JPH0214744A - Exhaust gas purification catalyst - Google Patents
Exhaust gas purification catalystInfo
- Publication number
- JPH0214744A JPH0214744A JP63162563A JP16256388A JPH0214744A JP H0214744 A JPH0214744 A JP H0214744A JP 63162563 A JP63162563 A JP 63162563A JP 16256388 A JP16256388 A JP 16256388A JP H0214744 A JPH0214744 A JP H0214744A
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- zirconia
- catalyst
- exhaust gas
- dimensional structure
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000000746 purification Methods 0.000 title abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 86
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 36
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 15
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 10
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000010419 fine particle Substances 0.000 claims description 13
- 230000009970 fire resistant effect Effects 0.000 claims description 4
- 239000002002 slurry Substances 0.000 abstract description 24
- 239000000843 powder Substances 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000006262 metallic foam Substances 0.000 description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001954 samarium oxide Inorganic materials 0.000 description 2
- 229940075630 samarium oxide Drugs 0.000 description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- 101100224485 Arabidopsis thaliana POL2B gene Proteins 0.000 description 1
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CMDNLASDNCWLDE-UHFFFAOYSA-N [La].[La].[Ce] Chemical compound [La].[La].[Ce] CMDNLASDNCWLDE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 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
- 230000005183 environmental health Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000001745 non-dispersive infrared spectroscopy Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
- F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ディーゼルエンジン排ガスあるいは可燃性炭
素系微粒子を含有する産業排ガス等の浄化触媒に関する
ものであり、特に高温酸化雰囲気のような厳しい条件下
で使用されても轟い浄化性能を有する耐久性に優れた排
ガス浄化用触媒に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a catalyst for purifying diesel engine exhaust gas or industrial exhaust gas containing combustible carbon-based fine particles, particularly under severe conditions such as high-temperature oxidizing atmosphere. The present invention relates to a highly durable exhaust gas purifying catalyst that has a roaring purifying performance even when used in a lower environment.
［従来の技術］
近年とくにディーゼルエンジン排ガス中の微粒子物質（
主として固体状炭素微粒子、硫酸塩などの硫黄系微粒子
、そして、液状ないし固体状の高分子酒炭化水素微粒子
などよりなる）が環境衛生上問題となっている。これら
微粒子はその粒子径がほとんど１ミクロン以下であり、
大気中に浮遊しやすく呼吸により人体内に取り込まれや
すいためである。したがってこれら微粒子のディーゼル
エンジンからの排出規制を厳しくしてい（方向で検討が
進められている。 これら微粒子の除去方法としては、
セラミックフオーム、セラミックハニカム、ワイヤーメ
ツシュ、金属発泡体、目封じタイプのセラミックハニカ
ムなどの耐火性三次元構造体に炭素系微粒子を燃焼させ
つる触媒物質を担持させ、ディーゼル排ガスなどに含ま
れる微粒子状物質を捕捉すると共に、通常の当該エンジ
ンの走行条件下でえられる排気ガスの排出条件（ガス組
成および温度）において（または電気ヒーター等での加
熱手段を用いて）、捕集した炭素系微粒子を燃焼浄化す
る触媒方式が検討されている。[Prior art] In recent years, particulate matter in diesel engine exhaust gas (
These mainly consist of solid carbon fine particles, sulfur-based fine particles such as sulfates, and liquid or solid polymeric liquor hydrocarbon fine particles, etc.) that have become a problem in terms of environmental health. Most of these fine particles have a particle size of 1 micron or less,
This is because they easily float in the atmosphere and are easily taken into the human body through breathing. Therefore, stricter regulations on the emission of these particulates from diesel engines are currently being considered.
A fire-resistant three-dimensional structure such as ceramic foam, ceramic honeycomb, wire mesh, metal foam, and sealed ceramic honeycomb is loaded with a catalytic material that burns carbon-based particulates, thereby eliminating the particulates contained in diesel exhaust gas, etc. In addition to capturing the substance, the captured carbon-based fine particles are A catalytic method for combustion purification is being considered.
一般にデイ−、ゼルエンジンの排ガス浄化用触媒として
は、炭素系微粒子の燃焼性能が高く、かつ出来るだけ低
温から着火すると共に、燃料として用いる軽油中に多量
に含まれるイオウ成分から発生する二酸化イオウ（８０
２）から三酸化イオウ（ＳＯｓ ）への転化率が低い性
能を有し、さらに高負荷での連続運転下でも耐えるいわ
ゆるａ温耐久性のある触媒が望まれている。In general, catalysts for purifying exhaust gas from diesel engines have high combustion performance for carbon-based particulates, ignite from as low a temperature as possible, and ignite sulfur dioxide (sulfur dioxide), which is generated from the sulfur component contained in large amounts in the light oil used as fuel. 80
There is a need for a catalyst that has a low conversion rate from 2) to sulfur trioxide (SOs) and has so-called A-temperature durability that can withstand continuous operation under high load.
しかし今迄この条件に十分適合する触媒は提案されてい
ないのが現状である。However, to date, no catalyst has been proposed that satisfactorily meets these conditions.
従来より、炭素系微粒子の浄化効率を高める目的で以下
の如き種々の提案がなされている。Conventionally, the following various proposals have been made for the purpose of increasing the purification efficiency of carbon-based fine particles.
