JPH06205973A - Oxidation catalyst - Google Patents
Oxidation catalystInfo
- Publication number
- JPH06205973A JPH06205973A JP5001103A JP110393A JPH06205973A JP H06205973 A JPH06205973 A JP H06205973A JP 5001103 A JP5001103 A JP 5001103A JP 110393 A JP110393 A JP 110393A JP H06205973 A JPH06205973 A JP H06205973A
- Authority
- JP
- Japan
- Prior art keywords
- group
- oxide
- zirconium
- oxidation catalyst
- 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- Withdrawn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 41
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- 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
- 239000002131 composite material Substances 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 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 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 229910021472 group 8 element Inorganic materials 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 241000264877 Hippospongia communis Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000243 solution Substances 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
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 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
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 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
- 239000000969 carrier Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000002156 mixing Methods 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
- 150000003609 titanium compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 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 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture 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
- 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
- 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
- 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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 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
- 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 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
- 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
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 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
- 239000002245 particle Substances 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
- 239000002002 slurry Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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- Catalysts (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 The catalytic combustion method of burning a combustible gas such as carbon monoxide, hydrogen, or hydrocarbon in the presence of an oxidation catalyst has been studied mainly for purifying automobile exhaust gas, and many oxidation catalysts have been developed. Has been done. 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
コージュ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
Using ceramics such as cordierite and mullite as the base material
And γ-Al on this substrate2O 3(Gamma alumina), di
Luconia, magnesia, α-Al2O3(Alpha Al
As a active ingredient, wash coat a carrier such as Mina)
Precious metals such as Pt, Pt + Pd, Pd, Pt + Rh,
Rubic acid of base metals such as cobalt, nickel and manganese
The compound 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 show high activity with respect to carbon monoxide and propane, they are inferior in performance to more stable methane, and at present, to methane. Many problems remain in its 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）ジルコニウム及びチタニウムの複合酸化物を担体
としてＩｂ族、Ｖａ族、VIａ族、VII ａ族、VIII族元素
の金属またはその酸化物を一種以上及び希土類元素の酸
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。The present invention provides (1) one or more metals of Ib group, Va group, VIa group, VIIa group, and VIII group elements or oxides thereof using a complex oxide of zirconium and titanium as a carrier. And an oxide of a rare earth element and zirconium oxide supported on the oxidation catalyst.
【０００９】（２）ジルコニウム及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）項記載の酸化触媒。(2) The oxidation catalyst according to (1) above, which is formed by molding a composite oxide of zirconium and titanium into a honeycomb shape.
【００１０】（３）コージェライト、ムライトまたはＭ
ｇＯ，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。である。(3) Cordierite, mullite or M
An oxidation catalyst comprising a honeycomb heat-resistant base material selected from crystalline composite oxides composed of gO, Al 2 O 3 and TiO 2 and coated with the catalyst according to the above item (1). Is.
【００１１】[0011]
【作用】本発明にいうジルコニウム及びチタニウムの複
合酸化物とは、ＺｒＯ2 ：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。The composite oxide of zirconium and titanium referred to in the present invention means that the weight ratio of ZrO 2 : TiO 2 is 5:95.
It is an amorphous material having a composition of ˜95: 5 (a part of which is crystallized but is amorphous as a whole) and is manufactured by the following method.
【００１２】 ジルコニウムの化合物及びチタニウム
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。A basic precipitant such as ammonia water or an aqueous solution of sodium carbonate is added to an aqueous solution of a zirconium compound and a titanium compound to wash the resulting precipitate, which is dried and calcined at 500 ° C. or higher.
【００１３】 ジルコ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。After mixing a hydroxide or oxide of zirconium with an aqueous solution of a titanium compound, a precipitant is added to wash the resulting precipitate, which is then dried and calcined at 500 ° C. or higher.
【００１４】 ジルコ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。After mixing a hydroxide or oxide of zirconium 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.
