JPH03131320A - Nitrogen oxide decomposing catalyst - Google Patents
Nitrogen oxide decomposing catalystInfo
- Publication number
- JPH03131320A JPH03131320A JP1269741A JP26974189A JPH03131320A JP H03131320 A JPH03131320 A JP H03131320A JP 1269741 A JP1269741 A JP 1269741A JP 26974189 A JP26974189 A JP 26974189A JP H03131320 A JPH03131320 A JP H03131320A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- oxide
- nitrogen oxide
- exhaust gas
- fired
- 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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract 3
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000395 magnesium oxide Substances 0.000 abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000292 calcium oxide Substances 0.000 abstract description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- -1 alkaline earth metal salt Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- SFKTYEXKZXBQRQ-UHFFFAOYSA-J thorium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Th+4] SFKTYEXKZXBQRQ-UHFFFAOYSA-J 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分解
本発明は、排ガス中に含まれる窒素酸化物を除去する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION Industrial Application Decomposition The present invention relates to a method for removing nitrogen oxides contained in exhaust gas.
従来の技術
従来排ガス中に含まれる窒素酸化物は、■窒素酸化物を
酸化しアルカリ吸収させる方法、■窒素酸化物をＮＨ３
、Ｒ２、ＣＯ等の還元剤により、Ｎ２とする方法などに
より除去ざ１−
れてきた。これらの方法は■の場合排水処理が必要とな
り、■の場合ＮＨ３等の還元剤が必要であるため処理コ
ストが高く、またこれらとＳＯｘとの反応による塩類生
成による活性低下があるなどの問題を有してきた。また
そのため還元剤を添加することなく窒素酸化物を直接分
解することができる触媒が提案されているが、これらは
活性が低く実用に供し得ないという問題点を有してきた
。Conventional technology Conventionally, nitrogen oxides contained in exhaust gas can be treated by: ■ oxidizing nitrogen oxides and absorbing alkali; ■ converting nitrogen oxides to NH3
It has been attempted to be removed by reducing agents such as , R2, and CO, and by using N2. These methods require wastewater treatment in the case of (2), and require reducing agents such as NH3 in the case of (2), resulting in high treatment costs and problems such as a decrease in activity due to the formation of salts due to the reaction between these and SOx. I have had it. For this reason, catalysts that can directly decompose nitrogen oxides without adding a reducing agent have been proposed, but these have had the problem of low activity and cannot be put to practical use.
発期が解決Ｕよ立と丈５問題点
本発明は、上記の欠点を解決し、還元剤を添加すること
なく窒素酸化物を高効率に還元分解することができる触
媒にかかるものである。The present invention solves the above-mentioned drawbacks and relates to a catalyst that can reductively decompose nitrogen oxides with high efficiency without adding a reducing agent.
朋題点な解決ｔゑだぬの手段
本発明にかかる触媒は、排ガス中に含有する窒素酸化物
を
（ａ）アルカリ土類金属酸化物と
（ｂ）Ｒｕ、Ｒ１１、Ｐｄ、Ａｇ、Ｐｔ、Ａｕから選択
される１種以上の金属もしくは、金属酸化物とからなる
触媒と接触させ、窒素酸化物を２−
Ｎ２と０２に分解することができる触媒である。Means for solving the problem The catalyst according to the present invention converts nitrogen oxides contained in exhaust gas into (a) alkaline earth metal oxides and (b) Ru, R11, Pd, Ag, Pt, Au. This is a catalyst that can decompose nitrogen oxides into 2-N2 and 02 when brought into contact with a catalyst consisting of one or more metals or metal oxides selected from the following.
本触媒は（ａ）と（ｂ）から選択される触媒成分もしく
はそれらの前駆体を用いて、公知の方法により調整する
ことができる。The present catalyst can be prepared by a known method using a catalyst component selected from (a) and (b) or a precursor thereof.
例えば
（１）アルカリ土類金属酸化物（マグネシア、カルシア
、酸化ストロンチウムなど）を任意の成形方法（押出成
形、打錠成形、球状成形など）により成形しその後３０
０°Ｃ〜１０００℃の温度条件で焼成し、これを（ｂ）
群から選択される金属塩水溶液浸漬し、乾燥後３００℃
〜８００℃の温度条件で焼成する。さらに必要に応じて
還元もしくは不活性雰囲気中で焼成焼成する。For example, (1) an alkaline earth metal oxide (magnesia, calcia, strontium oxide, etc.) is molded by any molding method (extrusion molding, tablet molding, spherical molding, etc.) and then
Fired at a temperature of 0°C to 1000°C, this is (b)
Immerse in an aqueous solution of a metal salt selected from the group and dry at 300°C.