白金族金属を炭素系微粒子燃焼用触媒として使用してい
る例としては、特開昭５５−２４５９７号公報において
、ロジウム乙５％／白金合金とか、白金／パラジウム−
５０１５０の混合物とか、酸化タンタルまたは酸化セリ
ウム上に担持したパラジウムあるいは、パラジウムと７
５重ｆｆｉ％以下の白金とからなる合金等が、Ｓ ＯＦ
（ｓｏｌｕｂｌｅｏｒｇａｎｉｃ ｆｒａｃｔｉｏｎ
）に対して効果があることが提案されている。Examples of using platinum group metals as carbon-based particulate combustion catalysts include 5% rhodium/platinum alloys and platinum/palladium alloys in JP-A-55-24597.
50150, palladium supported on tantalum oxide or cerium oxide, or palladium and 7
S OF
(soluble organic fraction
) has been proposed to be effective against
その他、特開昭６１−１２９０３０号、同６１−１４９
２２２号および同６１−１４６３１４号公報において、
パラジウムとロジウムを主な活性成分とし、さらにアル
カリ金属、アルカリ土類金属、銅、ランタン、亜鉛なら
びにマンガン等を添加した触媒組成物が効果があること
が提案されている。Others: JP-A-61-129030, JP-A No. 61-149
In No. 222 and No. 61-146314,
It has been proposed that a catalyst composition containing palladium and rhodium as the main active ingredients, with further additions of alkali metals, alkaline earth metals, copper, lanthanum, zinc, manganese, etc., is effective.
［発明が解決しようとする問題点］
しかし白金を触媒成分として含有する触媒は、排ガス中
の８０２の酸化能が高く、サルフェート（Ｓ０２が酸化
されてＳ０３や硫酸ミストとなったもの）を多量に生成
し、むしろ硫黄系微粒子の増加を招く結果となり好まし
くない。これに対しパラジウムは白金に比べてサルフェ
ート生成率が低く、炭素系微粒子の燃焼性能を有し、か
つ耐熱性もある、好ましい性能を有している。[Problems to be solved by the invention] However, catalysts containing platinum as a catalyst component have a high ability to oxidize 802 in exhaust gas, and produce a large amount of sulfate (S02 oxidized to S03 and sulfuric acid mist). This is not preferable since it results in an increase in sulfur-based fine particles. On the other hand, palladium has preferable properties such as a lower sulfate production rate than platinum, good combustion performance for carbon-based fine particles, and heat resistance.
しかしながら、ディーゼルエンジンの排ガス雰囲気に曝
されるとパラジウム表面の酸化状態が変化し、急速に活
性を失なうなどの欠点を有していた。However, when exposed to the exhaust gas atmosphere of a diesel engine, the oxidation state of the palladium surface changes, resulting in a rapid loss of activity.
従って現在までに提案されたパラジウムを含有する触媒
においてこの失活を抑制してなる触媒は提案されていな
い。Therefore, among the palladium-containing catalysts proposed to date, no catalyst has been proposed that suppresses this deactivation.
そこで、本発明の目的は炭素系微粒子の低温からの燃焼
性能を有し、かつサルフェートの生成率の低いパラジウ
ムの好ましい性能に着目し、その選択酸化性能を高めて
排ガス浄化能を高めると共に、ディーゼルエンジンの排
ガス雰囲気下において安定に、かつ長時間維持しつる耐
熱性、耐久性のある実用可能な炭素系微粒子を浄化する
排ガス浄化用触媒を提供することにある。Therefore, the purpose of the present invention is to focus on the favorable performance of palladium, which has the ability to burn carbon-based particulates from low temperatures and has a low rate of sulfate generation. It is an object of the present invention to provide a catalyst for exhaust gas purification that purifies carbon-based fine particles stably in the exhaust gas atmosphere of an engine, has heat resistance and durability that can be maintained for a long time, and can be used for practical purposes.
［問題点を解決、するための手段］
本発明者らは、上記目的を達成するためにディーゼル排
ガス中でのパラジウムの反応挙動に関して鋭意研究した
結果、ジルコニア基材上にパラジウムを含有させること
によって、低温からの炭素系微粒子の燃焼性能を有し、
かつサルフェートの生成率を低減する、優れた選択酸化
能を示すことを見い出した。さらに、ジルコニア基材上
にパラジウムとプラセオジム、セリウム、ランタン、ネ
オジウムおよびサマリウムからなる群から選ばれる少な
くとも１種の希土類元素の酸化物を含有させることによ
って、パラジウムならびにジルコニア基材の安定化が達
成され、高い選択酸化性能を有し、かつ４００℃以上の
高温でのディーゼルエンジン排ガス雰囲気下において長
時間その性能を維持しうる耐熱性ならびに耐久性を有す
るものであることを見い出し、本発明を完成するに至っ
た。[Means for Solving the Problems] In order to achieve the above object, the present inventors conducted extensive research on the reaction behavior of palladium in diesel exhaust gas, and found that by incorporating palladium on a zirconia base material, , has the combustion performance of carbon-based particulates from low temperatures,
It was also found that it exhibits excellent selective oxidation ability that reduces the rate of sulfate production. Further, by incorporating palladium and an oxide of at least one rare earth element selected from the group consisting of praseodymium, cerium, lanthanum, neodymium, and samarium on the zirconia base material, stabilization of palladium and the zirconia base material is achieved. discovered that it has high selective oxidation performance, and has heat resistance and durability that can maintain its performance for a long time in a diesel engine exhaust gas atmosphere at a high temperature of 400°C or higher, and completed the present invention. reached.