【００１５】以上の方法で調製したジルコニウム及びチ
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 ，Ｔｉ
Ｏ2 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、５０
０℃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 zirconium-titanium composite oxide prepared by the above method is molded into a honeycomb form by adding a binder, or a slurry of the composite oxide is formed by cordierite, mullite or MgO, Al 2 O 3 , Ti.
A honeycomb heat-resistant base material selected from the crystalline composite oxides of O 2 is dipped and wash-coated, and 50
By baking at 0 ° C. or higher, a honeycomb-shaped carrier can be obtained.
【００１６】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Ａｌ化合物及び
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 means a magnesium compound such as magnesia, magnesium carbonate, magnesium hydroxide,
A 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 titanium oxide at 1300 to 1700 ° C. .
【００１７】次に、このようにして得られたジルコニウ
ム及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、VII ａ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。Next, the thus-obtained composite oxide of zirconium and titanium or a honeycomb-shaped carrier is loaded with a 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 the oxide of the above element, the carrier may be immersed in a nitrate aqueous solution of each element and then baked, and the metal of the above element may be supported. In this case, the carrier can be prepared by immersing the carrier in an aqueous solution of a compound of each element and then reducing with hydrogen.
【００１８】また、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。When a rare earth element oxide or zirconium oxide is carried, a rare earth element nitrate aqueous solution,
The carrier may be baked after being dipped in the aqueous zirconium oxynitrate solution.
【００１９】Ｉｂ族、Ｖａ族、VIａ族、VII ａ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、
酸化ジルコニウムを担持する方法としては、上記の方法
でいずれかをあらかじめ担持した後、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。Group Ib, Group Va, Group VIa, Group VIIa, Group VIII
Group Group metals or their oxides and rare earth element oxides,
As a method of supporting zirconium oxide, after supporting any one of the above methods in advance, a method of supporting another oxide, or a method of supporting by calcination after immersing the carrier in an aqueous solution of a compound of both components Used.
【００２０】希土類元素の酸化物の一例としてはＬａ2
Ｏ3，ＣｅＯ2，Ｎｄ2Ｏ3などがあり、希土類元素の酸化
物、酸化ジルコニウムの担持量はジルコニウム及びチタ
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。La 2 is an example of an oxide of a rare earth element.
O 3 , CeO 2 , Nd 2 O 3 and the like are included, and the amount of the rare earth element oxide and zirconium oxide supported is preferably in the range of 1 to 30 parts by weight per 100 parts by weight of the zirconium and titanium composite oxide.
【００２１】Ｉｂ族、Ｖａ族、VIａ族、VII ａ族、VIII
族元素の金属または酸化物の一例としては、ＣｕＯ，Ｖ
2 Ｏ5 , Ｃｒ2 Ｏ3 ，ＭｎＯ2 ，Ｆｅ2 Ｏ3 , ＮｉＯ，
ＣｏＯ，ＰｄＯ，Ｐｔ，Ｐｄ，Ｒｈ，Ｒｕなどがあり、
その担持量はジルコニウム及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。Ib group, Va group, VIa group, VIIa group, VIII
As an example of a metal or oxide of a group element, CuO, V
2 O 5 , Cr 2 O 3 , MnO 2 , Fe 2 O 3 , NiO,
There are CoO, PdO, Pt, Pd, Rh, Ru, etc.,
The supported amount is preferably in the range of 0.1 to 100 parts by weight based on 100 parts by weight of zirconium and titanium composite oxide.
【００２２】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。The catalyst obtained as described above is suitable for the oxidation reaction of gases such as hydrogen, carbon monoxide and hydrocarbon gas.
It exhibited excellent activity and durability. Hereinafter, the present invention will be specifically described with reference to examples.
