JPH02122831A - Catalyst for removal of nitrogen oxide - Google Patents
Catalyst for removal of nitrogen oxideInfo
- Publication number
- JPH02122831A JPH02122831A JP63277693A JP27769388A JPH02122831A JP H02122831 A JPH02122831 A JP H02122831A JP 63277693 A JP63277693 A JP 63277693A JP 27769388 A JP27769388 A JP 27769388A JP H02122831 A JPH02122831 A JP H02122831A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- nitrate
- oxide
- group
- baked
- 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 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract 2
- 229910052697 platinum Inorganic materials 0.000 claims abstract 2
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract 2
- 229910052709 silver Inorganic materials 0.000 claims abstract 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 17
- 150000003839 salts Chemical class 0.000 abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 238000003776 cleavage reaction Methods 0.000 abstract 1
- 238000006894 reductive elimination reaction Methods 0.000 abstract 1
- 230000007017 scission Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- -1 alkali metal salt Chemical class 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
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 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
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NNIYFVYSVUWTOA-UHFFFAOYSA-N copper hydrochloride Chemical compound Cl.[Cu] NNIYFVYSVUWTOA-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011068 loading method Methods 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 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
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 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
- YPFBRNLUIFQCQL-UHFFFAOYSA-K tribromomolybdenum Chemical compound Br[Mo](Br)Br YPFBRNLUIFQCQL-UHFFFAOYSA-K 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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Ｑ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ＮＨ，
、Ｎ２、ＣＯ等の還元剤により、Ｎ２とする方法などに
より除去されてきた。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、特にＮＨ３を還元剤とする場合
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ＣＯを還元剤とする場合上
記問題点を有しないが、酸素の共存下ではＣＯが０２と
反応し、効率的に還元反応が起こらないという問題点が
あった。Conventional Q technology Conventionally, nitrogen oxides contained in exhaust gas are treated by: ■ oxidizing nitrogen oxides and absorbing alkali, ■ converting nitrogen oxides to NH,
, N2, CO, and other reducing agents. These methods require wastewater treatment in the case of ①, and require a reducing agent such as NH3 in the case of ①, resulting in high treatment costs.In particular, when NH3 is used as the reducing agent, activity decreases due to salt formation due to reaction with SOx. There have been some problems. Further, when CO is used as a reducing agent, the above-mentioned problems do not occur, but there is a problem that CO reacts with 02 in the presence of oxygen, and the reduction reaction does not occur efficiently.
発器が解決旦孟ｊ上す名利照点
本発明は、上記の欠点を解決し、還元剤ＣＯを添加し窒
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。SUMMARY OF THE INVENTION The present invention is directed to a catalyst that solves the above-mentioned drawbacks and is capable of highly efficiently reducing and decomposing nitrogen oxides by adding a reducing agent CO.
１０ 六 ′ １ の二
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）アルカリ金属及びもしくはアルカリ土類金属酸化
物
（ｂ）Ｃｏ３０ａ、Ｃｕ２Ｏ、Ｃｒ２Ｏ３、Ｍｎ２Ｏ３
、Ｎｉ０１ＰｂＯ，Ｂｉ２Ｏ３、ＭｏＯ２から選択され
る１種以上の金属酸化物及び（Ｃ）Ｒｕ％Ｒｈ、Ｐｄ、
Ａｇ５ＰｔＳＡｕ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ＣＯの共存下で接触さ
せ、窒素酸化物をＮ２とＣＯ２に還元分解することがで
きる触媒である。10 6' 1-2 The catalyst according to the present invention converts nitrogen oxides contained in exhaust gas into (a) alkali metal and/or alkaline earth metal oxides (b) Co30a, Cu2O, Cr2O3, Mn2O3
, one or more metal oxides selected from Ni01PbO, Bi2O3, MoO2, and (C) Ru%Rh, Pd,
This is a catalyst that can reduce and decompose nitrogen oxides into N2 and CO2 by bringing them into contact with a catalyst made of one or more metals selected from Ag5PtSAu or metal oxides in the coexistence of CO.
