 1000 ml
Alkyl trimethyl prepared by dissolving it in water
Ammonium (CnH2n + 1N+(CHThree)Three) Aqueous solution
The above-mentioned kanemite, which remains moist without drying.
Scattered. And these two kinds of dispersion liquids
Place in a 2000 ml flask and stir with a stirring motor.
Heat in an oil bath at 70 ° C for 3 hours with stirring
Then, add 2N hydrochloric acid aqueous solution to adjust the pH of the dispersion.
Adjust to 8.5 and stir for 3 hours at 70 ℃.
Heated. After heating, cool the dispersion to room temperature to produce a solid
The product was filtered off. The solid product obtained was treated with 1000 ml of
After washing a total of 5 times with on-exchanged water, dry to obtain powder
Was. These powders in air at 550 ° C for 6 hours
Firing was performed to obtain two types of layered silica porous bodies. Many of these
The pores with an alkyl chain length of n = 12 are called FSM-23.
Then, the one with n = 16 was designated as FSM-28.
【００１６】また、前記と同様の方法で焼成珪酸ソーダ
粉末から湿潤カネマイトを調整し、ヘキサデシルトリメ
チルアンモニウムクロライド０．１モルを１０００ｍｌ
の水に溶解させ、０．２モルのメシチレン（１，３，５
−トリメチルベンゼン）を添加したものと、０．８モル
のメシチレンを添加した水溶液をそれぞれ調整した。そ
して、これらの水溶液中に湿潤カネマイトを分散させ、
ＦＳＭ−２３あるいはＦＳＭ−２８を形成した時と同様
の方法で分散液を加熱、乾燥し粉末を得た。これらの粉
末を空気中において５５０℃で６時間焼成し、２種類の
層状シリカ多孔体を得た。これらの多孔体はメシチレン
０．２モルを添加させたものをＦＳＭ−４８とし、メシ
チレン０．８モルを添加させたものをＦＳＭ−５５とし
た。 （多孔体の結晶構造の測定）前記得られたＦＳＭ−２
３、ＦＳＭ−２８、ＦＳＭ−４８、ＦＳＭ−５５につい
て、理学電子ＲＡＤ−Ｂ装置を用いて、Ｃｕ−Ｋαを線
源としてＸ線回折を行った。なお、線源のスリットは、
ＲＳ１．０ｍｍ、ＳＳ１．０ｍｍ、Ｓ０．３ｍｍとし
た。ＦＳＭ−２３、ＦＳＭ−２８、ＦＳＭ−４８につい
て得られたＸ線回折（ＸＲＤ）パターンをそれぞれ図１
〜３に示す。Further, wet kanemite was prepared from calcined sodium silicate powder in the same manner as described above, and 1000 mol of hexadecyltrimethylammonium chloride (0.1 mol) was prepared.
Dissolved in water of 0.2 mol of mesitylene (1, 3, 5
-Trimethylbenzene) and an aqueous solution containing 0.8 mol of mesitylene were prepared. Then, disperse the wet kanemite in these aqueous solutions,
The dispersion was heated and dried in the same manner as when forming FSM-23 or FSM-28 to obtain a powder. These powders were fired in air at 550 ° C. for 6 hours to obtain two types of layered silica porous bodies. Regarding these porous materials, FSM-48 was prepared by adding 0.2 mol of mesitylene, and FSM-55 was prepared by adding 0.8 mol of mesitylene. (Measurement of crystal structure of porous body) FSM-2 obtained above
3, FSM-28, FSM-48, and FSM-55 were subjected to X-ray diffraction using Cu-Kα as a radiation source using a Rigaku Denshi RAD-B apparatus. In addition, the slit of the radiation source is
RS 1.0 mm, SS 1.0 mm, S 0.3 mm. The X-ray diffraction (XRD) patterns obtained for FSM-23, FSM-28, and FSM-48 are shown in FIG.
3 are shown.
【００１７】図１と図２より、ＦＳＭ−２３とＦＳＭ−
２８においては、六方構造を示すピークが見られた。し
かし、図３より、ＦＳＭ−４８においては、六方構造を
示すピークは見られなかった。また、図示しないが、Ｆ
ＳＭ−５５ついても六方構造を示すピークは見られなか
った。これらの結果より、ＦＳＭ−２３とＦＳＭ−２８
は結晶性が高いことがわかった。From FIGS. 1 and 2, the FSM-23 and FSM-
In 28, a peak showing a hexagonal structure was observed. However, from FIG. 3, in FSM-48, no peak showing a hexagonal structure was observed. Although not shown, F
With SM-55, no peak showing a hexagonal structure was observed. From these results, FSM-23 and FSM-28
Was found to be highly crystalline.
