JPH06304478A - Oxidation catalyst - Google Patents
Oxidation catalystInfo
- Publication number
- JPH06304478A JPH06304478A JP5093971A JP9397193A JPH06304478A JP H06304478 A JPH06304478 A JP H06304478A JP 5093971 A JP5093971 A JP 5093971A JP 9397193 A JP9397193 A JP 9397193A JP H06304478 A JPH06304478 A JP H06304478A
- Authority
- JP
- Japan
- Prior art keywords
- oxidation catalyst
- oxide
- group
- composite oxide
- carrier
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 6
- 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 abstract description 6
- 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 abstract description 5
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 5
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910021472 group 8 element Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 241000264877 Hippospongia communis Species 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 5
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 238000011156 evaluation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum compound Chemical class 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 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
- 150000003609 titanium compounds Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001072332 Monia Species 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910002674 PdO Inorganic materials 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite 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
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 150000002681 magnesium compounds Chemical class 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
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 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
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は酸化触媒、例えば水素、
一酸化炭素、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。This invention relates to oxidation catalysts such as hydrogen,
Regarding an oxidation catalyst for burning gases such as carbon monoxide and hydrocarbons, methane, which is the most difficult to oxidize among various combustible gases, is highly efficiently oxidized under conditions of low temperature and high gas flow rate / catalyst volume ratio The present invention relates to an oxidation catalyst that can be processed and has excellent heat resistance even at a high temperature of 1000 ° C. or higher.
【0002】[0002]
【従来の技術】一酸化炭素、水素、あるいは炭化水素な
ど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。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などに成形し
たり、あるいはアルミナやチタニアなどの担体に直接担
持させたものである。2. Description of the Related Art A catalytic combustion method in which a combustible gas such as carbon monoxide, hydrogen or hydrocarbon is burned in the presence of an oxidation catalyst has been studied mainly for the purpose of purifying automobile exhaust gas.
Many oxidation catalysts have been developed. The main ones are oxides of noble metals such as platinum and base metals such as copper and iron as active ingredients, and each active ingredient is formed into granules or honeycombs, or directly loaded on a carrier such as alumina or titania. It was made.
【0003】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、オイルなどを燃焼させ
る酸化触媒が研究されている。この触媒はハニカム型の
コージェライトやムライトなどのセラミックスを基材と
し、この基材にγ−Al2 O 3 (ガンマアルミナ)、ジ
ルコニア、マグネシア、α−Al2 O3 (アルファアル
ミナ)などの担体をウォッシュコートし、活性成分とし
てPt、Pt+Pd、Pd、Pt+Rhなどの貴金属、
あるいはコバルト、ニッケル、マンガンなどの卑金属の
酸化物を担持させたものである。On the other hand, recently, as part of the development of low NOx combustion method
Burning propane, low calorific value gas, oil, etc.
Oxidation catalysts are being studied. This catalyst is of honeycomb type
Ceramics such as cordierite and mullite are used as base materials
And γ-Al on this substrate2O 3(Gamma alumina), di
Luconia, magnesia, α-Al2O3(Alpha Al
Mina) and other carriers are wash-coated to make it the active ingredient.
Precious metals such as Pt, Pt + Pd, Pd, Pt + Rh,
Or base metals such as cobalt, nickel and manganese
An oxide is supported.
【0004】上記のような従来の酸化触媒は一酸化炭素
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 above-mentioned conventional oxidation catalysts have high activity with respect to carbon monoxide and propane, they are inferior in performance with respect to more stable methane, and are currently poor in performance with respect to methane. Many problems remain in the oxidation performance.
【0005】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)、またはアルカリ土
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。Further, recently, as a catalyst having heat resistance even at around 1000 ° C., a catalyst having a catalytically active component supported on a carrier having a composite oxide of aluminum and lanthanum as a main component (JP-A-60-12132), Alternatively, a catalyst containing a composite oxide of an alkaline earth metal element and aluminum as a main component (JP-A-62-153158) has been proposed.
【0006】[0006]
【発明が解決しようとする課題】従来の触媒は1000
℃以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。The conventional catalyst is 1000
If it is used at a temperature of ℃ or above, the carrier will be sintered by heat and the specific surface area will decrease sharply, so that it cannot be used in practice.