【００２３】[0023]
（例１）オキシ硝酸ジルコ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
濾過、水洗、乾燥後５００℃で焼成して担体１（ＺｒＯ
2 ：ＴｉＯ2 の重量比 ５０：５０）を得た。 (Example 1) Mixing of zirconium oxynitrate and titanium chloride
Precipitate obtained by adding sodium carbonate solution to the combined solution
After being filtered, washed with water, dried, and baked at 500 ° C, the carrier 1 (ZrO
2: TiO250:50) was obtained.
【００２４】Ｚｒ（ＯＨ）4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濾過、水洗し乾燥後１０００℃
で焼成してＺｒＯ2 ：ＴｉＯ2 比の異なる担体２（Ｚｒ
Ｏ2 ：ＴｉＯ2 の重量比 ９０：１０）、担体３（Ｚｒ
Ｏ2 ：ＴｉＯ2 の重量比 ２０：８０）及び担体４（Ｚ
ｒＯ2 ：ＴｉＯ2 の重量比 １０：９０）を得た。Zr (OH) 4 powder was added to water, aqueous ammonia was added to a solution prepared by adding an aqueous solution of titanium chloride, and the resulting precipitate was filtered, washed with water, dried and dried at 1000 ° C.
After firing in a carrier 2 (ZrO 2 : TiO 2 ratio different).
O 2 : TiO 2 weight ratio 90:10), carrier 3 (Zr
O 2 : TiO 2 weight ratio 20:80) and carrier 4 (Z
A weight ratio of rO 2 : TiO 2 of 10:90) was obtained.
【００２５】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、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、酸化ジルコニウムをそれぞれ５重量％（担体１０
０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。また担体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。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 each of lanthanum oxide and zirconium oxide. Carrier 10
The supported pellets were immersed in an aqueous palladium nitrate solution, dried, and calcined at 500 ° C. to prepare catalysts 1 to 4, respectively. Further, the pellets of the carrier 1 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. to prepare catalysts 5 to 7.
【００２６】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.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 [Table 2]
【００２９】（例２）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、硝酸ラン
タン、硝酸セリウム、硝酸ネオジウムの各水溶液及びオ
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, copper nitrate, vanadium nitrate, manganese nitrate, iron nitrate, nickel nitrate, cobalt nitrate aqueous solutions, lanthanum nitrate, cerium nitrate and neodymium nitrate were prepared. It was immersed in a mixed aqueous solution of an aqueous solution and an aqueous zirconium oxynitrate solution, dried and then calcined at 500 ° C. for 5 hours to prepare catalysts 8 to 13.
【００３０】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.
【００３１】[0031]
【表３】 [Table 3]
【００３２】（例３）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 Catalysts 8 to 13 prepared in Example 2 were immersed in an aqueous palladium nitrate solution and then calcined at 500 ° C. to prepare catalysts 14 to 19.
【００３３】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 using a gas containing 1% of methane (the balance of air) at a gas space velocity of 50,000 h −1 and a reaction temperature of 400 ° C., and the results are shown in Table 4. Table 4 also shows the results after the 1000-hour activity evaluation test.
【００３４】[0034]
【表４】 [Table 4]
【００３５】（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 ・５Ｓｉ
Ｏ2 ）基材またはＭｇＯ，Ａｌ2 Ｏ3 ，ＴｉＯ2 よりな
る結晶性複合酸化物（ＭｇＯ・４Ａｌ 2 Ｏ3 ・６ＴｉＯ
2 ）基材を用い、担体３のＺｒＯ2 ：ＴｉＯ2 （２０：
８０）粉末にＬａ2Ｏ3を５wt％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。ＺｒＯ2 ：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。Example 4 With a diameter of 1 inch, 1 square inch
Honeycomb having 200 openings (200 cells)
Cordierite (2MgO / 2Al)2O3・ 5Si
O2) Base material or MgO, Al2O3, TiO2More
Crystalline composite oxide (MgO.4Al 2O3・ 6TiO
2) Using a base material, ZrO of the carrier 32: TiO2(20:
80) La powder2O3The above-mentioned base material carrying 5 wt% of
Honeycomb by washcoating and baking at 1000 ℃
Carriers A and B were obtained. ZrO2: TiO2Hani coat amount
It was 40 parts by weight per 100 parts by weight of the cam carrier.