【００１８】また、ＦＳＭ−４８、ＦＳＭ−５５につい
て、線源のスリットを更に狭くして前記同様にＸ線回折
を行ったところ、得られたＸＲＤパターンにおいて六方
構造を示すピークが検出された。このことより、ＦＳＭ
−４８、ＦＳＭ−５５も結晶性が高いことがわかった。 （細孔径分布の測定）本実施例で形成された多孔体中に
分布する細孔の径は、多孔体に窒素を吸着させる窒素吸
着法により測定した。この方法は、まず多孔体に窒素を
吸着させ、その吸着量を測定して窒素吸着等温線を表す
図を作成し、この図からＣｒａｎｓｔｏｎ−Ｉｎｃｌａ
ｙ法により細孔容積（Ｖ）を細孔直径（Ｄ）で微分した
値（ｄＶ／ｄＤ）を計算して多孔体中の細孔径分布を求
める方法である。本窒素吸着測定は定容量法によって行
い、約５０ｍｇの多孔体試料を測定装置のサンプル管に
計り取り、管内の多孔体試料を１３０℃で加熱しながら
真空度が１０-3Ｔｏｒｒになるまで管内を１時間真空引
きし、多孔体中に分布する細孔内の空気を脱気した後、
サンプル管を液体窒素に浸して窒素の吸着測定を行っ
た。なお本測定装置は絶対圧型トランスデューサー（日
本エムケーエス（株）製Ｂａｒａｔｏｎ１２７ＡＡ）お
よびコントロールバルブ（日本エムケーエス（株）製２
４８Ａ）を装着した真空ラインを用いた。この窒素吸着
測定の結果より、細孔容積（Ｖ；ｃｃ／ｇ）を細孔直径
（Ｄ；Å）で微分した値（ｄＶ／ｄＤ；ｃｃ／ｇÅ）を
計算し、多孔体中にある細孔の細孔直径の分布を示す細
孔分布曲線を作成した。本実施例で形成した４種類の層
状シリカ多孔体（ＦＳＭ−２３、ＦＳＭ−２８、ＦＳＭ
−４８、ＦＳＭ−５５）の細孔分布曲線を図４〜７に示
す。また、本実施例の比較例としてシリカゲル多孔体
（５４０ＧＭ）およびアルミナ多孔体（γ−アルミナ）
の細孔分布曲線を図８および図９に示す。これらの図よ
り、それぞれの多孔体の中心細孔直径を求め、また、そ
の±５ｎｍの細孔直径を計算し、±５ｎｍ細孔範囲とし
て中心細孔直径の±５ｎｍの範囲内にある細孔直径範囲
を求めた。また、中心細孔直径の±５ｎｍの範囲内にあ
る細孔直径の細孔容量の全細孔容量に対する比率を±５
ｎｍ細孔率として細孔分布曲線の積分曲線から求めた。
本実施例で形成された多孔体の中心細孔直径、±５ｎｍ
細孔範囲および±５ｎｍ細孔率を、比較例のシリカゲル
多孔体（５４０ＧＭ）およびアルミナ多孔体（γ−アル
ミナ）で求められた値とともに表１に示す。When FSM-48 and FSM-55 were subjected to X-ray diffraction in the same manner as above with the slit of the radiation source further narrowed, a peak having a hexagonal structure was detected in the obtained XRD pattern. From this, FSM
It was found that -48 and FSM-55 also have high crystallinity. (Measurement of Pore Size Distribution) The diameter of the pores distributed in the porous body formed in this example was measured by a nitrogen adsorption method in which nitrogen is adsorbed in the porous body. In this method, first, nitrogen is adsorbed on a porous body, the adsorption amount is measured, and a diagram showing a nitrogen adsorption isotherm is created. From this diagram, Cranston-Incla
This is a method of obtaining a pore size distribution in a porous body by calculating a value (dV / dD) obtained by differentiating the pore volume (V) with the pore diameter (D) by the y method. This nitrogen adsorption measurement is performed by the constant volume method. About 50 mg of the porous body sample is weighed into a sample tube of the measuring device, and the inside of the tube is heated while heating the porous body sample in the tube at 130 ° C. until the vacuum degree becomes 10 −3 Torr. Is evacuated for 1 hour to deaerate the air in the pores distributed in the porous body,
The sample tube was immersed in liquid nitrogen to measure the adsorption of nitrogen. The measuring device is an absolute pressure type transducer (Barton 127AA manufactured by Nippon MKS Co., Ltd.) and a control valve (2 manufactured by Nippon MKS Co., Ltd.).