【0007】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 having excellent heat resistance even at high temperatures.
【0008】[0008]
【課題を解決するための手段】本発明は (1)アルミニウムおよびチタ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
素の金属またはその酸化物を一種以上および希土類元素
の酸化物、酸化ジルコニウムを担持させてなることを特
徴とする酸化触媒。 (2)アルミニウムおよびチタ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。 (3)コージェライト、ムライトまたはMgO、Al2
O3 、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。であ
る。The present invention provides (1) one or more metals of Group Ib, Va, VIa, VIIa and VIII elements or their oxides with a composite oxide of aluminum and titanium as a carrier. An oxidation catalyst comprising zirconium oxide, which is an oxide of a rare earth element. (2) The above (1), wherein the composite oxide of aluminum and titanium is formed into a honeycomb shape
Oxidation catalyst. (3) Cordierite, mullite or MgO, Al 2
An oxidation catalyst comprising a honeycomb heat-resistant base material selected from crystalline composite oxides of O 3 and TiO 2 coated with the catalyst of the above item (1). Is.
【0009】[0009]
【作用】本発明にいうアルミニウムおよびチタニウムの
複合酸化物とは、Al2 O3 、TiO2 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
ているものの全体としては非晶質)のもので下記方法で
製造される。 アルミニウムの化合物およびチタニウムの化合物の
水溶液にアンモニア水また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。 アルミニウムの水酸化物または酸化物をチタニウム
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。 チタ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、沈殿物を添加して生成
する沈殿を洗浄した後乾燥し、500℃以上で焼成す
る。The composite oxide of aluminum and titanium referred to in the present invention means that the weight ratio of Al 2 O 3 and TiO 2 is 5:
Amorphous having a composition of 95 to 95: 5 (partly crystallized but generally amorphous) is manufactured by the following method. A precipitate generated by adding a basic precipitant such as ammonia water or an aqueous solution of sodium carbonate to an aqueous solution of an aluminum compound and a titanium compound is washed, dried and calcined at 500 ° C. or higher. After mixing a hydroxide or oxide of aluminum with an aqueous solution of a titanium compound, a precipitating agent is added to wash the resulting precipitate, which is then dried and calcined at 500 ° C. or higher. A titanium hydroxide or oxide is mixed with an aqueous solution of an aluminum compound, and then a precipitate is added to wash the precipitate, which is then dried and calcined at 500 ° C. or higher.
【0010】以上の方法で調製したアルミニウムおよび
チタ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、または複合酸化物のスラリーにコー
ジェライト、ムライト、またはMgO、Al2 O3 、T
iO2 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、5
00℃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 titanium prepared by the above method is molded into a honeycomb by adding a binder, or a slurry of the composite oxide is made of cordierite, mullite, MgO, Al 2 O 3 or T.
Honeycomb-shaped heat-resistant base material selected from among crystalline complex oxides composed of iO 2 is dipped and wash-coated, and
A honeycomb-shaped carrier can be obtained by baking at a temperature of 00 ° C. or higher.
【0011】なお、上記のMgO、Al2 O3 、TiO
2 よりなる結晶性複合酸化物とはマグネシウム、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Al化合物およ
びアナターゼまたはルチル型酸化チタンのようなTi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。The above MgO, Al 2 O 3 , and TiO
The crystalline composite oxide consisting of 2 is a magnesium compound such as magnesium, magnesium carbonate, magnesium hydroxide,
Low-expansion product obtained by crystallization of a mixture of an Al compound such as alumina and aluminum hydroxide and a Ti compound such as anatase or rutile-type titanium oxide at 1300 to 1700 ° C. .