すなわち、本発明は、耐火性三次元構造体に、ジルコニ
アおよびパラジウムならびにプラセオジム、セリウム、
ランタン、ネオジムおよびサマリウムからなる群から選
ばれる少なくとも１種の希土類元素の酸化物を含有する
ことを特徴とする炭素系微粒子を浄化する排ガス浄化用
触媒である。That is, the present invention provides a refractory three-dimensional structure containing zirconia and palladium, as well as praseodymium, cerium,
This is an exhaust gas purifying catalyst for purifying carbon-based fine particles, characterized by containing an oxide of at least one rare earth element selected from the group consisting of lanthanum, neodymium, and samarium.
本発明における触媒成分であるパラジウムとプラセオジ
ム、セリウム、ランタン、ネオジムおよびサマリウムか
らなる群から選ばれる少なくとも１種の希土類元素は、
耐火性三次元構造体に担持されたジルコニア基材上に所
定の面を分散担持されている。At least one rare earth element selected from the group consisting of palladium, praseodymium, cerium, lanthanum, neodymium, and samarium, which is a catalyst component in the present invention, is
A predetermined surface is dispersed and supported on a zirconia base material supported on a fire-resistant three-dimensional structure.
本発明におけるパラジウムの出発原料としては、硝酸パ
ラジウム、塩化パラジウム、パラジウムテトラミンクロ
ライドおよびパラジウムスルフィｊ〜錯塩等から選ばれ
る。The starting material for palladium in the present invention is selected from palladium nitrate, palladium chloride, palladium tetramine chloride, palladium sulfide complex salts, and the like.
また、プラセオジム、セリウム、ランタン、ネオジムお
よびサマリウムの出発原料としては、市販の酸化物、塩
化物、硝酸塩、炭酸塩等の水あるいは有機溶媒可溶性塩
が好適に用いられる。触媒層を構成する各成分の担持量
は、ジルコニアとしては、三次元構造体１ノあたり３〜
１５０ｇ、好ましくは１０〜１２０ｇ、プラセオジム、
セリウム、ランタン、ネオジムおよびサマリウムからな
る群から選ばれる少なくとも１擾の希土類元素は、その
酸化物の合計重量として、構造体１１あたり１〜５０ｇ
、好ましくは５〜３０ｇ、パラジウムとしては構造体１
ノあたり０．１〜２Ｃ１，好ましくは１〜１０ｑの範囲
である。Further, as starting materials for praseodymium, cerium, lanthanum, neodymium and samarium, commercially available salts soluble in water or organic solvents such as oxides, chlorides, nitrates and carbonates are preferably used. The supported amount of each component constituting the catalyst layer is 3 to 3 per 3-dimensional structure as zirconia.
150 g, preferably 10-120 g, praseodymium,
At least one rare earth element selected from the group consisting of cerium, lanthanum, neodymium and samarium is present in an amount of 1 to 50 g per structure 11 as a total weight of its oxides.
, preferably 5 to 30 g, as palladium Structure 1
The amount is in the range of 0.1 to 2C1, preferably 1 to 10q.
本発明にかかる触媒調製法は、特定されないが、好まし
いものとしては以下の方法が一例としてあげられる。Although the method for preparing the catalyst according to the present invention is not specified, the following method is preferred as an example.
すなわら、ジルコニア粉体を湿式粉砕してスラリー化し
、該スラリーに三次元構造体を浸漬し、余分なスラリー
を取除き、乾燥、焼成してジルコニアコートした三次元
構造体をえる。That is, zirconia powder is wet-pulverized to form a slurry, a three-dimensional structure is immersed in the slurry, excess slurry is removed, and a zirconia-coated three-dimensional structure is obtained by drying and firing.
ここでジルコニア粉体の担持強度を高めるために、水溶
性のアルミナゾルおよび／またはシリカゾルをアルミナ
および／またはシリカの総ＩＩＩで、ジルコニアに対し
て２０重量％以下の割合で混入することは本発明の効果
を何ら妨げるものではない。Here, in order to increase the supporting strength of the zirconia powder, it is preferable in the present invention to mix a water-soluble alumina sol and/or silica sol in a total amount of alumina and/or silica in a proportion of 20% by weight or less based on the zirconia. It does not interfere with the effect in any way.
次に、ジルコニアコートした構造体をパラジウムとプラ
セオジム、セリウム、ランタン、ネオジムおよびサマリ
ウムからなる群から選ばれる少なくとも１種の希土類の
所定量を含有してなる水溶液中に浸漬して余分な溶液を
取除き空気雰囲気下で乾燥、焼成して調製する。Next, the zirconia-coated structure is immersed in an aqueous solution containing palladium and a predetermined amount of at least one rare earth element selected from the group consisting of praseodymium, cerium, lanthanum, neodymium, and samarium, and excess solution is removed. It is prepared by drying and firing in an air atmosphere.
耐火性三次元構造体としは、セラミックフオーム、セラ
ミックハニカム、ウオールフロータイブのハニカムモノ
リス、メタルハニカム、金属発泡体またはメタルメツシ
ュが用いられ、そのうちウオールフロータイブのハニカ
ムモノリス、セラミックハニカムおよびセラミックフオ
ームが好適に用いられる。As the refractory three-dimensional structure, ceramic foam, ceramic honeycomb, wall-flow type honeycomb monolith, metal honeycomb, metal foam or metal mesh are used, among which wall-flow type honeycomb monolith, ceramic honeycomb and ceramic foam are preferred. used.
