JPH04135641A - Oxidation catalyst - Google Patents
Oxidation catalystInfo
- Publication number
- JPH04135641A JPH04135641A JP2257121A JP25712190A JPH04135641A JP H04135641 A JPH04135641 A JP H04135641A JP 2257121 A JP2257121 A JP 2257121A JP 25712190 A JP25712190 A JP 25712190A JP H04135641 A JPH04135641 A JP H04135641A
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- catalyst
- aluminum
- zirconium
- oxidation catalyst
- 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 40
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 229910052878 cordierite Inorganic materials 0.000 claims description 5
- 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 claims description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 229910021472 group 8 element Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- -1 hydrogen carbon monoxide Chemical class 0.000 abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 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 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-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
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は酸化触媒、例えば水素、−酸化炭素、炭化水素
などのガスを燃焼させるための酸化触媒に関し、特に各
種可燃性ガスの中で最も酸化されにくいメタンを低温、
高いガス流量／触媒容積比の条件下で高効率で酸化する
ことができ、しかも１０００℃以上の高温においても優
れた耐熱性を有する酸化触媒に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an oxidation catalyst, for example, an oxidation catalyst for burning gases such as hydrogen, carbon oxide, hydrocarbons, etc. Methane, which is difficult to oxidize, at low temperature,
The present invention relates to an oxidation catalyst that can perform oxidation with high efficiency under conditions of a high gas flow rate/catalyst volume ratio and has excellent heat resistance even at high temperatures of 1000° C. or higher.
一酸化炭素、水素、あるいは炭化水素等の可燃性ガスを
酸化触媒の存在下で燃焼させる接触燃焼法は、主として
自動車排ガスの浄化を目的に研究され、多くの酸化触媒
が開発されている。The catalytic combustion method, in which combustible gases such as carbon monoxide, hydrogen, or hydrocarbons are burned in the presence of an oxidation catalyst, has been studied primarily for the purpose of purifying automobile exhaust gas, and many oxidation catalysts have been developed.
その主なものは白金のような貴金属、銅や鉄のような卑
金属の酸化物を活性成分とし、各活性成分を粒状やハニ
カム状等に成形したり、あるいはアルミナやチタニア等
の担体に直接担持させたものである。The main active ingredients are oxides of noble metals such as platinum or base metals such as copper and iron, and each active ingredient is formed into granules or honeycomb shapes, or directly supported on a carrier such as alumina or titania. This is what I did.
一方、最近では低ＮＯｘ燃焼法開発の一環として、プロ
パン、低熱量ガス、オイル等を燃焼させる酸化触媒が研
究されている。この触媒はハニカム型のコージエライト
やムライト等のセラミックスを基材とし、この基材にγ
−Ａ１２０゜（ガンマアルミナ） ジルコニア、マグネ
シア、α−ＡＩ２０３ （アルファアルミナ）等の担
体をウォシュコートし、活性成分としてＰｔ、 Ｐｔ＋
Ｐｄ。On the other hand, recently, as part of the development of low NOx combustion methods, oxidation catalysts for burning propane, low calorific value gas, oil, etc. have been researched. This catalyst uses honeycomb-shaped ceramics such as cordierite and mullite as a base material, and this base material has γ
-A120゜(gamma alumina) Wash coated with a carrier such as zirconia, magnesia, α-AI203 (alpha alumina), etc., and Pt, Pt+ as active ingredients
Pd.
Ｐｄ、 Ｐｔ＋Ｒｈ等の貴金属、あるいはコバルト、ニ
ッケル、マンガン等の卑金属の酸化物を担持させたもの
である。It supports oxides of noble metals such as Pd, Pt+Rh, or base metals such as cobalt, nickel, and manganese.
上記のような従来の酸化触媒は、−酸化炭素やプロパン
に対しては高活性を示すものの、より安定なメタンに対
してはいずれも性能が悪く、現在のところメタンに対し
てはその酸化性能において多くの問題点を残している。Although the conventional oxidation catalysts mentioned above show high activity against carbon oxide and propane, they have poor performance against methane, which is more stable, and their oxidation performance against methane is currently limited. Many problems remain.