本触媒は（ａ）（ｂ）と（Ｃ）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), (b) and (C) 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）と（ｂ）群から選択される
酸化物を予め混合し、任意の成形方法（押出成形、打錠
成形、球状成形など）により成形しその後３００℃〜８
００℃の温度条件で焼成し、これを（Ｃ）群から選択さ
れる金属及びもしくはアルカリ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雰囲気中で焼成する。For example, (1) an alkaline earth metal oxide (magnesia, calcia, strontium oxide, etc.) and an oxide selected from group (b) are mixed in advance, and any molding method (extrusion molding, tablet molding, spherical molding, etc.) is used. ) and then molded at 300℃~8
Calcined at a temperature of 00°C, immersed in a metal and/or alkali metal salt aqueous solution selected from group (C),
After drying, it is fired at a temperature of 300°C to 800°C. Further, if necessary, it is fired in a reducing atmosphere.
（２）アルカリ土類金属塩と（ｂ）群から選択される金
属の塩を水などに溶解しこれにアルカリ（アンモニア、
水酸化ナトリウムなど）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℃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
、球状成形など）により成形し、さらに必要に応じて３
００℃〜８００℃の温度条件で焼成し、これを（Ｃ）群
から選択される金属及びもしくはアルカリ金属塩水溶液
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雰囲気中で焼成する。(2) Dissolve an alkaline earth metal salt and a salt of a metal selected from group (b) in water, etc., and add alkali (ammonia,
Add a precipitant (such as sodium hydroxide) to form a precipitate, dry this, then sinter and crush at a temperature of 300°C to 800°C. ), and further 3 as necessary.
It is fired at a temperature of 00°C to 800°C, immersed in an aqueous solution of a metal and/or alkali metal salt selected from group (C), dried, and then fired at a temperature of 300°C to 800°C. Further, if necessary, it is fired in a reducing atmosphere.
（３）アルカリ金属塩、（ｂ）群から選択される金属塩
及び（Ｃ）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、水酸化ナトリウムなど）
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℃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℃〜８０
０℃の温度条件で焼成する。さらに場合によってはこれ
を還元雰囲気中で焼成してもよい。(3) Dissolving an alkali metal salt, a metal salt selected from group (b), and a metal salt selected from group (C) in water or the like,
Add to this an alkali (ammonia, sodium hydroxide, etc.)
A precipitant such as the like is added to form a precipitate, which is dried and then calcined at a temperature of 300°C to 800°C. This is crushed and molded by any molding method (extrusion molding, tablet molding, spherical molding, etc.), and further heated to 300°C to 800°C as necessary.
Fired at a temperature of 0°C. Furthermore, depending on the case, this may be fired in a reducing atmosphere.
これらの方法は本発明触媒の調整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
化カルシラＪい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が好ましい。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 strontium oxide. Hydroxides such as barium, magnesium nitrate, calcium nitrate,
These include water-soluble salts such as strontium nitrate and barium nitrate. As the precipitant, carbonate or alkali such as sodium hydroxide is preferable.
また本発明に用いることができる（ｂ）群の金属酸化物
はＣｏ３Ｏ４、Ｃｕ２Ｏ、Ｃｒ２Ｏ３Ｍｎ２Ｏ３、Ｎｉ
０％ＰｂＯ１Ｂｉ２０３、ＭｏＯ２であり、好ましい原
料である（ｂ）群の前駆体としては硝酸第１銅、硝酸第
１クロム、硝酸コバルト、硝酸マンガン、硝酸ニッケル
、硝酸鉛、硝酸ビスマス、モリブデン酸アンモニウムな
どの水溶性塩を挙げることができる。さらに（Ｃ）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。しかしこれらの成分の総量は触媒成分中の５０％
以下とすることが好ましい。Group (b) metal oxides that can be used in the present invention include Co3O4, Cu2O, Cr2O3Mn2O3, Ni
0% PbO1Bi203, MoO2, and the precursors of group (b), which are preferred raw materials, include cuprous nitrate, chromium nitrate, cobalt nitrate, manganese nitrate, nickel nitrate, lead nitrate, bismuth nitrate, ammonium molybdate, etc. Examples include water-soluble salts of Furthermore, as the metal or metal oxide of group (C), 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. However, the total amount of these components is 50% of the catalyst components.
The following is preferable.
本発明にかかる触媒は、（ａ）群、（ｂ）群及び（Ｃ）
群とからなるがこれらの好ましい組成比は原子比で（ａ
）群：（ｂ）群：（Ｃ）群が９０〜５０：５〜５０：０
．０１〜１０あり、より好ましくは９０〜７５：１０〜
２５：０．１〜５である。本発明者らはＮＯｘのＣＯに
よる還元分解の素反応が
２ＮＯ＋２ｅ ＋ ２ＮＯ（１）２ＮＯ→ Ｎ
、＋２０ （２）２０＋２ＣＯ−＋ Ｃｏ２
＋２ｅ （３）Ｃ０２→ Ｃ０２↑ （４
）
からなり、（ａ）群は（１） （２）の反応に、（ｂ）
群は（３）の反応に、（Ｃ）群は（４）の反応に関与し
ていると考えている。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、これらの原子比において、最も
還元分解活性を示す結果となった。The catalyst according to the present invention comprises group (a), group (b) and (C).