［作 用］
本発明のジルコニアとプラセオジム、セリウム２ランタ
ン、ネオジムおよびサマリウムからなる群から選ばれる
少なくとも１種の希土類元素の酸化物とパラジウムを含
有してなる炭素系微粒子を浄化する排ガス浄化用触媒は
、ジルコニアを基材として用いることによって低温から
の炭素系微粒子の燃焼性能を有し、かつサルフェートの
生成率を低減する選択酸化能に優れたものであり、さら
にはプラセオジム、セリウム、ランタン、ネオジムおよ
びサマリウムからなる群から選ばれる少なくとも１種の
希土類の添加により、パラジウムならびにジルコニアの
安定化が達成され、その優れた浄化性能を低温から再現
性よく、さらにはディーゼルエンジン排気ガスの排出条
件（ガス組成および温度）において長時間にわたって初
期活性を維持する耐熱性、耐久性を有する排ガス浄化用
触媒である。[Function] A catalyst for exhaust gas purification that purifies carbon-based fine particles containing zirconia of the present invention, an oxide of at least one rare earth element selected from the group consisting of praseodymium, cerium dilanthanum, neodymium, and samarium, and palladium. By using zirconia as a base material, it has the ability to burn carbon-based particulates from low temperatures and has excellent selective oxidation ability to reduce the rate of sulfate production. By adding at least one rare earth element selected from the group consisting of It is a heat-resistant and durable catalyst for exhaust gas purification that maintains its initial activity over a long period of time (composition and temperature).
［実 施 例］
以下、実施例および比較例を示し本発明を更に詳細に説
明するが、本発明はこれら実施例のみに限定されるもの
ではないことは言うまでもない。[Examples] Hereinafter, the present invention will be explained in more detail by showing Examples and Comparative Examples, but it goes without saying that the present invention is not limited only to these Examples.
実施例１
比表面積１３０ＴＩＬ２／ｇを有するジルコニア粉末２
Ｋｙを秤り取り、水を加え湿式粉砕してスラリー化し
、コージェライト製ウオールフロー型モノリス担体（ハ
ニカム型三次元構造体であり、両端面の隣接する８孔を
互い違いに閉塞させ隔壁からのみガスを通過させるよう
にした目封じタイプの構造体’） ５．６６インチ径Ｘ
６． Ｏ０インチ長さのものを該スラリーに浸漬し、
余分なスラリーを取り除き１５０℃で３′時間乾燥後、
５００℃で２時間焼成してジルコニアを担持した構造体
をえた。Example 1 Zirconia powder 2 having a specific surface area of 130 TIL2/g
Ky is weighed out, water is added and wet-pulverized to form a slurry, which is made into a cordierite wall-flow monolithic carrier (honeycomb-shaped three-dimensional structure, with 8 adjacent holes on both end faces alternately blocked to allow gas to flow only from the partition walls). 5.66 inch diameter
6. 0 inch length is immersed in the slurry,
After removing excess slurry and drying at 150°C for 3' hours,
A structure supporting zirconia was obtained by firing at 500° C. for 2 hours.
次いで、硝酸プラセオジム［Ｐｒ （ＮＯ３）３・６
Ｈ２０］ ６０８０とパラジウムとして２３ｇ含有する
硝酸パラジウムを脱イオン水に溶解させ２Ｊの溶液をえ
た。この溶液にジルコニア担持した三次元構造体を浸漬
させ、余分な溶液を取除き１５０℃で３時間乾燥し、次
いで５００℃で２時間焼成して完成触媒をえた。Next, praseodymium nitrate [Pr (NO3)3.6
H20] 6080 and palladium nitrate containing 23 g of palladium were dissolved in deionized water to obtain a 2 J solution. A three-dimensional structure carrying zirconia was immersed in this solution, excess solution was removed, it was dried at 150°C for 3 hours, and then calcined at 500°C for 2 hours to obtain a completed catalyst.
えられた触媒のジルコニア、パラジウム、ＷＩ化プラセ
オジム［Ｐｒ６Ｏ１１］それぞれの成分の担持間は構造
体１ｊ！あたり６０（１、１，５（Ｊ 、 １５！Ｉｔ
であった。The structure 1j! supports the components of the obtained catalyst, zirconia, palladium, and WI-based praseodymium [Pr6O11]. per 60 (1, 1, 5 (J, 15!It
Met.
実施例２
硝酸プラセオジムの替わりに硝酸セリウム［Ｃｅ （
ＮＯ３）３−６Ｈ２０］ ５８２にＪを用いた以外は、
実施例１におけると同様にして完成触媒をえた。えられ
た触媒のジルコニア、パラジウム、１ｌｌＩ化セリウム
［Ｃｅ ０２ ］の担持吊はそれぞれ構造体１１あたり
６０Ｇ 、１．！Ｍ 、１５Ｑであった。Example 2 Cerium nitrate [Ce (
NO3)3-6H20] Except for using J in 582,
A finished catalyst was obtained in the same manner as in Example 1. The supporting suspension of the obtained catalysts, zirconia, palladium, and cerium 1llI chloride [Ce 02 ], was 60 G per structure 11 and 1. ! M, 15Q.
実施例３
硝酸プラセオジムの替わりに硝酸ランタン［Ｌａ （
ＮＯ３）３−６８２０］６１３ａを用いた以外は、実施
例１におけると同様にして完成触媒をえた。えられた触
媒のジルコニア、パラジウム、酸化ランタン［Ｌａ ２
０３ ］の担持量はそれぞれ構造体１１あたり６０ｉ１
１ 、１．５０ 、１５（Ｊであった。Example 3 Lanthanum nitrate [La (
A finished catalyst was obtained in the same manner as in Example 1, except that NO3)3-6820]613a was used. The catalyst obtained was zirconia, palladium, and lanthanum oxide [La 2
03] is 60i1 per structure 11, respectively.