A vacuum line equipped with 48A) was used. From the results of this nitrogen adsorption measurement, the value (dV / dD; cc / gÅ) obtained by differentiating the pore volume (V; cc / g) by the pore diameter (D; Å) was calculated, and the fine particles in the porous body were calculated. A pore distribution curve showing the distribution of pore diameters of pores was created. Four types of layered silica porous bodies (FSM-23, FSM-28, FSM formed in this example
Pore distribution curves of -48, FSM-55) are shown in FIGS. As a comparative example of this example, a silica gel porous body (540GM) and an alumina porous body (γ-alumina) were used.
The pore distribution curves of are shown in FIGS. 8 and 9. From these figures, the central pore diameter of each porous body is determined, and the pore diameter of ± 5 nm is calculated, and the pores within the central pore diameter of ± 5 nm are defined as ± 5 nm pore range. The diameter range was determined. Further, the ratio of the pore volume of the pore diameter within the range of ± 5 nm of the central pore diameter to the total pore volume is ± 5.
The nm porosity was calculated from the integral curve of the pore distribution curve.
Central pore diameter of the porous body formed in this example, ± 5 nm
The pore range and the ± 5 nm porosity are shown in Table 1 together with the values obtained for the silica gel porous body (540GM) and the alumina porous body (γ-alumina) of Comparative Example.
【００１９】[0019]
【表１】 表１により、本実施例により形成した層状シリカ多孔体
は中心細孔直径が１〜１０ｎｍの範囲にあり、その±５
ｎｍ細孔率は６０％以上であるのに対し、シリカゲル多
孔体（５４０ＧＭ）およびアルミナ多孔体（γ−アルミ
ナ）の±５ｎｍ細孔率は６０％以下であることから、本
実施例により形成した層状シリカ多孔体中には、比較例
のシリカゲル多孔体およびアルミナ多孔体に比べ、細孔
直径１〜１０ｎｍの微細な細孔が均一に分布しているこ
とがわかる。 （Ｐｔ粒子の形成）中心細孔直径が２．８ｎｍである１
２０ｇの層状シリカ多孔体（ＦＳＭ−２８）を、１２０
ｇのＦＳＭ−２８に対してＰｔが２ｇ担持されるように
ジニトロジアンミン白金水溶液（４．５２６重量％Ｐｔ
含有；田中貴金属工業製）４４．１９ｇを希釈した水溶
液に浸し、ホットスターラーで加熱攪拌しながら水溶液
中の水分を蒸発させ、１１０℃の真空乾燥器で１０時間
乾燥させた。これを最高１２００℃の温度で加熱できる
加熱炉の炉内に設置した。そして、大気中で乾燥させた
多孔体を室温から所定の温度（以下、前処理温度と称す
る）まで２時間かけて昇温し、さらに前処理温度を２時
間保持して加熱を行い排ガス浄化用触媒（Ｐｔ／ＦＳ
Ｍ）を形成した。この加熱によってジニトロジアンミン
白金は熱分解し、Ｐｔが多孔体表面の細孔上で粒成長し
て、Ｐｔ粒子が形成された。[Table 1] According to Table 1, the layered silica porous material formed according to the present example has a central pore diameter in the range of 1 to 10 nm, and its ± 5
nm porosity is 60% or more, whereas ± 5 nm porosity of the silica gel porous body (540GM) and the alumina porous body (γ-alumina) is 60% or less. It can be seen that fine pores having a pore diameter of 1 to 10 nm are uniformly distributed in the layered silica porous body as compared with the silica gel porous body and the alumina porous body of Comparative Examples. (Pt particle formation) Central pore diameter is 2.8 nm 1
20 g of layered silica porous material (FSM-28)
dinitrodiammine platinum aqueous solution (4.526% by weight Pt so that 2 g of Pt is supported on 1 g of FSM-28).
(Containing; manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) 44.19 g was immersed in a diluted aqueous solution, the water content in the aqueous solution was evaporated while heating and stirring with a hot stirrer, and dried in a vacuum dryer at 110 ° C. for 10 hours. This was installed in the furnace of a heating furnace capable of heating at a temperature of up to 1200 ° C. Then, the porous body dried in the atmosphere is heated from room temperature to a predetermined temperature (hereinafter, referred to as pretreatment temperature) over 2 hours, and further, the pretreatment temperature is maintained for 2 hours to perform heating to purify exhaust gas. Catalyst (Pt / FS
M) was formed. By this heating, dinitrodiammine platinum was thermally decomposed, and Pt was grain-grown on the pores on the surface of the porous body to form Pt particles.