また最近では１０００℃前後でも耐熱性がある触媒とし
て、アルミニウムとランタンの複合酸化物を主成分とす
る担体に、触媒活性成分を担持した触媒（特開昭６０−
１２１３２号公報）又はアルカリ土類金属元素とアルミ
ニウムの複合酸化物を主成分とする触媒（特開昭６２−
１５３１５８号公報）などが提案されている。Recently, as a catalyst that is heat resistant even at around 1000 degrees Celsius, a catalyst in which a catalytically active component is supported on a carrier mainly composed of a composite oxide of aluminum and lanthanum (Japanese Unexamined Patent Application Publication No. 1989-1999-1) has been developed.
12132) or a catalyst whose main component is a composite oxide of an alkaline earth metal element and aluminum (Japanese Unexamined Patent Publication No. 12132-
153158) and the like have been proposed.
従来の触媒は１０００ｔＪａ上で使用すると担体が熱に
よりシンタリングし比表面積が急激に低下するため実用
上使用することができない。When conventional catalysts are used above 1000 tJa, the carrier is sintered by heat and the specific surface area is rapidly reduced, so that it cannot be used practically.
本発明は上記技術水準に鑑み、高温下でも耐熱性の優れ
た酸化触媒を提供しようとするものである。In view of the above-mentioned state of the art, the present invention aims to provide an oxidation catalyst that has excellent heat resistance even at high temperatures.
本発明は
（１） アルミニウム及びジルコニウムの複合酸化物
を担体としてＩｂ族、Ｖａ族、Ｖｉａ族、ＶＩＩａ族、
ＶＩＩＩ族元素の金属又はその酸化物を一種以上担持さ
せてなることを特徴とする酸化触媒。The present invention provides (1) Ib group, Va group, Via group, VIIa group, using a composite oxide of aluminum and zirconium as a carrier.
An oxidation catalyst characterized by supporting one or more group VIII metals or their oxides.
（２）アルミニウム及びジルコニウムの複合酸化物をハ
ニカム状に成型してなることを特徴とする上記第（１）
項の酸化触媒。(2) Item (1) above, characterized in that it is formed by molding a composite oxide of aluminum and zirconium into a honeycomb shape.
Section oxidation catalyst.
（３〕 コージェライト、ムライト又はＭｇＤ、 Ａ
ｌ１［１３゜７ｉＯ□よりなる結晶性複合酸化物のうち
から選択されるハニカム状耐熱基材に上記第（１）項の
触媒をコーティングしてなることを特徴とする酸化触媒
。(3) Cordierite, mullite or MgD, A
An oxidation catalyst characterized in that the catalyst of item (1) above is coated on a honeycomb-shaped heat-resistant base material selected from crystalline composite oxides consisting of 11[13°7iO□.
である。It is.
本発明にいうアルミニウム及びジルコニウムの複合酸化
物とは、Ａ１．０３ ： ＺｒＯ□の重量比で５＝９５
〜９５：５の組成を有する非晶質（一部は結晶化してい
るもの５全体としては非晶質）のもので下記方法で製造
される。The composite oxide of aluminum and zirconium referred to in the present invention has a weight ratio of A1.03:ZrO□ of 5=95.
It is amorphous (a part is crystallized but the whole is amorphous) having a composition of ~95:5 and is produced by the following method.
■ ジルコニウムの化合物及びアルミニウムの化合物の
水溶液にアンモニア水又は炭酸ソーダ水溶液などの塩基
性の沈殿剤を添加して生成する沈殿を洗浄した後乾燥し
、５００℃以上で焼成する。(2) A basic precipitant such as ammonia water or sodium carbonate aqueous solution is added to an aqueous solution of a zirconium compound and an aluminum compound, and the resulting precipitate is washed, dried, and fired at 500°C or higher.
■ ジルコニウムの水酸化物または酸化物をアルミニウ
ムの化合物の水溶液に混合した後、沈殿剤を添加して生
成する沈殿を洗浄した後乾燥し、５００℃以上で焼成す
る。(2) After mixing zirconium hydroxide or oxide with an aqueous solution of an aluminum compound, a precipitant is added and the resulting precipitate is washed, dried, and fired at 500°C or higher.