1, 1.50, 15 (J).
実施例４
硝酸プラセオジムの替わりに硝酸ネオジム［Ｎｄ ＜
ＮＯｓ ）３ ・６Ｈ２０］ ６０１ｇを用いる以外は
、実施例１におけると同様にして完成触媒をえた。えら
れた触媒のジルコニア、パラジウム、Ｆｉ化ネオジム［
Ｎｄ ２０ｓ ］の担持量はそれぞれ構造体１１あたり
６０（Ｊ 、１．５Ｕ 、１５ａであった。Example 4 Neodymium nitrate [Nd<
A finished catalyst was obtained in the same manner as in Example 1, except that 601 g of NOs )3 .6H20] was used. The catalyst obtained was zirconia, palladium, and neodymium oxide [
The supported amounts of Nd 20s ] were 60 (J , 1.5 U, and 15 a per structure 11), respectively.
実施例５
硝酸プラセオジムの替わりに硝酸サマリウム［Ｓｍ
（ＮＯ３）３ ・６Ｈ２０］ ５８８（ｌを用いた以外
は、実施例１におけると同様にして完成触媒をえた。え
られた触媒のジルコニア、パラジウム、酸化サマリウム
［Ｓｍ ２０３］の担持間はそれぞれ構造体１ｊ！あた
り６ａｇ、１．５（１，１５（１であった。Example 5 Samarium nitrate [Sm
A completed catalyst was obtained in the same manner as in Example 1 except that (NO3)3 .6H20]588(l) was used. It was 6ag, 1.5(1,15(1) per body 1j!
実施例６
比表面積１３０ｍ２／（Ｊを有するジルコニア粉末１
ｋＱに硝酸セリウム５００ｏ、硝酸プラセオジム４４０
ｇを溶解した水溶液１１を投入し充分かきまぜた後１５
０℃で６時間乾燥後、５００℃で２時間焼成して酸化セ
リウムおよび酸化プラセオジムを含有したジルコニア粉
末を得た。Example 6 Zirconia powder 1 having a specific surface area of 130 m2/(J
kQ with 500o cerium nitrate and 440o praseodymium nitrate
After adding aqueous solution 11 in which g was dissolved and stirring thoroughly, 15
After drying at 0°C for 6 hours, it was fired at 500°C for 2 hours to obtain zirconia powder containing cerium oxide and praseodymium oxide.
該粉体１都を湿式粉砕してスラリー化し、該スラリーに
実施例１で用いたのと同様の三次元構造体を浸漬し、余
分なスラリーを取除き、１５０℃で３時間乾燥後、５０
０℃で２時間焼成して、酸化セリウムおよび酸化サマリ
ウム含有ジルコニアを担持した構造体をえた。The powder was wet-pulverized to form a slurry, a three-dimensional structure similar to that used in Example 1 was immersed in the slurry, excess slurry was removed, and after drying at 150°C for 3 hours,
By firing at 0° C. for 2 hours, a structure supporting zirconia containing cerium oxide and samarium oxide was obtained.
次いでパラジウムとして３５ａを含有する塩化パラジウ
ムを脱イオン水に溶解させ２１の溶液をえた。この溶液
に該酸化セリウムおよび酸化プラセオジムを含有するジ
ルコニアを担持した構造体を浸漬させ、パラジウムを吸
着させた後、余分な溶液を取り除き、１５０℃で２時間
乾燥後、８００℃で１時間焼成して完成触媒をえた。え
られた触媒のジルコニア、酸化セリウム、Ｍ化プラセオ
ジム、パラジウム、それぞれの担持量は構造体１１あた
り３０！ＩＩ 、 ６０ 、５ＣＩ 、 ２．３（ｌで
あった。Next, palladium chloride containing 35a as palladium was dissolved in deionized water to obtain a solution of 21. A structure supporting zirconia containing cerium oxide and praseodymium oxide was immersed in this solution to adsorb palladium, then excess solution was removed, dried at 150°C for 2 hours, and then baked at 800°C for 1 hour. A completed catalyst was obtained. The supported amount of each of the obtained catalysts, zirconia, cerium oxide, praseodymium M, and palladium, was 30 per structure 11! II, 60, 5CI, 2.3 (l).
実施例７
比表面積４６ｍ、／（Ｊを有するジルコニア粉末ｌｋｏ
を秤り取り水湿式粉砕してスラリー化し、ジルコニアを
４０重層％含有するスラリーを２．５８！Ｊをえた。該
スラリーにアルミナを２０ｆｆｉｌｉ１％含有する市販
のアルミナゾル５００ｇを投入しで、溶解性アルミナを
含有したジルコニアスラリーを得Ｉこ 。Example 7 Zirconia powder lko with specific surface area 46 m, /(J
was weighed and wet-pulverized to form a slurry, and a slurry containing 40% zirconia was obtained at 2.58%! I got J. A zirconia slurry containing soluble alumina was obtained by adding 500 g of a commercially available alumina sol containing 20 ffili1% of alumina to the slurry.
該スラリーに実施例１で用いたのと同様の三次元構造体
を浸漬し、余分なスラリーを取除き、１５０℃で３時間
乾燥後、４００℃で２時間焼成してジルコニアを担持し
た構造体をえた。A three-dimensional structure similar to that used in Example 1 was immersed in the slurry, excess slurry was removed, dried at 150°C for 3 hours, and then fired at 400°C for 2 hours to obtain a structure supporting zirconia. I got it.