The preferred composition ratio of these groups is (a
) group: (b) group: (C) group is 90-50:5-50:0
．． 01-10, more preferably 90-75:10
25:0.1-5. The present inventors found that the elementary reaction of reductive decomposition of NOx by CO is 2NO+2e + 2NO(1)2NO→N
, +20 (2)20+2CO-+ Co2
+2e (3) C02→ C02↑ (4
), and group (a) responds to reactions (1) and (2), and group (b)
We believe that group (C) is involved in reaction (3) and group (C) is involved in reaction (4). Although the contribution of each of these to the reaction rate is unclear, the results showed the highest reductive decomposition activity at these atomic ratios.
本発明の触媒が高い還元分解活性を示す温度は３００℃
〜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、５Ｖ＝５００
〜５００００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 reductive decomposition activity is 300°C.
~800°C. Also preferred temperature is 400-600℃
It is. At this temperature, the catalyst of the present invention has a voltage of 5V=500
~50,000 can be used.
発器の効果
以上の様に本発明によれば（ａ）群（ｂ）群及び（Ｃ）
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ＣＯを添加し、還元分解除去す
ることが可能となったのである。As described above, according to the present invention, group (a), group (b), and group (C)
By using a catalyst containing a catalyst component selected from the group, it has become possible to reduce and decompose nitrogen oxides in the exhaust gas temperature range of 300°C to 800°C by adding a reducing agent CO. be.
以下に実施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 described below with reference to Examples, but the present invention is in no way limited by these Examples.
実施例１゜
硝酸マグネシウム、硝酸コバルトを各々酸化物基準で９
０ｇ、９ｇ秤量しこれを１見のイオン交換水中に溶解し
た。この水溶液中に充分な撹拌を行ないながら、炭酸ソ
ーダ水溶液をｐＨ７，０となるまで添加し、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１００℃で１８時間乾燥後５００℃３時間
焼成した。この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５０ｇ、水
２００ｍＵ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−Ｃｏ３Ｏ４を
該ハニカムに担持した。その担持率は１５９％であった
。Example 1゜ Magnesium nitrate and cobalt nitrate were each 9% on an oxide basis.
0g and 9g were weighed and dissolved in 1 amount of ion-exchanged water. An aqueous sodium carbonate solution was added to this aqueous solution with sufficient stirring until the pH reached 7.0 to complete the neutralization reaction. (Neutralization time: 1 hour) Thereafter, the mixture was aged for 30 minutes, washed with water, dried at 100°C for 18 hours, and then calcined at 500°C for 3 hours. This fired product was pulverized using a sample mill with a screen of 0.5 mmφ. A corrugated honeycomb made of ceramic fibers with a porosity of 81% and a pitch of 4 mm was immersed in a slurry in which 50 g of this pulverized material was poured into 200 mU of water and sufficiently stirred, and MgO--Co3O4 was supported on the honeycomb. The loading rate was 159%.
これを常温通風乾燥後１００℃１８時間乾燥した。この
乾燥物を塩化金酸水溶液（Ａｕとして３３ｇ／見）中に
浸漬し、常温通風乾燥後１００℃１８時間乾燥し、５０
０℃３時間焼成した。This was air-dried at room temperature and then dried at 100° C. for 18 hours. This dried product was immersed in a chloroauric acid aqueous solution (33 g/application as Au), dried with ventilation at room temperature, and then dried at 100°C for 18 hours.
It was baked at 0°C for 3 hours.
実施例２゜
実施例１の方法において、硝酸マグネシウム、硝酸コバ
ルトを酸化物基準で各々７５ｇと２４ｇ（実施例２−１
） 、５０：４９ （実施例２−２）とした。Example 2 In the method of Example 1, magnesium nitrate and cobalt nitrate were added to 75 g and 24 g, respectively, on an oxide basis (Example 2-1).
), 50:49 (Example 2-2).
実施例３゜
実施例１の方法において、塩化金酸水溶液濃度をＡｕと
して１６５ｇ／込とした。Example 3 In the method of Example 1, the concentration of the chloroauric acid aqueous solution was set to 165 g/containing Au.