【００２０】得られた排ガス浄化用触媒は粉末Ｘ線回折
法によってＸ線回折を行った。得られたＸ線回折パター
ンから、Ｐｔ結晶の（１１１）面の回折による２θ＝３
９．８°における回折ピークの半値幅を求め、数１に従
って多孔体表面のＰｔの平均粒径を求めた。数１におい
てＬとＢはそれぞれＰｔ粒径（Å）と半値幅（ｄｅ
ｇ．）を示す。Ｘ線回折パターンは理学電子ＲＡＤ−Ｂ
装置を用い、Ｃｕ−Ｋαを線源として測定した。The obtained exhaust gas-purifying catalyst was subjected to X-ray diffraction by a powder X-ray diffraction method. From the obtained X-ray diffraction pattern, 2θ = 3 by the diffraction of the (111) plane of the Pt crystal
The full width at half maximum of the diffraction peak at 9.8 ° was obtained, and the average particle diameter of Pt on the surface of the porous body was obtained according to equation 1. In Equation 1, L and B are the Pt particle size (Å) and the full width at half maximum (de), respectively.
g. ). X-ray diffraction pattern is RAD-B
Using the apparatus, Cu-Kα was measured as a radiation source.
【００２１】[0021]
【数１】 層状シリカ多孔体にジニトロジアンミン白金水溶液を含
浸させ、これを乾燥した後、大気中でそれぞれ５００
℃、６００℃、７００℃、８００℃、９００℃、１００
０℃の前処理温度で加熱して形成された６種の排ガス浄
化用触媒のＰｔの平均粒径および比表面積を表２に示
す。[Equation 1] The layered silica porous material was impregnated with a dinitrodiammine platinum aqueous solution, dried, and then dried in air at 500
℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 100
Table 2 shows the average particle size and specific surface area of Pt of the six types of exhaust gas-purifying catalysts formed by heating at the pretreatment temperature of 0 ° C.
【００２２】[0022]
【表２】 ※はＸ線回折を用いた粒径測定法によってＰｔの粒径が
求められなかったので、ＣＯ吸着法で求めた値を用い
た。[Table 2] * Means that the particle size of Pt could not be obtained by the particle size measurement method using X-ray diffraction, so the value obtained by the CO adsorption method was used.
【００２３】表２より、加熱における前処理温度を６０
０〜１０００℃の範囲内で採用した場合、層状シリカ多
孔体上に形成されるＰｔ粒子の平均粒径は１０〜３０ｎ
ｍの範囲内にあることがわかる。また、比表面積は高比
表面積を保ったままであり、担体の構造が変化していな
いことが確認される。さらに、シリカゲル多孔体および
アルミナ多孔体を担体として、それぞれの担体にジニト
ロジアンミン白金水溶液を含浸させ、これらを乾燥した
後、大気中で所定の前処理温度で２時間加熱して２種類
の排ガス浄化用触媒（Ｐｔ／ＳｉＯ2、Ｐｔ／Ａｌ2 Ｏ
3 ）を形成した。このとき、所定の前処理温度を５００
〜１０００℃の範囲内から採用し、得られた各排ガス浄
化用触媒のＰｔ粒子の平均粒径を調べた結果を、前記Ｐ
ｔ／ＦＳＭのＰｔ粒子の平均粒径とあわせて図１０に示
す。図１０より、前処理温度を６００〜１０００℃の範
囲内から採用した場合、Ｐｔ／ＦＳＭが最も１０〜３０
ｎｍのＰｔ粒子を形成しやすいことがわかる。 （排ガスの浄化試験）本実施例で得られた排ガス浄化用
触媒を用いて、酸素過剰下にあってＮＯX およびＨＣを
含む混合気体のＮＯX の浄化試験を行い、各排ガス浄化
用触媒の最大ＮＯX 浄化率（％）を調べた。From Table 2, the pretreatment temperature for heating is 60
When adopted in the range of 0 to 1000 ° C., the average particle diameter of Pt particles formed on the layered silica porous body is 10 to 30 n.
It can be seen that it is within the range of m. Further, the specific surface area remains high, confirming that the structure of the carrier has not changed. Further, using a silica gel porous body and an alumina porous body as a carrier, each carrier is impregnated with a dinitrodiammine platinum aqueous solution, dried, and then heated at a predetermined pretreatment temperature in the air for 2 hours to purify two kinds of exhaust gas. Catalyst (Pt / SiO 2 , Pt / Al 2 O
3 ) formed. At this time, the predetermined pretreatment temperature is set to 500
The result obtained by examining the average particle diameter of Pt particles of each of the obtained exhaust gas-purifying catalysts adopted from the range of up to 1000 ° C.