■ アルミニウムの水酸化物または酸化物をジルコニウ
ムの化合物の水溶液に混合した後、沈殿剤を添加して生
成する沈殿を洗浄した後乾燥し、５００℃以上で焼成す
る。(2) After mixing aluminum hydroxide or oxide with an aqueous solution of a zirconium compound, a precipitant is added and the resulting precipitate is washed, dried, and fired at 500°C or higher.
以上の方法で調製したアルミニウム及びジルコニウムの
複合酸化物は、バインダーを添加してハニカム状に成型
したり、又は複合酸化物のスラリーにコージェライト、
ムライト、又はＭｇＯ、Ａｌ２Ｄ３ 、 ＴｉＯ２より
なる結晶性複合酸化物のうちから選択されるハニカム状
耐熱基材を浸漬して、ウォッシュコートし、５００℃以
上で焼付けることによりハニカム状の担体にすることが
できる。The composite oxide of aluminum and zirconium prepared by the above method is formed into a honeycomb shape by adding a binder, or by adding cordierite to a slurry of the composite oxide.
A honeycomb-shaped heat-resistant base material selected from mullite or a crystalline composite oxide consisting of MgO, Al2D3, and TiO2 is immersed, wash-coated, and baked at 500°C or higher to form a honeycomb-shaped carrier. I can do it.
なお、上記のＭｇＯ、Ａｌ２Ｏ３，ＴｉＯ２よりなる結
晶性複合酸化物とは、マグネシア、炭酸マグネシウム、
水酸化マグネシウムのようなＭｇ化合物、アルミナ、水
酸化アルミニウムのようなＡＩ化合物及びアナターゼ又
はルチル型酸化チタンのようなＴ】化合物の混合物を、
１３００〜１７００℃で焼成して結晶化することによっ
て得られた低膨張性のものを意味する。In addition, the above-mentioned crystalline composite oxide consisting of MgO, Al2O3, and TiO2 refers to magnesia, magnesium carbonate,
A mixture of Mg compounds such as magnesium hydroxide, alumina, AI compounds such as aluminum hydroxide, and T compounds such as anatase or rutile titanium oxide,
It means a low-expansion product obtained by crystallizing by firing at 1300 to 1700°C.
次に、このようにして得られたアルミニウム及びジルコ
ニウムの複合酸化物又はハニカム状の担体にＩｂ族、Ｖ
ａ族、ＶＩａ族、ＶＩＩａ族、ＶＩＩＩ族元素の金属又
はその酸化物を担持させる方法は、従来から用いられて
いる方法でよく、例えば上記元素の酸化物を担持させる
場合には、各元素の硝酸塩水溶液に担体を浸漬後焼成す
ればよく、また上記元素の金属を担持させる場合には、
各元素の化合物の水溶液に担体を浸漬機水素還元すれば
調製できる。Next, the composite oxide of aluminum and zirconium obtained in this way or the honeycomb-shaped support was coated with Ib group, V
The method for supporting metals of group a, group VIa, group VIIa, and group VIII elements or their oxides may be any conventionally used method. For example, when supporting oxides of the above elements, It is sufficient to immerse the carrier in a nitrate aqueous solution and then sinter it, and when supporting the metals of the above elements,
It can be prepared by immersing a carrier in an aqueous solution of a compound of each element and subjecting it to hydrogen reduction.
Ｉｂ族、Ｖａ族、ＶＩａ族、ＶＩＩａ族、ＶＩＩＩ族元
素の金属又は酸化物の一例としては、ＣｕＯ、Ｖ２Ｏ５
゜ＣｒｗＯｓ 、 ＭｎＯ２，Ｆｅ２Ｏ３，ＮｉＯ、Ｃ
ｏｏ 、 Ｐｔ 、 Ｐｄ 。Examples of metals or oxides of group Ib, Va, VIa, VIIa, and VIII elements include CuO, V2O5
゜CrwOs, MnO2, Fe2O3, NiO, C
oo, Pt, Pd.