次いで硝酸ランタン６１３ｇと硝酸ネオジム４２０ｇと
パラジウムとして６５ｇ含有する硝酸パラジウムを脱イ
オン水に溶解させ２〕の溶液をえた。この溶液にジルコ
ニアを担持した三次元構造体を浸漬させ、余分な溶液を
取除き１５０℃で３時間乾燥し、次いで５００℃で２時
間焼成して完成触媒をえた。Next, 613 g of lanthanum nitrate, 420 g of neodymium nitrate, and palladium nitrate containing 65 g of palladium were dissolved in deionized water to obtain a solution 2). A three-dimensional structure supporting zirconia was immersed in this solution, excess solution was removed, dried at 150°C for 3 hours, and then calcined at 500°C for 2 hours to obtain a completed catalyst.
えられた触媒のジルコニア、アルミナ、酸化ランタン、
酸化ネオジム、パラジウムそれぞれの成分の担持量は構
造体１ｆ！あたり８０ｇ、８（１。The resulting catalysts are zirconia, alumina, lanthanum oxide,
The supported amount of each component of neodymium oxide and palladium is 1f of the structure! 80g per, 8(1.
１０ｇ、７０．４．２ＣＩであった。10 g, 70.4.2 CI.
実施例８
比表面積２ＴｒＬ２／９、平均粒径３０μｍを有するジ
ルコニア粉末１ Ｋｇをシリカを２０重量％含有する市
販のシリカゾル１ Ｋｌに投入し充分混合してスラリー
化し、該スラリーに実施例１で用いたのと同様の三次元
構造体を浸漬し、余分なスラリーを取除き、１５０℃で
３時間乾燥後、５００℃で２時間焼成して、ジルコニア
を担持した構造体をえた。Example 8 1 kg of zirconia powder having a specific surface area of 2TrL2/9 and an average particle size of 30 μm was added to a commercially available silica sol 1 Kl containing 20% by weight of silica, thoroughly mixed to form a slurry, and the slurry was used in Example 1. A three-dimensional structure similar to the one shown above was immersed, excess slurry was removed, and after drying at 150°C for 3 hours, it was fired at 500°C for 2 hours to obtain a structure supporting zirconia.
次いて硝酸プラセオジム２９２ｇ、硝酸セリウム２３２
Ｑ、硝酸サマリウム１４１ｇおよびパラジウムとして２
３（ｌを含有する硝酸パラジウムを脱イオン水に溶解さ
せ２１の溶液をえた。この溶液に該ジルコニア担持構造
体を浸漬させ、余分な溶液を取除き１５０℃で３時間乾
燥し、次いで５００℃で２時間焼成して完成触媒をえた
。Next, 292 g of praseodymium nitrate, 232 g of cerium nitrate
Q, 141g of samarium nitrate and 2 as palladium
A solution of 21 was obtained by dissolving palladium nitrate containing 3(l) in deionized water. The zirconia support structure was immersed in this solution, excess solution was removed, and the structure was dried at 150°C for 3 hours, then at 500°C. After firing for 2 hours, a completed catalyst was obtained.
えられた触媒のジルコニア、シリカ、ＷＩ化プラセオジ
ム、酸化セリウム、酸化サマリウム、パラジウムの担持
量はそれぞれ構造体１Ｊｌあたり５０ａ、１０ｇ、６ｇ
、５ｇ、３ｇ、１．９ｇであった。The supported amounts of zirconia, silica, WI-based praseodymium, cerium oxide, samarium oxide, and palladium of the obtained catalyst were 50a, 10g, and 6g per 1Jl of the structure, respectively.
, 5g, 3g, and 1.9g.
実施例９
実施例１において三次元構造体としてウオールフロー型
ハニカムモノリスを用いる酔わりに、コージエライ１〜
発泡体（７：ＩＪ密度０．３５＋１／ａ 、空孔率８
７．５％、容積２．５１＞を用いた以外は実施＠１にお
けると同様にして完成触媒をえた。Example 9 In Example 1, a wall flow type honeycomb monolith was used as the three-dimensional structure.
Foam (7: IJ density 0.35+1/a, porosity 8
The finished catalyst was obtained as in Run @1 except that 7.5%, volume 2.51> was used.
えられた触媒のジルコニア、Ｍ化プラセオジム。The obtained catalyst is zirconia and praseodymium M.
パラジウムのそれぞれの担持量は構造体１１当り６０ｑ
、１５ｑ 、１．５ｇであった。The amount of palladium supported is 60q per 11 structures.
, 15q, 1.5g.
比較例１
比表面積１５０ｍ２／ｇを有するアルミナ粉末２ Ｋｇ
を秤り取り水と湿式粉砕してスラリー化し、該スラリー
に実施例１で用いたのと同様の三次元構造体を浸漬し、
余分なスラリー取除き１５０℃で、３時間乾燥１５００
℃で２時間焼成してアルミナを担持した構造体をえた。Comparative Example 1 Alumina powder with a specific surface area of 150 m2/g 2 kg
was weighed and wet-pulverized with water to form a slurry, and a three-dimensional structure similar to that used in Example 1 was immersed in the slurry,
Remove excess slurry and dry at 150℃ for 3 hours.
A structure supporting alumina was obtained by firing at ℃ for 2 hours.
次いでパラジウムとして２３ｇ含有する硝酸パラジウム
を脱イオン水に溶解させ２１の溶液をえた。この溶液に
アルミナ担持した三次元構造体を浸漬させ、余分な溶液
を取除き１５０℃で３時間乾燥した侵、５００℃で２時
間焼成して完成触媒をえた。Next, palladium nitrate containing 23 g of palladium was dissolved in deionized water to obtain a solution of No. 21. The three-dimensional structure supporting alumina was immersed in this solution, excess solution was removed, the structure was dried at 150°C for 3 hours, and then calcined at 500°C for 2 hours to obtain a completed catalyst.
