JP2018047425A - Oxygen absorbing and releasing material - Google Patents
Oxygen absorbing and releasing material Download PDFInfo
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- JP2018047425A JP2018047425A JP2016184426A JP2016184426A JP2018047425A JP 2018047425 A JP2018047425 A JP 2018047425A JP 2016184426 A JP2016184426 A JP 2016184426A JP 2016184426 A JP2016184426 A JP 2016184426A JP 2018047425 A JP2018047425 A JP 2018047425A
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- 239000001301 oxygen Substances 0.000 title claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000002131 composite material Substances 0.000 claims abstract description 44
- 238000006467 substitution reaction Methods 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims description 16
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 2
- 239000010436 fluorite Substances 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 42
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 42
- 239000007789 gas Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000446 fuel Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 229910014211 My O Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
Description
本発明は、セリア・ジルコニア系複合酸化物からなる酸素吸放出材料に関し、特に排ガス浄化触媒における助触媒として使用される酸素吸放出量の大きな酸素吸放出材料に関するものである。 The present invention relates to an oxygen storage / release material comprising a ceria / zirconia composite oxide, and more particularly to an oxygen storage / release material having a large oxygen storage / release amount used as a co-catalyst in an exhaust gas purification catalyst.
ガソリンエンジンの排ガス浄化に使用される三元触媒において、貴金属の働きを高めるためには、燃料と空気の比（空燃比）を一定（理論空燃比）に保つのが好ましいが加速、減速、低速走行、高速走行等の運転状況に応じて空燃比は大きく変化する。このため、酸素センサーを用いたフィードバック制御によりエンジンの作動条件によって変動する空燃比Ａ（空気）／Ｆ（燃料）を一定に保つようにしているが、フィードバック時間に応じたＡ／Ｆの時間的な変動が発生するため、エンジン制御のみで排気ガス雰囲気を理論空燃比あるいはその近傍に保持することは難しいため、触媒側で排ガス雰囲気を微調整する必要が有る。 In the three-way catalyst used for exhaust gas purification of gasoline engines, it is preferable to keep the ratio of fuel to air (air-fuel ratio) constant (theoretical air-fuel ratio) to enhance the function of precious metals, but acceleration, deceleration, and low-speed The air-fuel ratio changes greatly depending on the driving situation such as running and high-speed running. For this reason, the air-fuel ratio A (air) / F (fuel), which fluctuates depending on the operating conditions of the engine, is kept constant by feedback control using an oxygen sensor. Therefore, it is difficult to maintain the exhaust gas atmosphere at or near the stoichiometric air-fuel ratio only by engine control, so it is necessary to finely adjust the exhaust gas atmosphere on the catalyst side.