Ｒｈ、Ｒｕなどがあり、その担持量は、アルミニウム及
びジルコニウムの複合酸化物１０Ｄ重量部当たり０．１
〜３０重量部の範囲が好ましい。Rh, Ru, etc. are supported in an amount of 0.1 per 10D weight part of aluminum and zirconium composite oxide.
A range of 30 parts by weight is preferred.
以上のようにして得られた触媒は水素、−酸化炭素、炭
化水素ガスなどのガスの酸化反応に対し、優れた活性、
耐久性を示した。The catalyst obtained as described above has excellent activity and
It showed durability.
以下、実施例により本発明を具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
〔実施例１〕
硝酸アルミニウムと硝酸ジルコニウムの混合水溶液に炭
酸ソーダ水溶液を添加して得られる沈殿を濾過、水洗、
乾燥後５００℃で焼成して担体１ （ＺｒＤｚ ：
Ａ１２［］３の重量比 ５０：５０）を得た。[Example 1] A precipitate obtained by adding a sodium carbonate aqueous solution to a mixed aqueous solution of aluminum nitrate and zirconium nitrate was filtered, washed with water,
After drying, it was fired at 500°C to form carrier 1 (ZrDz:
A12[]3 weight ratio 50:50) was obtained.
ベーマイトＡｌ０（ＤＨ）粉末を水に添加し、さらにオ
キシ塩化ジルコニウム水溶液を添加した溶液にアンモニ
ア水を添加して得られる沈殿を濾過、水洗し乾燥後１０
００℃で焼成してＺｒＯ２：へ１２０３比の異なる担体
２ （ＺｒＯ２：＾１２０．の重量比 ９０：１０）、
担体３ （Ｚｒ０２ ： Ａ１２［１３の重量比 ２０
：８０）及び担体４ （ＺｒＬ：八１□０３の重量比
１０：９０）を得た。Boehmite Al0(DH) powder was added to water, and aqueous ammonia was added to a solution containing an aqueous solution of zirconium oxychloride. The precipitate obtained was filtered, washed with water, and dried for 10 minutes.
Supports 2 with different ratios of ZrO2:1203 (weight ratio of ZrO2:120.90:10) by firing at 00°C,
Support 3 (Zr02:A12[13 weight ratio 20
:80) and carrier 4 (ZrL:81□03 weight ratio
10:90) was obtained.
担体１〜４を粒径２〜４ ｍｍのペレットに成形した後
、塩化パラジウム水溶液に浸漬し乾燥後、４００℃で水
素還元し触媒１〜４を各々調製した。担体１のペレット
を塩化白金酸水溶液、塩化ルテニウム水溶液、塩化ロジ
ウム水溶液各々に浸漬し乾燥後、４００℃で水素還元し
触媒５〜７を調製した。Supports 1 to 4 were formed into pellets with a particle size of 2 to 4 mm, immersed in an aqueous palladium chloride solution, dried, and then reduced with hydrogen at 400°C to prepare catalysts 1 to 4, respectively. The pellets of carrier 1 were immersed in a chloroplatinic acid aqueous solution, a ruthenium chloride aqueous solution, and a rhodium chloride aqueous solution, dried, and then subjected to hydrogen reduction at 400° C. to prepare catalysts 5 to 7.
これらの触媒を表１の条件（可燃ガスを空気で希釈）で
活性評価を行い、その結果を表２に示す。The activity of these catalysts was evaluated under the conditions shown in Table 1 (combustible gas diluted with air), and the results are shown in Table 2.
表 １
〔実施例２〕
実施例１で調製した担体２のペレットを用い、硝酸銅、
硝酸バナジウム、硝酸クロム、硝酸マンガン、硝酸鉄、
硝酸ニッケル、硝酸コバルトの各水溶液に浸漬し、乾燥
後５００℃で５時間焼成し触媒８〜１３を調製した。Table 1 [Example 2] Using pellets of carrier 2 prepared in Example 1, copper nitrate,
Vanadium nitrate, chromium nitrate, manganese nitrate, iron nitrate,
Catalysts 8 to 13 were prepared by immersing them in aqueous solutions of nickel nitrate and cobalt nitrate, drying them, and then calcining them at 500°C for 5 hours.