実施例４゜
実施例１の方法において、塩化金酸水溶ｉαに替えて塩
化白金酸水溶液（Ｐｔとして３３ｇ／免）を用いた。Example 4 In the method of Example 1, an aqueous chloroplatinic acid solution (33 g/min as Pt) was used in place of the aqueous chloroauric acid iα.
実施例５゜
実施例１の方法において、塩化金酸水溶液に替えて塩化
ルテニウム水ｉｔ＆ （Ｒｕとして３３ｇ／免）を用い
た。Example 5 In the method of Example 1, ruthenium chloride water it& (33 g/min as Ru) was used instead of the chloroauric acid aqueous solution.
実施例６゜
実施例１の方法において塩化白金酸水溶液に替えて硝酸
銀水溶液（Ａ ｇ ２０として７１ｇ／免）を用いた。Example 6 In the method of Example 1, a silver nitrate aqueous solution (71 g/min as A g 20) was used in place of the chloroplatinic acid aqueous solution.
実施例７゜
実施例１の方法において硝酸コバルトに替えて塩化第１
銅塩酸水溶液＜ｒａ化物として９ｇ）を中和剤としてア
ンモニアに替えてＮａＯＨを用い、また中和ｐＨを３．
０とした。Example 7゜In the method of Example 1, cobalt chloride was replaced with cobalt nitrate.
Copper hydrochloric acid aqueous solution <9 g as ra compound) was used as a neutralizing agent instead of ammonia with NaOH, and the neutralization pH was adjusted to 3.
It was set to 0.
実施例８゜
実施例１の方法において硝酸コバルトに替えて硝酸第１
クロム水溶液（酸化物として９ｇ）を用いｐ）（を５．
５とした。Example 8゜In the method of Example 1, nitric acid nitrate was used instead of cobalt nitrate.
Using a chromium aqueous solution (9 g as oxide) p) (5.
I gave it a 5.
実施例肌
実施例４の方法において硝酸コバルトに替えて硝酸マン
ガンを用い、中和時に空気酸化を行ない中和ｐＨを８．
５とした。Example Skin In the method of Example 4, manganese nitrate was used instead of cobalt nitrate, air oxidation was performed during neutralization, and the neutralization pH was adjusted to 8.
I gave it a 5.
実施例１０゜
実施例４の方法において硝酸コバルトに替えて硝酸ニッ
ケルを用いた。Example 10° Nickel nitrate was used in place of cobalt nitrate in the method of Example 4.
実施例１１゜
実施例４の方法において硝酸コバルトに替えて硝酸鉛を
用いた。Example 11 In the method of Example 4, lead nitrate was used instead of cobalt nitrate.
実施例１２゜
実施例４の方法において硝酸コバルト水溶液に替えて硝
酸ビスマス硝酸水溶液を用いた。Example 12 In the method of Example 4, an aqueous solution of bismuth nitrate and nitric acid was used in place of the aqueous cobalt nitrate solution.
実施例１３゜
実施例４の方法において硝酸コバルトに替えて臭化モリ
ブデンを用いた。Example 13 In the method of Example 4, molybdenum bromide was used in place of cobalt nitrate.
実施例１４゜
実施例７の方法において塩化金酸水溶液に替えて硝酸ロ
ジウム水溶液を用いた。Example 14 In the method of Example 7, a rhodium nitrate aqueous solution was used in place of the chloroauric acid aqueous solution.
実施例１５゜
実施例７の方法において塩化金酸水溶液に替えて塩化パ
セジウム水溶液を用いた。Example 15 In the method of Example 7, an aqueous solution of passedium chloride was used in place of the aqueous chloroauric acid solution.
実施例１６゜
実施例４の方法において塩化白金酸水溶液濃度を１６ｇ
／見（実施例１６−１）、６６３／見（実施例１６−２
）とした。Example 16゜In the method of Example 4, the concentration of the chloroplatinic acid aqueous solution was 16 g.
/view (Example 16-1), 663/view (Example 16-2)
).
実施例１７゜
実施例４の方法において硝酸コバルトに替えて硝酸コバ
ルトと硝酸クロムを酸化物基準で４５ｇと４５ｇとした
。Example 17 In the method of Example 4, cobalt nitrate and chromium nitrate were used in place of cobalt nitrate in amounts of 45 g and 45 g on an oxide basis.