Calcinate at a temperature of ~800°C. Further, if necessary, firing is performed in a reducing or inert atmosphere.
（２）アルカリ土類金属塩にアルカリ（アンモニア、水
酸化すトリウムなと）など沈澱剤を加え沈澱を生成し、
これを乾燥し、その後３００℃〜１０００℃の温度条件
で焼成し粉砕し、任意の成形方法（押出成形、打錠成形
、球状底３−
形など）により成形し、さらに必要に応じて３００℃〜
８００℃の温度条件で焼成し、これを（ｂ）群から選択
される金属塩水溶液に浸漬し、乾燥後３００℃〜８００
℃の温度条件で焼成する。さらに必要に応じて還元もし
くは不活性雰囲気中で焼成する。(2) A precipitant such as alkali (ammonia, thorium hydroxide, etc.) is added to the alkaline earth metal salt to form a precipitate.
This is dried, then fired and pulverized at a temperature of 300°C to 1000°C, molded by any molding method (extrusion molding, tablet molding, spherical bottom shape, etc.), and further heated to 300°C as necessary. ~
Calcined at a temperature of 800°C, immersed in an aqueous solution of a metal salt selected from group (b), and dried at a temperature of 300°C to 800°C.
Fired at a temperature of ℃. Further, if necessary, it is fired in a reducing or inert atmosphere.
（３）アルカリ土類金属塩、及び（ｂ）群から選択され
る金属塩を水などに溶解し、これにアルカリ（アンモニ
ア、水酸化すｌ・リウムなと）など沈澱剤を加え、沈澱
を生成し、これを乾燥し、その後３００℃〜８００°Ｃ
の温度条件で焼成する。これを粉砕し任意の成形方法（
押出成形、打錠成形、球状成形など）により成形し、さ
らに必要に応じて３００℃〜８００°Ｃの温度条件で焼
成する。さらに場合によってはこれを還元もしくは不活
性雰囲気中で焼成してもよい。(3) An alkaline earth metal salt and a metal salt selected from group (b) are dissolved in water, etc., and a precipitant such as an alkali (ammonia, sulfur/lium hydroxide, etc.) is added thereto to precipitate. produced, dried, and then heated at 300°C to 800°C
Fired under the following temperature conditions. Grind this and use any molding method (
(extrusion molding, tablet molding, spherical molding, etc.) and, if necessary, calcining at a temperature of 300°C to 800°C. Further, depending on the case, this may be fired in a reducing or inert atmosphere.
これらの方法は本発明触媒の調製方法を例示したもので
あり、これに特定されるものではなく、触媒成分が同じ
ものであれば同等の効４−
果が得られる。These methods are illustrative of methods for preparing the catalyst of the present invention, and are not limited thereto, and equivalent effects can be obtained if the catalyst components are the same.
本発明に用いることができる（ａ）群の金属酸化物は酸
化マグネシウム、酸化カルシウム、酸化ストロンチウム
であり、（ａ）群の前駆体は水酸化マグネシウム、水酸
化カルシウム、水酸化ストロンチウム、水酸化バリウム
などの水酸化物、硝酸マグネシウム、硝酸カルシウム、
硝酸ストロンチウム、硝酸バリウムなど水溶性塩などで
ある。なおこれらの沈澱剤としては炭酸塩あるいは水酸
化ナトリウムなどのアルカリを挙げることができる。The metal oxides of group (a) that can be used in the present invention are magnesium oxide, calcium oxide, and strontium oxide, and the precursors of group (a) are magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. hydroxides, magnesium nitrate, calcium nitrate, etc.
These include water-soluble salts such as strontium nitrate and barium nitrate. Note that examples of these precipitants include carbonates and alkalis such as sodium hydroxide.
また（ｂ）群の金属もしくは金属酸化物としては、前駆
体を用いることが好ましく塩化ルテニウム、硝酸ロジウ
ム、塩化パラジウム、硝酸銀、塩化白金酸、塩化金酸な
どの水溶性塩を挙げることができる。またこれらの成分
以外にチタニア、アルミナ、シリカなどの公知の担体成
分、粘土などの成形助剤成分、ガラスセンイなどの補強
剤を添加してもよい。Further, as the metal or metal oxide of group (b), it is preferable to use a precursor, and examples thereof include water-soluble salts such as ruthenium chloride, rhodium nitrate, palladium chloride, silver nitrate, chloroplatinic acid, and chloroauric acid. In addition to these components, known carrier components such as titania, alumina, and silica, molding aid components such as clay, and reinforcing agents such as glass fiber may be added.