It is shown in FIG. 10 together with the average particle size of Pt particles of t / FSM. From FIG. 10, when the pretreatment temperature is adopted from the range of 600 to 1000 ° C., Pt / FSM is most 10 to 30.
It can be seen that Pt particles of nm are easily formed. (Exhaust Gas Purification Test) Using the exhaust gas purification catalyst obtained in this example, a NO X purification test of a mixed gas containing NO X and HC under an excess of oxygen was conducted, and each exhaust gas purification catalyst The maximum NO x purification rate (%) was investigated.
【００２４】中心細孔直径２．８ｎｍの層状シリカ多孔
体（ＦＳＭ−２８）を担体とし、ジニトロジアンミン白
金水溶液を含浸させ、これを乾燥した後、大気中で９通
りの前処理温度で加熱してＰｔ粒子を形成し、Ｐｔ粒子
の平均粒径が異なる９種の排ガス浄化用触媒を得た。こ
れらの排ガス浄化用触媒を用いて排ガス浄化試験を行
い、Ｐｔ粒子の平均粒径が異なる各排ガス浄化用触媒の
最大ＮＯX 浄化率を調べ、Ｐｔ粒子の平均粒径による排
ガス浄化用触媒のＮＯX の浄化効果の違いを明らかにし
た。その結果を図１１に示す。図１１より、Ｐｔ粒子の
平均粒径が１０〜３０ｎｍの範囲内にある時、高いＮＯ
X の浄化効果を有することがわかる。この結果より、粒
径が１０〜３０ｎｍの範囲内にあるＰｔ粒子は高いＮＯ
X の浄化活性を有していることがわかる。A layered silica porous material (FSM-28) having a central pore diameter of 2.8 nm was used as a carrier, impregnated with a dinitrodiammineplatinum aqueous solution, dried, and then heated in the atmosphere at 9 pretreatment temperatures. Thus, Pt particles were formed to obtain 9 kinds of exhaust gas purifying catalysts having different Pt particle average particle diameters. An exhaust gas purification test is carried out using these exhaust gas purification catalysts, the maximum NO x purification rate of each exhaust gas purification catalyst having different Pt particle average particle diameters is investigated, and NO of the exhaust gas purification catalyst based on the average particle diameter of Pt particles is examined. Clarified the difference in the purification effect of X. The result is shown in FIG. From FIG. 11, when the average particle diameter of Pt particles is in the range of 10 to 30 nm, high NO
It can be seen that X has a purifying effect. From this result, Pt particles having a particle size in the range of 10 to 30 nm have high NO.
It can be seen that it has X- purifying activity.
【００２５】中心細孔直径２．８ｎｍの層状シリカ多孔
体（ＦＳＭ−２８）、およびＦＳＭ−２８に４重量％の
アルミナ（Ａｌ2 Ｏ3 ）を担持させたもの（Ａｌ2 Ｏ3
／ＦＳＭ−２８）、シリカゲル多孔体（５４０ＧＭ）を
それぞれ担体として、これらの担体にジニトロジアンミ
ン白金水溶液を含浸させ、これらを乾燥した後、大気中
で所定の前処理温度で２時間加熱して３種類の排ガス浄
化用触媒（Ｐｔ／ＦＳＭ、Ｐｔ／Ａｌ2 Ｏ3 ／ＦＳＭ、
Ｐｔ／５４０ＧＭ）を形成した。このとき、所定の前処
理温度を５００〜１０００℃の範囲内から採用し、得ら
れた各排ガス浄化用触媒の最大ＮＯX 浄化率を調べた結
果を図１２に示す。図１２より、６００℃を越える前処
理温度によって加熱された場合においては、Ｐｔ／ＦＳ
ＭおよびＰｔ／Ａｌ2 Ｏ3 ／ＦＳＭはＰｔ／５４０ＧＭ
よりも高い最大ＮＯX 浄化率を有することがわかる。こ
の結果より、Ｐｔ／ＦＳＭがＰｔ／５４０ＧＭより排ガ
ス浄化用触媒として優れていることがわかる。また、Ａ
ｌ2 Ｏ3 ／ＦＳＭにＰｔを担持したＰｔ／Ａｌ2 Ｏ3 ／
ＦＳＭもＰｔ／５４０ＧＭより優れていることがわか
る。A layered silica porous material (FSM-28) having a central pore diameter of 2.8 nm, and one obtained by supporting 4% by weight of alumina (Al 2 O 3 ) on FSM-28 (Al 2 O 3
/ FSM-28) and silica gel porous material (540GM) as a carrier, these carriers are impregnated with an aqueous dinitrodiammineplatinum solution, dried, and then heated at a predetermined pretreatment temperature in the atmosphere for 2 hours. Exhaust gas purification catalysts (Pt / FSM, Pt / Al 2 O 3 / FSM,
Pt / 540GM) was formed. At this time, a predetermined pretreatment temperature was adopted from the range of 500 to 1000 ° C., and the results of examining the maximum NO x purification rate of each obtained exhaust gas purification catalyst are shown in FIG. From FIG. 12, it can be seen that Pt / FS when heated by a pretreatment temperature exceeding 600 ° C.