すなわち、触媒側で雰囲気を排ガス中の酸素濃度が高いときには酸素を吸蔵し、排ガス中の酸素濃度が低いときには酸素を放出して微調整する必要が有り、セリア（酸化セリウムＣｅＯ２）は、排ガス中の酸素濃度が高いときに酸素を吸蔵でき、排ガス中の酸素濃度が低いときに酸素を放出できる酸素吸放出能（Ｏｘｙｇｅｎ Ｓｔｏｒａｇｅ Ｃａｐａｃｉｔｙ、以下単に「ＯＳＣ」ということがある）を有するため、自動車排ガス浄化用触媒の酸素分圧調整用の助触媒として広く用いられている。これはＣｅ３＋／Ｃｅ４＋のレドックス反応を利用したものである。前記セリアは、一般にその特性を高めるためジルコニア（酸化ジルコニウムＺｒＯ２）と固溶させたセリア・ジルコニア系複合酸化物として使用されている。セリア・ジルコニア系複合酸化物に求められるＯＳＣ能として酸素吸放出量（以下単に「ＯＳＣ量」ということがある）がある。排ガス雰囲気を理論空燃比に長く保持するために、ＯＳＣ量が高い、すなわちＣｅ利用率［複合酸化物のＯＳＣ理論値（Ｃｅが１００％ＯＳＣに使用された場合のＯＳＣ）に対する、ＯＳＣ実測値の割合（実測値／理論値）］が高いセリア・ジルコニア複合酸化物が求められている。 That is, when the oxygen concentration in the exhaust gas is high on the catalyst side, oxygen must be occluded, and when the oxygen concentration in the exhaust gas is low, oxygen must be released and finely adjusted. Ceria (cerium oxide CeO 2 ) Oxygen storage capacity (hereinafter sometimes simply referred to as “OSC”) that can store oxygen when the oxygen concentration in the exhaust gas is high and can release oxygen when the oxygen concentration in the exhaust gas is low. It is widely used as a co-catalyst for adjusting the oxygen partial pressure of exhaust gas purification catalysts. This utilizes the redox reaction of Ce 3+ / Ce 4+ . In general, the ceria is used as a ceria / zirconia-based composite oxide which is solid-solved with zirconia (zirconium oxide ZrO 2 ) in order to enhance its properties. As the OSC ability required for the ceria / zirconia composite oxide, there is an oxygen absorption / release amount (hereinafter sometimes simply referred to as “OSC amount”). In order to keep the exhaust gas atmosphere at the stoichiometric air-fuel ratio for a long time, the amount of OSC is high, that is, the Ce utilization factor [the OSC theoretical value of composite oxide (OSC when Ce is used for 100% OSC)] A ceria / zirconia composite oxide having a high ratio (measured value / theoretical value) is required.
セリア・ジルコニア系酸化物のＯＳＣ量に関する先行技術としては、例えば、特許文献１、特許文献２、特許文献３が有り、ＯＳＣ量の増加に向けて組成や構造より開発がなされていた。 For example, Patent Document 1, Patent Document 2, and Patent Document 3 are prior arts related to the amount of OSC of ceria / zirconia-based oxide, and development has been made from the composition and structure to increase the amount of OSC.
すなわち、特許文献１では、Ｃｅ含有量が５〜１５ｍａｓｓ％のセリア・ジルコニア系酸化物に特定量の希土類元素を含有させることでＣｅ利用率が９０％以上にできるとしている。しかしながら、Ｃｅ含有量が５〜１５ｍａｓｓ％のセリア・ジルコニア系酸化物のＯＳＣ理論量は７３〜２２０μｍｏｌ−Ｏ２／ｇであり、一般的なセリア・ジルコニア複合酸化物と比較してＯＳＣ量が高い材料ではない。 That is, in Patent Document 1, the Ce utilization rate can be increased to 90% or more by adding a specific amount of rare earth element to a ceria / zirconia oxide having a Ce content of 5 to 15 mass%. However, the ceria / zirconia-based oxide having a Ce content of 5 to 15 mass% has a theoretical amount of OSC of 73 to 220 μmol-O 2 / g, and the amount of OSC is higher than that of a general ceria / zirconia composite oxide. Not a material.
特許文献２では、コアが平均粒子径Ｄ５０は、９ｎｍ〜２５ｎｍであるジルコニア、コアの表面にセリア・ジルコニアが存在しているＯＳＣ材であり、そのＯＳＣ材のＣｅ利用率は８００℃において９１％〜９７％を示す材料であるとしている。しかしながら、Ｃｅ含有量が１０〜２０ｍｏｌ％のセリア・ジルコニア系酸化物のＯＳＣ理論量は７３〜２２０μｍｏｌ％−Ｏ２／ｇであり、一般的なセリア・ジルコニア複合酸化物と比較してＯＳＣ量が高い材料ではない。 In Patent Document 2, the core is an OSC material having an average particle diameter D50 of 9 nm to 25 nm and ceria / zirconia on the surface of the core, and the Ce utilization rate of the OSC material is 91% at 800 ° C. It is said that the material exhibits ˜97%. However, the ceria / zirconia-based oxide having a Ce content of 10 to 20 mol% has a theoretical OSC amount of 73 to 220 μmol% -O 2 / g, and has a higher OSC amount than a general ceria / zirconia composite oxide. Not a material.