これらの触媒をプロパン又はメタノールを含有する空気
を原料として、反応温度５００℃、ガス空塔速度１０，
０００ｈ−’の条件で活性評価試験を行い、その結果を
表３に示す。These catalysts were prepared using air containing propane or methanol as a raw material at a reaction temperature of 500°C and a superficial gas velocity of 10.
An activity evaluation test was conducted under the conditions of 000h-' and the results are shown in Table 3.
表 ３
〔実施例３〕
実施例２で調製した触媒８〜１３を硝酸白金水溶液に浸
漬し、４００℃で水素還元を行い触媒１４〜１９を調製
した。Table 3 [Example 3] Catalysts 8 to 13 prepared in Example 2 were immersed in an aqueous platinum nitrate solution and subjected to hydrogen reduction at 400°C to prepare catalysts 14 to 19.
これらの触媒をメタン１％（残部空気）含有ガスを用い
、ガス空塔速度５０．０００ｈ−’、反応温度８００℃
の条件で活性評価を行い、その結果を表４に示す。表４
には、１０００時間活性評価試験後の結果も併記する。Using a gas containing 1% methane (balance air), the superficial gas velocity was 50,000 h-', and the reaction temperature was 800°C.
The activity was evaluated under the following conditions, and the results are shown in Table 4. Table 4
The results after the 1000-hour activity evaluation test are also listed.
〔実施例４コ
直径１インチで、１平方インチ当たり２００個の開口部
（２００セル）を有するハニカム状のコージェライト
（２Ｍｇ０・２＾Ｉ２Ｏ３・５８１０□）基材又はＭｇ
Ｏ、Ａｌ２Ｏ３、ＴｌＯ３よりなる結晶性複合酸化物（
ＭｇＯ・４Ａ１２［１３・６Ｔｉ０２）基材を用い、担
体３のＺｒＯ２” Ａｌ２Ｏ３（２０： ８０ ）粉末
を上記基材にウォッシュコートし、１［）００℃で焼付
けてハニカム担体Ａ、Ｂを得た。ＺｒＯ，・Ａｌ２Ｏ３
コート量はハニカム担体１００重量部当たり２０重量部
であった。[Example 4] Honeycomb-shaped cordierite with a diameter of 1 inch and 200 openings (200 cells) per square inch.
(2Mg0・2^I2O3・5810□) Base material or Mg
Crystalline composite oxide (
Using a MgO・4A12[13・6Ti02) base material, the ZrO2'' Al2O3 (20:80) powder of carrier 3 was wash coated on the base material and baked at 1[)00°C to obtain honeycomb carriers A and B. .ZrO, ・Al2O3
The coating amount was 20 parts by weight per 100 parts by weight of the honeycomb carrier.
担体Ａ、Ｂそれぞれ永を塩化パラジウムと塩化白金の混
合水溶液に浸漬し乾燥後４００℃で水素還元を行い触媒
２０．２１を得た。Supports A and B were each immersed in a mixed aqueous solution of palladium chloride and platinum chloride, dried, and then subjected to hydrogen reduction at 400°C to obtain catalyst 20.21.
これらの触媒及び、さらに１２００℃で１０００時間焼
成した触媒を、メタン３％（残部空気）含有ガスを用い
、ガス空塔速度３００，０００ｈ−１、触媒層入口ガス
温度４００℃の条件で活性評価を行い、表５の結果を得
た。These catalysts and the catalysts calcined for 1000 hours at 1200°C were evaluated for their activity using a gas containing 3% methane (remaining air) at a superficial gas velocity of 300,000 h-1 and a gas temperature at the inlet of the catalyst layer of 400°C. The results shown in Table 5 were obtained.
以上詳述したように本発明によれば、活性が高くかつ耐
熱性に優れた酸化触媒を提供できる。As detailed above, according to the present invention, an oxidation catalyst having high activity and excellent heat resistance can be provided.