えられた触媒のアルミナ、パラジウムのそれぞれの担持
量は、構造体１１あたり６０ｇ、１．５ｇであった。The supported amounts of alumina and palladium in the obtained catalyst were 60 g and 1.5 g per structure 11, respectively.
比較例２
パラジウムとして２３ｇ含有する硝酸パラジウムを脱イ
オン水に溶解させた２１の溶液に、実施例１におけると
同様にして調製したアルミナ担持三次元構造体を浸漬さ
せ、余分な溶液を取除き１５０℃で３時間乾燥した後、
５００℃で２時間焼成して完成触媒をえた。Comparative Example 2 An alumina-supported three-dimensional structure prepared in the same manner as in Example 1 was immersed in a solution of 21 in which palladium nitrate containing 23 g of palladium was dissolved in deionized water, and the excess solution was removed. After drying for 3 hours at °C,
A completed catalyst was obtained by calcining at 500°C for 2 hours.
えられた触媒のジルコニア、パラジウムのそれぞれの担
持量は、構造体１１あたり６０ｏ、１５σ、１．５（Ｊ
であった。The supported amounts of zirconia and palladium in the obtained catalyst were 60o, 15σ, and 1.5 (J
Met.
上記実施例１〜９ならびに比較例１〜２の各触媒組成物
の構造体１１あたりの担１ｍを表−１に示した。Table 1 shows 1 m of support per structure 11 for each of the catalyst compositions of Examples 1 to 9 and Comparative Examples 1 to 2.
［発明の効果］
実施例１〜９、比較例１〜２でえられた触媒について、
排気１２３００ｃｃ、４気筒デイーゼルエンジンを用い
て、触媒の評価試験を行なった。エンジン回転数２５０
Ｏｒ９１、ｔ’ルク４．０に０・−の条件で微粒子の捕
捉約２時間を行ない、次いでトルクを０．５ｋｏ−ｓ間
隔で５分毎に上昇させて、触媒層の圧損変化を連続的に
記録し、微粒子が触媒上で排ガス温度上昇に伴ない、微
粒子の蓄積による圧力上昇と微粒子の燃焼による圧力降
下とが等しくなる温度（Ｔｅ ＞と着火燃焼、圧損が急
激に降下する温度（Ｔｉ ）を求めた。[Effect of the invention] Regarding the catalysts obtained in Examples 1 to 9 and Comparative Examples 1 to 2,
A catalyst evaluation test was conducted using a 4-cylinder diesel engine with an exhaust of 12,300 cc. Engine speed 250
Or91, particle capture was carried out for about 2 hours under the conditions of t' torque 4.0 and 0 -, and then the torque was increased every 5 minutes at 0.5 ko-s intervals to continuously observe pressure drop changes in the catalyst layer. As the exhaust gas temperature rises on the catalyst, the temperature at which the pressure increase due to the accumulation of the particles is equal to the pressure drop due to the combustion of the particles (Te > and the temperature at which ignition combustion and pressure drop rapidly decreases (Ti ) was sought.
又、Ｓ０２のＳＯ３への転化率を排ガス温度４００℃で
求めた。８０２の転化率は入口ガス、出口ガスの８０２
濃度を非分散型赤外分析計（ＮＤＩＲ法）で分析し、次
の算出式よりＳ０２の転化率（％）を求めた。In addition, the conversion rate of SO2 to SO3 was determined at an exhaust gas temperature of 400°C. The conversion rate of 802 is the inlet gas and outlet gas.
The concentration was analyzed using a non-dispersive infrared analyzer (NDIR method), and the conversion rate (%) of S02 was determined using the following formula.
入口８０２１度（ＤＥｌ量）−
次に、エンジン回転数２５００ｒｐ■の全負荷、触媒入
口温度６００℃での触媒耐久試験を行ない、３００時間
後の活性を初期の評価と同じ方法で評価し、活性劣化を
測定した。Inlet 8021 degrees (DEL amount) - Next, a catalyst durability test was conducted at a full load engine speed of 2500 rpm and a catalyst inlet temperature of 600 degrees Celsius, and the activity after 300 hours was evaluated using the same method as the initial evaluation. Deterioration was measured.
以上の測定結果を第２表に示す。The above measurement results are shown in Table 2.
第２表より本発明に開示するジルコニアとプラセオジム
、セリウム、ランタン、ネオジムおよびサマリウムから
選ばれた１種又は２種以上の希土類元素とパラジウムを
共存させた触媒は、高い浄化性能を有すると共に、高温
酸化雰囲気のような厳しい条件下においても劣化の少な
い、耐久性にも優れた触媒であることは明らかである。From Table 2, the catalyst disclosed in the present invention in which palladium coexists with zirconia and one or more rare earth elements selected from praseodymium, cerium, lanthanum, neodymium, and samarium has high purification performance and high temperature It is clear that this is a highly durable catalyst that exhibits little deterioration even under severe conditions such as an oxidizing atmosphere.
Claims (3)
ウムならびにプラセオジム、セリウム、ランタン、ネオ
ジムおよびサマリウムからなる群から選ばれる少なくと
も１種の希土類元素の酸化物を含有することを特徴とす
る炭素系微粒子を浄化する排ガス浄化用触媒。(1) Carbon-based fine particles characterized in that a fire-resistant three-dimensional structure contains zirconia and palladium, and an oxide of at least one rare earth element selected from the group consisting of praseodymium, cerium, lanthanum, neodymium, and samarium. A catalyst for purifying exhaust gas.