M and Pt / Al 2 O 3 / FSM are Pt / 540GM
It can be seen that it has a higher maximum NO x purification rate than. These results show that Pt / FSM is superior to Pt / 540GM as an exhaust gas purification catalyst. Also, A
Pt / Al 2 O 3 / Pt supported on l 2 O 3 / FSM
It can be seen that FSM is also superior to Pt / 540GM.
【００２６】中心細孔直径が２．３ｎｍの層状シリカ多
孔体（ＦＳＭ−２３）、２．８ｎｍの層状シリカ多孔体
（ＦＳＭ−２８）、および４．８ｎｍの層状シリカ多孔
体（ＦＳＭ−４８）を担体として、それぞれの担体にジ
ニトロジアンミン白金水溶液を含浸させ、これらを乾燥
した後、大気中で６００℃で２時間加熱して３種類の排
ガス浄化用触媒を形成した。得られた各排ガス浄化用触
媒の最大ＮＯX 浄化率を調べた結果を図１３に示す。図
１３より、どの排ガス浄化用触媒も高い最大ＮＯX 浄化
率を有することがわかる。この結果より、中心細孔直径
が１〜１０ｎｍの範囲内であって微細な細孔直径の細孔
が均一に分布する多孔体を担体として用いた排ガス浄化
用触媒は、高いＮＯX 浄化活性を有することがわかる。Layered silica porous body (FSM-23) having a central pore diameter of 2.3 nm, 2.8 nm layered silica porous body (FSM-28), and 4.8 nm layered silica porous body (FSM-48). As a carrier, each carrier was impregnated with a dinitrodiammine platinum aqueous solution, dried, and then heated in the air at 600 ° C. for 2 hours to form three kinds of exhaust gas-purifying catalysts. FIG. 13 shows the result of examining the maximum NO x purification rate of each of the obtained exhaust gas-purifying catalysts. From FIG. 13, it can be seen that any exhaust gas purification catalyst has a high maximum NO x purification rate. From these results, the exhaust gas-purifying catalyst using as the carrier a porous body having a central pore diameter in the range of 1 to 10 nm and fine pores having fine pore diameters uniformly distributed has a high NO x purification activity. You know that you have.
【００２７】[0027]
【発明の効果】本発明の排ガス浄化用触媒によって排ガ
ス中の有害物質、とりわけＮＯX を浄化することができ
る。また、本発明の排ガス浄化用触媒の製造方法によっ
てＮＯ X に対して高い浄化活性を有する貴金属粒子を均
一に担体上に形成することができる。EFFECTS OF THE INVENTION Exhaust gas is exhausted by the exhaust gas purifying catalyst of the present invention.
Harmful substances in gas, especially NOXCan purify
You. In addition, according to the method for producing an exhaust gas purifying catalyst of the present invention,
NO XThe precious metal particles with high purification activity against
First, it can be formed on a carrier.
【図１】この図は、層状シリカ多孔体（ＦＳＭ−２３）
のＸ線回折パターンを示した図である。FIG. 1 shows a layered silica porous material (FSM-23).
It is a figure showing the X-ray diffraction pattern of.
【図２】この図は、層状シリカ多孔体（ＦＳＭ−２８）
のＸ線回折パターンを示した図である。FIG. 2 shows a layered silica porous material (FSM-28).
It is a figure showing the X-ray diffraction pattern of.
【図３】この図は、層状シリカ多孔体（ＦＳＭ−４８）
のＸ線回折パターンを示した図である。FIG. 3 shows a layered silica porous body (FSM-48).
It is a figure showing the X-ray diffraction pattern of.
【図４】この図は、層状シリカ多孔体（ＦＳＭ−２３）
の細孔直径の分布を示した細孔分布曲線である。FIG. 4 shows a layered silica porous material (FSM-23).