【0012】次に、このようにして得られたアルミニウ
ムおよびチタニウムの複合酸化物またはハニカム状の担
体にIb族、Va族、VIa族、 VIIa族、VIII族元素の
金属また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後水素還元すれ
ば調製できる。希土類元素の酸化物、酸化ジルコニウム
を担持する場合には希土類元素の硝酸塩水溶液、オキシ
硝酸ジルコニウム水溶液に担体を浸漬後焼成すればよ
い。Ib族、Va族、VIa族、 VIIa族、VIII族元素の
金属またはその酸化物と希土類元素の酸化物、酸化ジル
コウニムを担持する方法としては上記の方法でいずれか
を予じめ担持した後、他の酸化物を担持する方法、また
は両成分の化合物の水溶液に担体を浸漬後焼成すること
により担持する方法が用いられる。Next, the thus-obtained composite oxide of aluminum and titanium or the honeycomb-shaped carrier is loaded with the metal of the Ib group, Va group, VIa group, VIIa group, or VIII group element or its oxide. The method may be a conventionally used method, for example, in the case of supporting an oxide of the above element, it may be calcined after immersing the carrier in an aqueous nitrate solution of each element, and in the case of supporting a metal of the above element. It can be prepared by immersing the carrier in an aqueous solution of a compound of each element and then reducing with hydrogen. When the oxide of a rare earth element or zirconium oxide is supported, the carrier may be immersed in an aqueous solution of a nitrate of a rare earth element or an aqueous solution of zirconium oxynitrate and then baked. As a method of supporting the metal of the group Ib, the group of Va, the group of VIa, the group of VIIa, the group of VIII or the oxide thereof and the oxide of the rare earth element, zirconium oxide, after carrying out any one of the above-mentioned methods in advance, A method of supporting another oxide, or a method of supporting by immersing the carrier in an aqueous solution of a compound of both components and baking the carrier is used.
【0013】希土類元素の酸化物、酸化ジルコニウム担
持量はそれぞれアルミニウムおよびチタニウムの複合酸
化物100重量部当たり1〜30重量部の範囲が好まし
い。希土類元素の酸化物の一例としてはLa2 O3 、C
eO2 :Nd2 O3 などがあげられる。The amounts of the rare earth element oxide and zirconium oxide supported are preferably in the range of 1 to 30 parts by weight per 100 parts by weight of the composite oxide of aluminum and titanium, respectively. Examples of rare earth element oxides are La 2 O 3 and C.
eO 2 : Nd 2 O 3 and the like.
【0014】Ib族、Va族、VIa族、 VIIa族、VIII
族元素の金属またはその酸化物の一例としてはCuO、
V2 O5 、Cr2 O3 、MnO2 、Fe2 O3 、Ni
O、CoO、PdO、Pt、Pd、Rh、Ruなどがあ
り、その担持量はアルミニウムおよびチタニウムの複合
酸化物100重量部当たり0.1〜100重量部の範囲
が好ましい。以上のようにして得られた触媒は水素、一
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。以下、実施例により本発明
を具体的に説明する。Group Ib, Group Va, Group VIa, Group VIIa, VIII
As an example of the metal of the group element or its oxide, CuO,
V 2 O 5 , Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Ni
O, CoO, PdO, Pt, Pd, Rh, Ru and the like are included, and the supported amount thereof is preferably in the range of 0.1 to 100 parts by weight per 100 parts by weight of the composite oxide of aluminum and titanium. The catalyst obtained as described above showed excellent activity and durability for the oxidation reaction of gases such as hydrogen, carbon monoxide, and hydrocarbon gas. Hereinafter, the present invention will be specifically described with reference to examples.
【0015】[0015]
(実施例1)硝酸アルミニウムと塩化チタニウムの混合
水溶液に炭酸ソーダ水溶液を添加して得られる沈殿をろ
過、水洗、乾燥後500℃で焼成して担体1(Al2 O
3 :TiO2 の重量比50:50)を得た。Example 1 A precipitate obtained by adding an aqueous solution of sodium carbonate to a mixed aqueous solution of aluminum nitrate and titanium chloride was filtered, washed with water, dried, and then baked at 500 ° C. to obtain a carrier 1 (Al 2 O).
A 50:50 weight ratio of 3 : TiO 2 was obtained.
【0016】ベーマイトAlO(OH)粉末を水に添加
し、さらに塩化チタ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ろ過、水洗し乾燥後
1000℃で焼成してAl2 O3 :TiO2 比の異なる
担体2(Al2 O3 :TiO 2 の重量比90:10)、
担体3(Al2 O3 :TiO2 の重量比20:80)及
び担体4(Al2 O3 :TiO2 の重量比10:90)
を得た。Add boehmite AlO (OH) powder to water
The solution added with an aqueous solution of titanium chloride.
The precipitate obtained by adding monia water is filtered, washed with water, and dried.