しかしこれらの成分の総量は触媒成分中の５５− ０％以下とすることが好ましい。However, the total amount of these components is 55- It is preferably 0% or less.
本発明にかかる触媒は、（ａ）群と、（ｂ）群からなる
がこれらの好ましい組成比は重量比で（ａ）群：（ｂ）
群が９０〜９９．９９： １０〜０．０１、より好まし
くは９５〜９９．９：５〜０．１である。本発明者らは
ＮＯｘの接触分解の素反応が
２ＮＯ＋２ｅ −＋ ２ＮＯ−’ （１）２
ＮＯ−’ → Ｎ２＋２０−１（２）２０−’
−＋ ０２＋２ｅ （３）０２
→ ０２↑ （４）からなり、（ａ）群は（
１）の反応に、（ｂ）群は（２Ｘ３Ｘ４）の反応に、関
与していると考えている。しかしこれらのそれぞれの反
応速度への寄与は定かではないが、これらの重量比にお
いて、最も分解活性を示す結果となった。The catalyst according to the present invention consists of group (a) and group (b), and the preferred composition ratio of these is group (a): group (b) in terms of weight ratio.
The group is 90-99.99: 10-0.01, more preferably 95-99.9: 5-0.1. The present inventors found that the elementary reaction of catalytic decomposition of NOx is 2NO+2e −+ 2NO−′ (1)2
NO-' → N2+20-1(2)20-'
-+ 02+2e (3)02
→ 02↑ Consists of (4), and group (a) is (
It is believed that group (b) is involved in the reaction (2X3X4) in the reaction 1). However, although the contribution of each of these to the reaction rate is unclear, the results showed that the decomposition activity was highest at these weight ratios.
本発明の触媒が高い分解活性を示す温度は３００°Ｃ〜
８００℃である。また好ましい温度４００〜６００℃で
ある。この温度において本発明触媒は、好ましくは５Ｖ
＝５００〜５６−
０００において使用することができる。The temperature at which the catalyst of the present invention exhibits high decomposition activity is 300°C ~
The temperature is 800°C. Further, the preferred temperature is 400 to 600°C. At this temperature, the catalyst of the present invention preferably has a voltage of 5 V
=500 to 56-000.
光肌の効果
以上の様に本発明によれば（ａ）群と（ｂ）群より選ば
れた触媒成分を含有する触媒を用いることによって、排
ガス温度が３００℃〜８００℃の温度域において窒素酸
化物を還元剤を添加することなく分解除去することが可
能となったのである。As described above, according to the present invention, by using a catalyst containing catalyst components selected from groups (a) and (b), nitrogen is reduced in the exhaust gas temperature range of 300°C to 800°C. This made it possible to decompose and remove oxides without adding a reducing agent.
以下に実施例とともに参考例を挙げて本発明を説明する
が、本発明はこれらの実施例により何ら限定されるもの
ではない。The present invention will be explained below by giving reference examples together with Examples, but the present invention is not limited to these Examples in any way.
実施例１゜
硝酸マグネシウムを酸化物基準で９０ｇＰＰ量しこれを
１見のイオン交換水中に溶解した。Example 1 Magnesium nitrate was dissolved in an amount of 90 g PP (based on oxide) in ion-exchanged water.
この水溶液中に充分な撹拌を行ないながら、炭酸ソーダ
をｐＨ７，０となるまで添加し、中和反応を終了した。Sodium carbonate was added to this aqueous solution with sufficient stirring until the pH reached 7.0 to complete the neutralization reaction.
（中和時間１時間）その後３０分熟成後ろ過水洗を行な
い１００°Ｃて１８時間乾燥後５００℃３時間焼成した
。(Neutralization time: 1 hour) Thereafter, the mixture was aged for 30 minutes, washed with water, dried at 100°C for 18 hours, and then fired at 500°C for 3 hours.