【００３６】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 dipped in an aqueous solution of palladium nitrate, dried and calcined at 500 ° C., further dipped in an aqueous solution of zirconium oxynitrate, dried and calcined at 500 ° C. to obtain catalysts 20 and 21.
【００３７】これらの触媒、及びさらに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 further 1 at 1100 ° C.
The activity of the catalyst calcined for 000 hours was evaluated under the conditions of gas space velocity 300,000 h −1 and catalyst layer inlet gas temperature 400 ° C. using a gas containing 3% of methane (the balance of air).
Got the result.
【００３８】[0038]
【表５】 [Table 5]
【００３９】[0039]
【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 23/84 ３０１ Ｍ 8017−4Ｇ ３１１ Ｍ 8017−4Ｇ 23/89 Ｍ 8017−4Ｇ Continuation of front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location B01J 23/84 301 M 8017-4G 311 M 8017-4G 23/89 M 8017-4G
Claims (3)
物を担体としてＩｂ族、Ｖａ族、VIａ族、VII ａ族、VI
II族元素の金属またはその酸化物を一種以上及び希土類
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, and VI using a complex oxide of zirconium and titanium as a carrier.
An oxidation catalyst comprising a group II element metal or one or more oxides thereof, a rare earth element oxide, and zirconium oxide.
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の酸化触媒。2. The oxidation catalyst according to claim 1, which is obtained by molding a composite oxide of zirconium 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 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 |
|---|---|---|---|
| JP5001103A JPH06205973A (en) | 1993-01-07 | 1993-01-07 | Oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5001103A JPH06205973A (en) | 1993-01-07 | 1993-01-07 | Oxidation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06205973A true JPH06205973A (en) | 1994-07-26 |
Family
ID=11492154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5001103A Withdrawn JPH06205973A (en) | 1993-01-07 | 1993-01-07 | Oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06205973A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001314763A (en) * | 2000-05-10 | 2001-11-13 | Johnson Matthey Japan Inc | CARRIER FOR NOx ABSORBING AND REDUCING CATALYST AND NOx ABSORBING AND REDUCING CATALYST USING THE SAME |
| US6582671B1 (en) * | 1997-07-16 | 2003-06-24 | Mitsubishi Heavy Industries, Ltd. | Method for reducing oxygen content in a boiler exhaust gas |
| JP2009101257A (en) * | 2007-10-19 | 2009-05-14 | Inst Nuclear Energy Research Rocaec | Carbon monoxide selective oxidation catalyst using vermiculite (expanded vermiculite) as support |
| JP2012126616A (en) * | 2010-12-16 | 2012-07-05 | Toyota Central R&D Labs Inc | Co oxidation catalyst and exhaust gas cleaning method using the same |
-
1993
- 1993-01-07 JP JP5001103A patent/JPH06205973A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6582671B1 (en) * | 1997-07-16 | 2003-06-24 | Mitsubishi Heavy Industries, Ltd. | Method for reducing oxygen content in a boiler exhaust gas |
| JP2001314763A (en) * | 2000-05-10 | 2001-11-13 | Johnson Matthey Japan Inc | CARRIER FOR NOx ABSORBING AND REDUCING CATALYST AND NOx ABSORBING AND REDUCING CATALYST USING THE SAME |
| JP2009101257A (en) * | 2007-10-19 | 2009-05-14 | Inst Nuclear Energy Research Rocaec | Carbon monoxide selective oxidation catalyst using vermiculite (expanded vermiculite) as support |
| JP2012126616A (en) * | 2010-12-16 | 2012-07-05 | Toyota Central R&D Labs Inc | Co oxidation catalyst and exhaust gas cleaning method using the same |
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