Al fired at 1000 ° C2O3: TiO2Different ratio
Carrier 2 (Al2O3: TiO 2Weight ratio of 90:10),
Carrier 3 (Al2O3: TiO2Weight ratio of 20:80)
And carrier 4 (Al2O3: TiO2Weight ratio of 10:90)
Got
【0017】担体1〜4を粒径2〜4mmのペレットに
成形した後、硝酸ランタンおよびオキシ硝酸ジルコニウ
ムの水溶液に浸漬し500℃で焼成することにより酸化
ランタンおよび酸化ジルコニウムをそれぞれ5重量%
(担体100重量部当たり)担持したペレットを硝酸パ
ラジウム水溶液に浸漬し乾燥後、500℃で焼成し触媒
1〜4を各々調製した。After the carriers 1 to 4 were molded into pellets having a particle size of 2 to 4 mm, they were immersed in an aqueous solution of lanthanum nitrate and zirconium oxynitrate and baked at 500 ° C. to give 5% by weight of lanthanum oxide and zirconium oxide, respectively.
(Per 100 parts by weight of carrier) The supported pellets were immersed in an aqueous palladium nitrate solution, dried, and then calcined at 500 ° C to prepare catalysts 1 to 4, respectively.
【0018】また、担体1を粒径2〜4mmのペレット
に成形した後、硝酸ランタンおよびオキシ硝酸ジルコニ
ウムの水溶液に浸漬し500℃で焼成することにより酸
化ランタンおよび酸化ジルコニウムをそれぞれ5重量%
(担体100重量部当たり)担持したペレットを塩化白
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。Further, after the carrier 1 is molded into pellets having a particle size of 2 to 4 mm, it is immersed in an aqueous solution of lanthanum nitrate and zirconium oxynitrate and calcined at 500 ° C. to give 5% by weight each of lanthanum oxide and zirconium oxide.
(Per 100 parts by weight of the carrier) The supported pellets were immersed in an aqueous solution of chloroplatinic acid, an aqueous solution of ruthenium chloride and an aqueous solution of rhodium chloride, dried and then reduced with hydrogen at 400 ° C.
7 was prepared.
【0019】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 (flammable gas was diluted with air), and the results are shown in Table 2.
【0020】[0020]
【表1】 [Table 1]
【0021】[0021]
【表2】 [Table 2]
【0022】(実施例2)実施例1で調製した担体3の
ペレットを用い、硝酸銅、硝酸バナジウム、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と
硝酸ランタンの水溶液およびオキシ硝酸ジルコニウム水
溶液の混合水溶液に浸漬し、乾燥後500℃で5時間焼
成し触媒8〜13を調製した。Example 2 Using the pellets of the carrier 3 prepared in Example 1, each aqueous solution of copper nitrate, vanadium nitrate, manganese nitrate, iron nitrate, nickel nitrate, cobalt nitrate, an aqueous solution of lanthanum nitrate and zirconium oxynitrate was used. The catalysts 8 to 13 were prepared by immersing in a mixed aqueous solution of aqueous solutions, drying and firing at 500 ° C. for 5 hours.
【0023】これらの触媒をプロパンまたはメタノール
を含有する空気を原料として、反応温度500℃、ガス
空間速度10,000h-1の条件で活性評価試験を行
い、その結果を表3に示す。An activity evaluation test was conducted on these catalysts using air containing propane or methanol as a raw material under the conditions of a reaction temperature of 500 ° C. and a gas space velocity of 10,000 h −1 , and the results are shown in Table 3.
【0024】[0024]
【表3】 [Table 3]
【0025】(実施例3)実施例2で調製した触媒8〜
13を硝酸パラジウム水溶液に浸漬した後、500℃で
焼成し触媒14〜19を調製した。(Example 3) Catalyst 8 prepared in Example 2
13 was immersed in an aqueous palladium nitrate solution and then calcined at 500 ° C. to prepare catalysts 14 to 19.
【0026】これらの触媒をメタン1%(残部空気)含
有ガスを用い、ガス空間速度50,000h-1、反応温
度400℃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。The activity of these catalysts was evaluated under the conditions of gas space velocity of 50,000 h −1 and reaction temperature of 400 ° C. using a gas containing 1% of methane (the balance of air). The results are shown in Table 4. Table 4 also shows the results after the 1000-hour activity evaluation test.