この焼成物をスクリーンが０．５ｍｍφである７−
サンプルミルにて粉砕した。この粉砕物を５０ｇ、水２
００Ｉｌ＋ｕ中に投入し充分撹拌を行なったスラリー中
に空隙率８１％、ピッチ４ｍｍのセラミックファイバー
製コルゲート状ハニカムを浸漬し、ＭｇＯを該ハニカム
に担持した。その担持率は１４３％であった。これを常
温通風乾燥後１００°Ｃ１８時間乾燥した。This fired product was pulverized using a 7-sample mill with a screen of 0.5 mmφ. 50g of this crushed material, 22g of water
A corrugated honeycomb made of ceramic fibers with a porosity of 81% and a pitch of 4 mm was immersed in the slurry that had been poured into 00Il+u and sufficiently stirred, and MgO was supported on the honeycomb. The loading rate was 143%. This was air-dried at room temperature and then dried at 100°C for 18 hours.
この乾燥物を塩化パラジウム水溶液（ＰｄＯとして３３
ｇ／Ｑ）中に浸漬し、常温通風乾燥後１００℃１８時間
乾燥し、５００°Ｃ３時間焼成した。この触媒中のＰｄ
Ｏ：ＭｇＯは重量基準で１．００：１００であった。This dried material was dissolved in a palladium chloride aqueous solution (33% as PdO).
g/Q), air-dried at room temperature, dried at 100°C for 18 hours, and fired at 500°C for 3 hours. Pd in this catalyst
O:MgO was 1.00:100 on a weight basis.
実施例２、
硝酸アルミニウムを酸化物基準で２５ｇ秤量しこれを１
見のイオン交換水中に溶解した。Example 2: Weighed 25g of aluminum nitrate on an oxide basis and added 1
Dissolved in ion-exchanged water.
この水溶液中に充分な撹拌を行ないながら、アンモニア
を吹き込みｐＨ７，０として中和反応を終了した。（中
和時間１時間）その後３０分熟成後ろ過水洗を行ない１
００°Ｃて１８時間乾燥後５００℃３時間焼成した。こ
の＝８−
焼成物をスクリーンが０．５ｍｍφであるサンプルミル
にて粉砕した。この粉砕物を２５ｇと水酸化マグネシウ
ムを６５０°Ｃ１時間焼成したマグネシア（比表面積５
３η？／ｇ）７５ｇを水４００截に投入し、遊星ミルに
て３０分分間式粉砕を行った。このスラリー中に空隙率
８１％、ピッチ４ｍｍのセラミックファイバー製コルゲ
ート状ハニカムを浸漬し、Ａｌ２Ｏ３に担持されたＭｇ
Ｏを該ハニカムに担持した。その担持率は１５６％であ
った。以下実施例１と同様にして触媒を得た。この触媒
中のＰｄＯ：ＭｇＯは重量基準で１．００：１００であ
った。Ammonia was blown into this aqueous solution with sufficient stirring to adjust the pH to 7.0 and complete the neutralization reaction. (Neutralization time: 1 hour) After aging for 30 minutes, rinse with water.1
After drying at 00°C for 18 hours, it was fired at 500°C for 3 hours. This =8- fired product was pulverized in a sample mill with a screen of 0.5 mmφ. Magnesia (specific surface area: 5
3η? /g) was added to 400 g of water and pulverized for 30 minutes in a planetary mill. A ceramic fiber corrugated honeycomb with a porosity of 81% and a pitch of 4 mm was immersed in this slurry, and Mg supported on Al2O3 was
O was supported on the honeycomb. The loading rate was 156%. Thereafter, a catalyst was obtained in the same manner as in Example 1. The PdO:MgO ratio in this catalyst was 1.00:100 on a weight basis.
実施例３゜
実施例２の方法において、硝酸マグネシウムに替えて硝
酸カルシウムを用いて触媒を得た。Example 3 A catalyst was obtained using the method of Example 2, but using calcium nitrate instead of magnesium nitrate.
この触媒中のＰｄＯ：ＣａＯは重量基準で０．９５：１
００であった。PdO:CaO in this catalyst is 0.95:1 on a weight basis
It was 00.
実施例４゜ 実施例２の方法において、塩化パラジウム水９− 溶液濃度なＰｄＯとして１６５ｇ／見とした。Example 4゜ In the method of Example 2, palladium chloride water 9- The solution concentration of PdO was 165 g/view.
この時触媒中のＰｄＯ：ＭｇＯは重量基準で４、δ０：
１００であった。At this time, PdO:MgO in the catalyst is 4 on a weight basis, δ0:
It was 100.