3 is a pore distribution curve showing the distribution of pore diameters of
【図５】この図は、層状シリカ多孔体（ＦＳＭ−２８）
の細孔直径の分布を示した細孔分布曲線である。FIG. 5 shows a layered silica porous body (FSM-28).
3 is a pore distribution curve showing the distribution of pore diameters of
【図６】この図は、層状シリカ多孔体（ＦＳＭ−４８）
の細孔直径の分布を示した細孔分布曲線である。FIG. 6 shows a layered silica porous body (FSM-48).
3 is a pore distribution curve showing the distribution of pore diameters of
【図７】この図は、層状シリカ多孔体（ＦＳＭ−５５）
の細孔直径の分布を示した細孔分布曲線である。FIG. 7 shows a layered silica porous material (FSM-55).
3 is a pore distribution curve showing the distribution of pore diameters of
【図８】この図は、シリカゲル多孔体（５４０ＧＭ）の
細孔直径の分布を示した細孔分布曲線である。FIG. 8 is a pore distribution curve showing the distribution of pore diameters of a silica gel porous body (540GM).
【図９】この図は、アルミナ多孔体（γ−アルミナ）の
細孔直径の分布を示した細孔分布曲線である。FIG. 9 is a pore distribution curve showing the distribution of pore diameters of an alumina porous body (γ-alumina).
【図１０】この図は、層状シリカ多孔体、シリカゲル多
孔体およびアルミナ多孔体を担体として白金を担持させ
加熱して得られた排ガス浄化用触媒の白金粒径を、加熱
における前処理温度に対して示した図である。FIG. 10 is a graph showing the platinum particle diameter of an exhaust gas purifying catalyst obtained by loading and heating platinum using a layered silica porous material, silica gel porous material and alumina porous material as a carrier, with respect to the pretreatment temperature during heating. FIG.
【図１１】この図は、層状シリカ多孔体（ＦＳＭ−２
８）を担体として白金を担持させ加熱して得られた排ガ
ス浄化用触媒の最大ＮＯX 浄化率を、排ガス浄化用触媒
に形成された白金粒子の平均粒径に対して示した図であ
る。FIG. 11 shows a layered silica porous material (FSM-2).
FIG. 8 is a diagram showing the maximum NO x purification rate of an exhaust gas purifying catalyst obtained by supporting and heating platinum using 8) as a carrier, with respect to the average particle diameter of platinum particles formed in the exhaust gas purifying catalyst.
【図１２】この図は、層状シリカ多孔体およびシリカゲ
ル多孔体を担体として白金を担持させ加熱して得られた
排ガス浄化用触媒の最大ＮＯX 浄化率を、加熱における
前処理温度に対して示した図である。FIG. 12 shows the maximum NO x purification rate of an exhaust gas purifying catalyst obtained by heating platinum with a layered silica porous material and a silica gel porous material as a carrier, against the pretreatment temperature during heating. It is a figure.
【図１３】この図は、中心細孔直径の異なる層状シリカ
多孔体を担体として白金を担持させ加熱して得られた各
排ガス浄化用触媒の最大ＮＯX 浄化率を、層状シリカ多
孔体の中心細孔直径に対して示した図である。FIG. 13 shows the maximum NO x purification rate of each exhaust gas-purifying catalyst obtained by loading and heating platinum with a layered silica porous material having different central pore diameters as a carrier, and It is the figure shown with respect to the pore diameter.
───────────────────────────────────────────────────── 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 １０２Ｂ (72)発明者 福嶋 喜章 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (72)発明者 高田 保夫 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical indication location B01D 53/36 102B (72) Inventor Yoshiaki Fukushima Nagakute-cho, Aichi-gun, Aichi Naga 41 No. 1 Toyota Central Research Institute Co., Ltd. (72) Inventor Yasuo Takada 41 Nagamite, Nagakute-cho, Aichi-gun, Aichi Prefecture
Claims (8)
金属とよりなる排ガス浄化用触媒であって、 該担体は、該担体が有する細孔の直径のうち最も数の多
い細孔直径（以下、中心細孔直径と称する）が１〜１０
ｎｍの範囲内にあって、全細孔の６０％以上の細孔が該
中心細孔直径の±５ｎｍの範囲内の直径を有する多孔体
であり、かつ該貴金属は平均粒径が１０〜３０ｎｍの範
囲内にある金属粒子であることを特徴とする排ガス浄化
用触媒。1. A catalyst for exhaust gas purification comprising a porous carrier and a noble metal supported on the carrier, wherein the carrier has the largest number of pore diameters of the pores of the carrier. (Hereinafter referred to as central pore diameter) is 1 to 10
In the range of nm, 60% or more of all the pores are porous bodies having a diameter within the range of the central pore diameter of ± 5 nm, and the noble metal has an average particle diameter of 10 to 30 nm. An exhaust gas purifying catalyst, characterized in that it is a metal particle within the range.