【0027】[0027]
【表4】 [Table 4]
【0028】(実施例4)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(2MgO・2Al2 O3 ・5
SiO2 )基材またはMgO、Al2 O3 、ZrO2 よ
りなる結晶性複合酸化物(MgO・4Al 2 O3 ・6T
iO2 )基材を用い、担体3のAl2 O3 :TiO
2 (20:80)粉末にLa2 O3 を5重量%担持した
ものを上記基材にウォッシュコートし、1000℃で焼
付けてハニカム担体A、Bを得た。La2 O3 担持Al
2 O3 :TiO2 コート量はハニカム担体100重量部
当たり40重量部であった。(Embodiment 4) Diameter 1 inch, 1 square in
Hani with 200 openings per cell (200 cells)
Cam-shaped cordierite (2MgO / 2Al2O3・ 5
SiO2) Base material or MgO, Al2O3, ZrO2Yo
Crystalline compound oxide (MgO.4Al 2O3・ 6T
iO2) Using a base material, Al of the carrier 32O3: TiO
2(20:80) La powder2O3Carried 5% by weight
The above base material is wash-coated and baked at 1000 ° C.
Then, honeycomb carriers A and B were obtained. La2O3Supported Al
2O3: TiO2The coating amount is 100 parts by weight of the honeycomb carrier.
It was 40 parts by weight.
【0029】担体A、Bそれぞれを硝酸パラジウム水溶
液に浸漬し乾燥後500℃で焼成し、さらにオキシ硝酸
ジルコニウム水溶液に浸漬し乾燥後500℃で焼成し触
媒20、21を得た。Each of the carriers A and B was immersed in an aqueous solution of palladium nitrate, dried and calcined at 500 ° C., further immersed in an aqueous solution of zirconium oxynitrate, dried and calcined at 500 ° C. to obtain catalysts 20 and 21.
【0030】これらの触媒およびさらに1100℃で1
000時間焼成した触媒を、メタン3%(残部空気)含
有ガスを用い、ガス空間速度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 additionally 1 at 1100 ° C.
The catalyst calcined for 000 hours was subjected to activity evaluation using a gas containing 3% of methane (remainder air) under the conditions of a gas space velocity of 300,000 h −1 and a catalyst layer inlet gas temperature of 400 ° C., and the results shown in Table 5 were obtained.
【0031】[0031]
【表5】 [Table 5]
【0032】[0032]
【発明の効果】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 described above in detail, according to the present invention, an oxidation catalyst having high activity and excellent heat resistance can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 B01J 23/64 M 8017−4G 23/76 M 8017−4G 23/89 M 8017−4G ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location B01J 23/64 M 8017-4G 23/76 M 8017-4G 23/89 M 8017-4G
Claims (3)
化物を担体としてIb族、Va族、VIa族、 VIIa族、
VIII族元素の金属またはその酸化物を一種以上および希
土類元素の酸化物、酸化ジルコニウムを担持させてなる
ことを特徴とする酸化触媒。1. A group Ib group, a Va group, a VIa group, a VIIa group using a composite oxide of aluminum and titanium as a carrier.
An oxidation catalyst comprising one or more metals of Group VIII elements or oxides thereof, a rare earth element oxide, and zirconium oxide.
化物をハニカム状に成型してなることを特徴とする請求
項1記載の酸化触媒。2. The oxidation catalyst according to claim 1, which is formed by molding a composite oxide of aluminum and titanium into a honeycomb shape.
O、Al2 O3 、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に請求項1記載
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 Mg
An oxidation catalyst comprising a honeycomb heat-resistant base material selected from the crystalline composite oxides of O, Al 2 O 3 and TiO 2 coated with the catalyst of claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5093971A JPH06304478A (en) | 1993-04-21 | 1993-04-21 | Oxidation catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5093971A JPH06304478A (en) | 1993-04-21 | 1993-04-21 | Oxidation catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06304478A true JPH06304478A (en) | 1994-11-01 |
Family
ID=14097297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5093971A Withdrawn JPH06304478A (en) | 1993-04-21 | 1993-04-21 | Oxidation catalyst |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH06304478A (en) |
-
1993
- 1993-04-21 JP JP5093971A patent/JPH06304478A/en not_active Withdrawn
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