実施例５゜
実施例２の方法において、塩化パラジウム水溶液に替え
て塩化白金水溶液を用いた。この時ｐｔ濃度を１６ｇ／
見（実施例５５−１）３３／見（実施例５５−２）６６
／見（実施例５−３）とした。この時触媒中のＰｔ：Ｍ
ｇｏは重量基準でそれぞれ０．４６： １００゜０．９
８：Ｉｏｏ、２．０１ ：１００であった。Example 5 In the method of Example 2, a platinum chloride aqueous solution was used instead of the palladium chloride aqueous solution. At this time, the pt concentration was set to 16g/
See (Example 55-1) 33/See (Example 55-2) 66
/view (Example 5-3). At this time, Pt in the catalyst: M
go is 0.46: 100°0.9 on a weight basis, respectively.
8:Ioo, 2.01:100.
実施例６゜
実施例２の方法において塩化パラジウム酸水溶液に替え
て塩化ルテニウム水溶液（Ｒｕとして３３ ｇ／Ｑ）を
用いた。この時触媒中のＲｕ：ＭｇＯは重量基準て０．
９７：１００であった。Example 6 In the method of Example 2, a ruthenium chloride aqueous solution (33 g/Q as Ru) was used in place of the chloropalladate aqueous solution. At this time, Ru:MgO in the catalyst is 0.0% by weight.
It was 97:100.
実施例７゜
実施例２の方法において塩化パラジウム水溶１０−
液に替えて硝酸銀水溶液（Ａｇ２０として７１ ｇｚ４
Ｑ、）を用いた。この時触媒中のＡｇ２Ｏ：ＭｇＯは重
量基準で２．４３：１００であった。Example 7 In the method of Example 2, an aqueous solution of silver nitrate (71 gz4 as Ag20) was used instead of an aqueous solution of palladium chloride.
Q,) was used. At this time, the ratio of Ag2O:MgO in the catalyst was 2.43:100 on a weight basis.
実施例８゜
実施例２の方法において塩化パラジウムに替えて塩化金
酸水溶液（Ａｕとして３３ｇ／Ｑ、）を用いた。この時
触媒中のＡｕ：ＭｇＯは重量基準て０．９５：１００て
あった。Example 8 In the method of Example 2, an aqueous chloroauric acid solution (33 g/Q as Au) was used in place of palladium chloride. At this time, the ratio of Au:MgO in the catalyst was 0.95:100 on a weight basis.
実施例９゜
１産化学製スノーテックス０とメタチタン酸ゾル（メタ
チタン酸を硝酸により解膠したもの）とを酸化物換算で
１２．５ｇ、１２．５ｇ秤量し、充分混合した後１００
℃１８時間乾燥し７００℃３時間焼成した。この焼成物
を実施例２同様に粉砕した。この粉砕物２５ｇと塩基性
炭酸ストロンチウ１１を６５０℃１時間焼成したカルシ
ア（比表面積３８ｔ＋ｒ／ｇ）７５ｇを用い以下実施例
２と同様にして触媒を得た。この時触媒中のＰｄＯ：Ｓ
ｒＯは重１１−
量基準て１．０５：１００てあった。Example 9 Weighed 12.5 g of 12.5 g of 12.5 g of oxide equivalent of Snowtex 0 manufactured by Sankagaku Co., Ltd. and metatitanic acid sol (metatatitanic acid peptized with nitric acid), and mixed them thoroughly.
It was dried for 18 hours at 700°C and fired for 3 hours at 700°C. This fired product was pulverized in the same manner as in Example 2. A catalyst was obtained in the same manner as in Example 2 using 25 g of this pulverized material and 75 g of calcia (specific surface area: 38 t+r/g) obtained by calcining basic strontium carbonate 11 at 650° C. for 1 hour. At this time, PdO:S in the catalyst
rO was 1.05:100 based on weight.
実施例１０゜
実施例９の方法において塩化パラジウムに替えて塩化白
金酸水溶液を用いた。この時触媒中のＰｔ：ＳｒＯは重
量基準で０．９４：１００であった。Example 10 In the method of Example 9, an aqueous chloroplatinic acid solution was used in place of palladium chloride. At this time, the ratio of Pt:SrO in the catalyst was 0.94:100 on a weight basis.
実施例１１゜
実施例９の方法において塩化パラジウムに替えて硝酸ロ
ジウム水溶液を用いた。この時触媒中のＲｈ：ＳｒＯは
重量基準で０．９５：１００であった。Example 11 In the method of Example 9, an aqueous rhodium nitrate solution was used instead of palladium chloride. At this time, Rh:SrO in the catalyst was 0.95:100 on a weight basis.