状シリカ−金属酸化物多孔体からなる請求項１記載の排
ガス浄化用触媒。2. The exhaust gas purifying catalyst according to claim 1, wherein the carrier comprises a layered silica porous body or a layered silica-metal oxide porous body.
ら選ばれる少なくとも１種の貴金属である請求項１記載
の排ガス浄化用触媒。3. The exhaust gas purifying catalyst according to claim 1, wherein the noble metal is at least one noble metal selected from Pt, Rh, Pd, and Ir.
ばれる少なくとも１種の金属の酸化物が添加されている
請求項１記載の排ガス浄化用触媒。4. The exhaust gas purifying catalyst according to claim 1, wherein an oxide of at least one metal selected from Al, Mg, and Ti is added to the noble metal.
あって、全細孔の６０％以上の細孔が該中心細孔直径の
±５ｎｍの範囲内の直径を有する担体に貴金属を担持さ
せる担持工程と、 貴金属が担持された該担体を、酸素・燃料比が４以上で
ある混合気体の雰囲気、又は炭化水素を含まず酸素を含
む雰囲気中で６００〜１０００℃に加熱する加熱工程
と、 からなることを特徴とする排ガス浄化用触媒の製造方
法。5. A carrier having a central pore diameter in the range of 1 to 10 nm, and 60% or more of all the pores have a diameter within ± 5 nm of the central pore diameter. A supporting step of supporting and a heating step of heating the carrier on which the noble metal is supported to 600 to 1000 ° C. in an atmosphere of a mixed gas having an oxygen / fuel ratio of 4 or more, or an atmosphere not containing a hydrocarbon and containing oxygen. And a method for producing an exhaust gas-purifying catalyst, comprising:
状シリカ−金属酸化物多孔体からなる請求項５記載の排
ガス浄化用触媒の製造方法。6. The method for producing an exhaust gas purifying catalyst according to claim 5, wherein the carrier is a layered silica porous body or a layered silica-metal oxide porous body.
ら選ばれる少なくとも１種の貴金属である請求項５記載
の排ガス浄化用触媒の製造方法。7. The method for producing an exhaust gas purifying catalyst according to claim 5, wherein the noble metal is at least one kind of noble metal selected from Pt, Rh, Pd and Ir.
ばれる少なくとも１種の金属の酸化物が添加されている
請求項５記載の排ガス浄化用触媒の製造方法。8. The method for producing an exhaust gas purifying catalyst according to claim 5, wherein an oxide of at least one metal selected from Al, Mg, and Ti is added to the noble metal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04641196A JP3555712B2 (en) | 1996-03-04 | 1996-03-04 | Exhaust gas purification catalyst and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04641196A JP3555712B2 (en) | 1996-03-04 | 1996-03-04 | Exhaust gas purification catalyst and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09234378A true JPH09234378A (en) | 1997-09-09 |
| JP3555712B2 JP3555712B2 (en) | 2004-08-18 |
Family
ID=12746420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04641196A Expired - Fee Related JP3555712B2 (en) | 1996-03-04 | 1996-03-04 | Exhaust gas purification catalyst and method for producing the same |
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| Country | Link |
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| JP (1) | JP3555712B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8258075B2 (en) | 2007-02-06 | 2012-09-04 | Mitsubishi Heavy Industries, Ltd. | Catalyst for treating exhaust gases, method for producing the same, and method for treating exhaust gases |
| JP2016511139A (en) * | 2013-01-28 | 2016-04-14 | ビーエーエスエフ コーポレーション | Catalyst article, system and method for oxidizing nitric oxide |
-
1996
- 1996-03-04 JP JP04641196A patent/JP3555712B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8258075B2 (en) | 2007-02-06 | 2012-09-04 | Mitsubishi Heavy Industries, Ltd. | Catalyst for treating exhaust gases, method for producing the same, and method for treating exhaust gases |
| US8501133B2 (en) | 2007-02-06 | 2013-08-06 | Mitsubishi Heavy Industries, Ltd. | Catalyst for treating exhaust gases, method for producing the same, and method for treating exhaust gases |
| JP2016511139A (en) * | 2013-01-28 | 2016-04-14 | ビーエーエスエフ コーポレーション | Catalyst article, system and method for oxidizing nitric oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3555712B2 (en) | 2004-08-18 |
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