実施例１８゜
実施例１の方法において塩化金酸水溶液に替えてＮａを
含有する塩化金酸水溶液（Ａｕとして３３ｇ／見、Ｎａ
として３ｇ／見）を用いた。Example 18 In the method of Example 1, a chloroauric acid aqueous solution containing Na (33 g/view as Au, Na
3 g/view) was used.
実施例１９゜
実施例４によって得た触媒をＮ２−Ｎ２（１：ｌ）の還
元性ガスで４００℃１時間処理した。Example 19 The catalyst obtained in Example 4 was treated with a reducing gas of N2-N2 (1:l) at 400 DEG C. for 1 hour.
実施例２０゜
実施例１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（実施例２Ｏ−１）硝酸ストロンチウム（実
施例２Ｏ−２）硝酸バノウム（実施例２Ｏ−３）を用い
た。Example 20° Calcium nitrate (Example 2O-1), strontium nitrate (Example 2O-2), and vanium nitrate (Example 2O-3) were used in place of magnesium nitrate in the method of Example 1.
実施例１〜１９、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なった。Tests were conducted using the catalysts obtained in Examples 1 to 19 and Reference Example 1 under the following test conditions.
（１）ガス組成
Ｎｏ ２００ｐｐｍ
Ｃｏ ２００ｐｐｍ
０２ ２ ％
Ｈ２０ｌｏ ％
Ｎ２ 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. 200 ppm Co 200 ppm 02 2% H20lo % N2 Balance (2) SV 1000 (3) Reaction temperature 300.400.500°C The test results are shown in Table 1.
Claims (1)
窒素酸化物を還元分解除去する触媒において （ａ）アルカリ金属及びもしくはアルカリ土類金属酸化
物 （ｂ）Ｃｏ＿３Ｏ＿４、Ｃｕ＿２Ｏ、Ｃｒ＿２Ｏ＿３、
Ｍｎ＿２Ｏ＿３、ＮｉＯ、ＰｂＯ、Ｂｉ＿２Ｏ＿３、Ｍ
ｏＯ＿２から選択される１種以上の金属酸化物及び （Ｃ）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Ｃｏによる窒素酸化物還元分解触媒[Claims] Contacting a gas containing nitrogen oxides in the coexistence of CO,
In the catalyst for reducing and decomposing nitrogen oxides, (a) alkali metal and/or alkaline earth metal oxides (b) Co_3O_4, Cu_2O, Cr_2O_3,
Mn_2O_3, NiO, PbO, Bi_2O_3, M
Co characterized by consisting of one or more metal oxides selected from oO_2 and (C) one or more metals or metal oxides selected from Ru, Rh, Pd, Ag, Pt, and Au. Nitrogen oxide reduction decomposition catalyst by
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63277693A JPH02122831A (en) | 1988-11-02 | 1988-11-02 | Catalyst for removal of nitrogen oxide |
| EP89202496A EP0362960A3 (en) | 1988-10-05 | 1989-10-03 | Use of a catalyst composition for denitrization and denitrizing catalysts |
| US07/417,422 US5128305A (en) | 1988-10-05 | 1989-10-05 | Catalyst for denitrization |
| US07/518,560 US5049364A (en) | 1988-10-05 | 1990-06-06 | Methods for denitrization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63277693A JPH02122831A (en) | 1988-11-02 | 1988-11-02 | Catalyst for removal of nitrogen oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02122831A true JPH02122831A (en) | 1990-05-10 |
Family
ID=17586989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63277693A Pending JPH02122831A (en) | 1988-10-05 | 1988-11-02 | Catalyst for removal of nitrogen oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02122831A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4831193A (en) * | 1971-08-27 | 1973-04-24 | ||
| JPS4921379A (en) * | 1972-06-20 | 1974-02-25 | ||
| JPS49122893A (en) * | 1973-03-29 | 1974-11-25 | ||
| JPS508771A (en) * | 1973-05-28 | 1975-01-29 | ||
| JPS52148495A (en) * | 1976-06-04 | 1977-12-09 | Ube Ind Ltd | No# reduction and purification catalyst |
-
1988
- 1988-11-02 JP JP63277693A patent/JPH02122831A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4831193A (en) * | 1971-08-27 | 1973-04-24 | ||
| JPS4921379A (en) * | 1972-06-20 | 1974-02-25 | ||
| JPS49122893A (en) * | 1973-03-29 | 1974-11-25 | ||
| JPS508771A (en) * | 1973-05-28 | 1975-01-29 | ||
| JPS52148495A (en) * | 1976-06-04 | 1977-12-09 | Ube Ind Ltd | No# reduction and purification catalyst |
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