実施例１２゜
シリンゾル（１産化学製スノーテックスＯ）と硝酸バリ
ウムとを酸化物換算でそれぞれ１２．５ｇ、ｇ秤量し、
充分混合した後１００°Ｃ乾燥し７００°Ｃ３時間焼成
した。以下実施例９と同様にして触媒を得た。この時触
媒中のＰｄＯ：ＢａＯは重量基準で１．１０：１００で
あった。Example 12 Weighed 12.5g of syrinsol (Snowtex O manufactured by Ichisan Kagaku) and barium nitrate in terms of oxide, and
After thorough mixing, the mixture was dried at 100°C and fired at 700°C for 3 hours. Thereafter, a catalyst was obtained in the same manner as in Example 9. At this time, the ratio of PdO:BaO in the catalyst was 1.10:100 on a weight basis.
実施例１３゜
１２一
実施例４によって得た触媒をＮ２ Ｎ２ （１：１）
の還元ガスで４００℃１時間処理した。Example 13゜12-The catalyst obtained in Example 4 was mixed with N2 N2 (1:1).
was treated with reducing gas at 400°C for 1 hour.
参考例１
モーピル石油製ＺＳＭ−５，５０ｇを０． ＩＮ濃度の
酢酸鋼溶液に浸漬し、還流器付圧ソロフラスコ中で９０
８Ｃ〜１００℃で１２時間撹拌し、ろ過した。得られた
ケーキを用いて同様の操作を繰返し置換量を４．８％（
重量）とした。以下実施例１と同様の操作により触媒を
得た。Reference Example 1 50g of ZSM-5 manufactured by Mopil Oil Co., Ltd. Immersed in a steel acetate solution with a concentration of
Stir at 8C to 100C for 12 hours and filter. Using the obtained cake, the same operation was repeated until the amount of substitution was 4.8% (
weight). A catalyst was obtained by the same operation as in Example 1.
実施例１〜１３、参考例１により得られた触媒を用いて
以下の試験条件にて試験を行った。Tests were conducted using the catalysts obtained in Examples 1 to 13 and Reference Example 1 under the following test conditions.
（１）ガス組成
Ｎｏ １％
Ｈｅ バランス
（２） ＳＶ １０００
（３）反応温度 ３００．４００．５００℃試験結果
を第１表に示した。(1) Gas composition No. 1% He balance (2) SV 1000 (3) Reaction temperature 300.400.500°C The test results are shown in Table 1.
なお第１表中の値はＮ２への転換率を表している。Note that the values in Table 1 represent the conversion rate to N2.
１３− 第１表 ４13- Table 1 4
Claims (1)
解除去する触媒において （ａ）アルカリ土類金属酸化物 （ｂ）Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｐｔ、Ａｕから選択さ
れる１種以上の金属もしくは、金属酸化物とからなるこ
とを特徴とする窒素酸化物分解触媒[Claims] A catalyst that decomposes and removes nitrogen oxides by contacting with a gas containing nitrogen oxides (a) alkaline earth metal oxides (b) Ru, Rh, Pd, Ag, Pt, Au A nitrogen oxide decomposition catalyst comprising one or more metals or metal oxides selected from
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1269741A JPH03131320A (en) | 1989-10-16 | 1989-10-16 | Nitrogen oxide decomposing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1269741A JPH03131320A (en) | 1989-10-16 | 1989-10-16 | Nitrogen oxide decomposing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03131320A true JPH03131320A (en) | 1991-06-04 |
Family
ID=17476514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1269741A Pending JPH03131320A (en) | 1989-10-16 | 1989-10-16 | Nitrogen oxide decomposing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03131320A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03221143A (en) * | 1990-01-26 | 1991-09-30 | Agency Of Ind Science & Technol | Exhaust gas purifying catalyst |
| US5665321A (en) * | 1994-02-04 | 1997-09-09 | Goal Line Environmental Technologies | Process for the reaction and absorption of gaseous air pollutants, apparatus therefor and method of making same |
-
1989
- 1989-10-16 JP JP1269741A patent/JPH03131320A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03221143A (en) * | 1990-01-26 | 1991-09-30 | Agency Of Ind Science & Technol | Exhaust gas purifying catalyst |
| US5665321A (en) * | 1994-02-04 | 1997-09-09 | Goal Line Environmental Technologies | Process for the reaction and absorption of gaseous air pollutants, apparatus therefor and method of making same |
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