Claims (3)
体として I ｂ族、Ｖａ族、VIａ族、VIIａ族、VIII族元
素の金属又はその酸化物を一種以上担持させてなること
を特徴とする酸化触媒。(1) An oxidation catalyst characterized in that one or more metals of group Ib, group Va, group VIa, group VIIa, group VIII elements or their oxides are supported on a composite oxide of aluminum and zirconium as a carrier.
ニカム状に成型してなることを特徴とする特許請求の範
囲第（１）項の酸化触媒。(2) The oxidation catalyst according to claim (1), which is formed by molding a composite oxide of aluminum and zirconium into a honeycomb shape.
Ｏ＿３、ＴｉＯ＿２よりなる結晶性複合酸化物のうちか
ら選択されるハニカム状耐熱基材に特許請求の範囲第（
１）項の触媒をコーティングしてなることを特徴とする
酸化触媒。(3) Cordierite, mullite or MgO, Al_2
A honeycomb-shaped heat-resistant base material selected from crystalline composite oxides consisting of O_3 and TiO_2 is
An oxidation catalyst characterized by being coated with the catalyst of item 1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2257121A JPH04135641A (en) | 1990-09-28 | 1990-09-28 | Oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2257121A JPH04135641A (en) | 1990-09-28 | 1990-09-28 | Oxidation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04135641A true JPH04135641A (en) | 1992-05-11 |
Family
ID=17302023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2257121A Pending JPH04135641A (en) | 1990-09-28 | 1990-09-28 | Oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04135641A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006511333A (en) * | 2002-12-20 | 2006-04-06 | 本田技研工業株式会社 | Alkali-containing catalyst formulation for hydrogen production at medium and low temperatures |
| WO2008054026A1 (en) * | 2006-11-01 | 2008-05-08 | Toyota Jidosha Kabushiki Kaisha | Automobile exhaust gas purifying catalyst and method for producing the same |
| CN105797577A (en) * | 2016-04-27 | 2016-07-27 | 华北电力大学 | Process and catalyst for catalytically reducing NOX by using methane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4886789A (en) * | 1972-01-27 | 1973-11-15 | ||
| JPS4910163A (en) * | 1972-04-12 | 1974-01-29 | ||
| JPS61197037A (en) * | 1985-02-22 | 1986-09-01 | Matsushita Electric Ind Co Ltd | Oxidizing catalytic material for purifying waste gas |
| JPS62261803A (en) * | 1986-05-09 | 1987-11-14 | Toyo C C I Kk | Contact burning method |
| JPS6334781A (en) * | 1986-07-28 | 1988-02-15 | Fuji Photo Film Co Ltd | Production of magnetic tape cassette protection film layer |
-
1990
- 1990-09-28 JP JP2257121A patent/JPH04135641A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4886789A (en) * | 1972-01-27 | 1973-11-15 | ||
| JPS4910163A (en) * | 1972-04-12 | 1974-01-29 | ||
| JPS61197037A (en) * | 1985-02-22 | 1986-09-01 | Matsushita Electric Ind Co Ltd | Oxidizing catalytic material for purifying waste gas |
| JPS62261803A (en) * | 1986-05-09 | 1987-11-14 | Toyo C C I Kk | Contact burning method |
| JPS6334781A (en) * | 1986-07-28 | 1988-02-15 | Fuji Photo Film Co Ltd | Production of magnetic tape cassette protection film layer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006511333A (en) * | 2002-12-20 | 2006-04-06 | 本田技研工業株式会社 | Alkali-containing catalyst formulation for hydrogen production at medium and low temperatures |
| WO2008054026A1 (en) * | 2006-11-01 | 2008-05-08 | Toyota Jidosha Kabushiki Kaisha | Automobile exhaust gas purifying catalyst and method for producing the same |
| US8288310B2 (en) | 2006-11-01 | 2012-10-16 | Toyota Jidosha Kabushiki Kaisha | Automobile exhaust gas purification catalyst and method of production of same |
| CN105797577A (en) * | 2016-04-27 | 2016-07-27 | 华北电力大学 | Process and catalyst for catalytically reducing NOX by using methane |
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