造体１リットル当り、それぞれ３〜１５０ｇ、０．１〜
２０ｇ担持されていることを特徴とする請求項（１）の
触媒。(2) Zirconia and palladium are 3 to 150 g and 0.1 to 150 g, respectively, per 1 liter of the fire-resistant three-dimensional structure.
The catalyst according to claim 1, wherein 20g is supported.
次元構造体１リットル当り１〜５０ｇ担持されているこ
とを特徴とする請求項（１）の触媒。(3) The catalyst according to claim (1), wherein the total amount of the rare earth element oxide supported is 1 to 50 g per liter of the refractory three-dimensional structure.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63162563A JPH0214744A (en) | 1988-07-01 | 1988-07-01 | Exhaust gas purification catalyst |
| DE3853258T DE3853258T2 (en) | 1987-11-07 | 1988-11-03 | Catalytic converter for exhaust gas cleaning of diesel engines. |
| CA000582078A CA1319141C (en) | 1987-11-07 | 1988-11-03 | Exhaust gas purification catalyst |
| EP88118309A EP0315896B1 (en) | 1987-11-07 | 1988-11-03 | Diesel engine exhaust gas purification catalyst |
| KR1019880014616A KR940000862B1 (en) | 1987-11-07 | 1988-11-07 | Exhust gas purification catalyst |
| US07/488,389 US5000929A (en) | 1987-11-07 | 1990-02-23 | Exhaust gas purification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63162563A JPH0214744A (en) | 1988-07-01 | 1988-07-01 | Exhaust gas purification catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0214744A true JPH0214744A (en) | 1990-01-18 |
Family
ID=15756969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63162563A Pending JPH0214744A (en) | 1987-11-07 | 1988-07-01 | Exhaust gas purification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0214744A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002343207A (en) * | 2001-05-18 | 2002-11-29 | Saginomiya Seisakusho Inc | Pressure switch |
| KR100384015B1 (en) * | 2000-12-02 | 2003-05-14 | 현대자동차주식회사 | Improved NOx conversion and thermal durable Pd only three way catalyst |
| WO2006068022A1 (en) * | 2004-12-20 | 2006-06-29 | Tanaka Kikinzoku Kogyo K.K. | Combustion catalyst for treating diesel exhaust gas and method for treating diesel exhaust gas |
| JP2007083224A (en) * | 2005-08-23 | 2007-04-05 | Mazda Motor Corp | Diesel particulate filter |
| JP2008105027A (en) * | 2006-10-23 | 2008-05-08 | Haldor Topsoe As | Method and apparatus for purification of exhaust gas from compression ignition engine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5687430A (en) * | 1979-12-19 | 1981-07-16 | Toyota Central Res & Dev Lab Inc | Catalyst for purifying exhaust gas |
| JPS62241554A (en) * | 1986-04-11 | 1987-10-22 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas and preparation thereof |
| JPS6467256A (en) * | 1987-09-08 | 1989-03-13 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPH0558775A (en) * | 1991-09-02 | 1993-03-09 | Fujitsu Ltd | Molecular-beam epitaxy device |
-
1988
- 1988-07-01 JP JP63162563A patent/JPH0214744A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5687430A (en) * | 1979-12-19 | 1981-07-16 | Toyota Central Res & Dev Lab Inc | Catalyst for purifying exhaust gas |
| JPS62241554A (en) * | 1986-04-11 | 1987-10-22 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas and preparation thereof |
| JPS6467256A (en) * | 1987-09-08 | 1989-03-13 | Matsushita Electric Ind Co Ltd | Catalyst for purifying exhaust gas |
| JPH0558775A (en) * | 1991-09-02 | 1993-03-09 | Fujitsu Ltd | Molecular-beam epitaxy device |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100384015B1 (en) * | 2000-12-02 | 2003-05-14 | 현대자동차주식회사 | Improved NOx conversion and thermal durable Pd only three way catalyst |
| JP2002343207A (en) * | 2001-05-18 | 2002-11-29 | Saginomiya Seisakusho Inc | Pressure switch |
| WO2006068022A1 (en) * | 2004-12-20 | 2006-06-29 | Tanaka Kikinzoku Kogyo K.K. | Combustion catalyst for treating diesel exhaust gas and method for treating diesel exhaust gas |
| JPWO2006068022A1 (en) * | 2004-12-20 | 2008-06-12 | 田中貴金属工業株式会社 | Combustion catalyst for diesel exhaust gas treatment and diesel exhaust gas treatment method |
| JP4501012B2 (en) * | 2004-12-20 | 2010-07-14 | 田中貴金属工業株式会社 | Combustion catalyst for diesel exhaust gas treatment and diesel exhaust gas treatment method |
| US7875572B2 (en) | 2004-12-20 | 2011-01-25 | Tanaka Kikinzoku Kogyo K.K. | Combustion catalyst for treating diesel exhaust gas and method for treating diesel exhaust gas |
| JP2007083224A (en) * | 2005-08-23 | 2007-04-05 | Mazda Motor Corp | Diesel particulate filter |
| JP2008105027A (en) * | 2006-10-23 | 2008-05-08 | Haldor Topsoe As | Method and apparatus for purification of exhaust gas from compression ignition engine |
| US8603941B2 (en) | 2006-10-23 | 2013-12-10 | Haldor Topsoe A/S | Method and apparatus for the purification of exhaust gas from a compression ignition engine |
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