特許文献３では、パイロクロア構造のセリア・ジルコニア系酸化物は多くの酸素を吸放出でき、Ｃｅ利用率は１００％程度を示す。しかし、パイロクロア構造にするためにはセリア・ジルコニアの調製工程に還元雰囲気かつ高温での焼成工程が追加されるために、製造コストの面でデメリットが生じる。また、高温での焼成を行うために比表面積が数ｍ２／ｇと小さく、ガスとの接触面積が少ない点もデメリットとして挙げられる。 In Patent Document 3, the ceria / zirconia oxide having a pyrochlore structure can absorb and release a large amount of oxygen, and the Ce utilization rate is about 100%. However, since a pyrochlore structure is added to the ceria / zirconia preparation process, a reducing atmosphere and a high-temperature baking process are added, resulting in a disadvantage in terms of manufacturing cost. Another disadvantage is that the specific surface area is as small as several m 2 / g and the contact area with the gas is small in order to perform firing at a high temperature.
上述のようにセリア・ジルコニア系酸化物は、これまで自動車排ガス浄化触媒等において貴金属の働きを高めるため、高いＯＳＣ値や大きな比表面積が要求され、それらに対応した開発が行われてきた。 As described above, ceria / zirconia oxides have so far been required to have a high OSC value and a large specific surface area in order to enhance the action of noble metals in automobile exhaust gas purification catalysts and the like, and have been developed accordingly.
しかし、蛍石型結晶構造かつＣｅ含有量が３０ｍｏｌ％以上のセリア・ジルコニア系酸化物においてＣｅ利用率が高いＯＳＣ材はなかったのが実情である。 However, there is no OSC material having a high Ce utilization rate in ceria / zirconia oxides having a fluorite crystal structure and a Ce content of 30 mol% or more.
本発明は、上記実情に鑑みてなしたものであり、Ｃｅ含有量が３０ｍｏｌ％以上でＣｅ利用率が９０％以上となる立方晶系（蛍石型結晶構造）であるセリア・ジルコニア系複合酸化物からなる酸素吸放出材料を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is a ceria-zirconia composite oxide that is a cubic system (fluorite-type crystal structure) in which the Ce content is 30 mol% or more and the Ce utilization rate is 90% or more. An object of the present invention is to provide an oxygen storage / release material composed of a material.
本発明者らは、上記課題を解決すべく鋭意研究し、セリア・ジルコニア系複合酸化物は格子定数５３４ｐｍ以上にすることで、ＯＳＣ量が高い、すなわちＣｅ利用率が９０％以上である酸素吸放出材料とすることができることを見出し、本発明を完成するに至った。 The present inventors have intensively studied to solve the above-mentioned problems, and by setting the ceria-zirconia composite oxide to have a lattice constant of 534 pm or higher, the oxygen absorption is high, that is, the Ce utilization is 90% or higher. The present inventors have found that the material can be a release material and have completed the present invention.
すなわち、本発明の要旨は、以下のとおりである。 That is, the gist of the present invention is as follows.
（１）セリア・ジルコニア系複合酸化物ＣｅｘＺｒ１−ｘ−ｙＭｙＯ２−ｙ／２であって、Ｃｅ含有量ｘが０．３０を超え、置換元素Ｍの含有量ｙが０を超え０．２以下で、ＭにはＣｅ４＋イオン半径より大きなイオン半径を有する少なくとも３種類のＣｅを除く希土類元素およびアルカリ土類金属元素を含み、立方晶系であって結晶の格子定数ａが５３４ｐｍ以上であることを特徴とする酸素吸放出材料。 (1) Ceria / zirconia composite oxide Ce x Zr 1- xy My O 2 -y / 2 , Ce content x exceeds 0.30, and substitution element M content y is 0 More than 0.2 and less than or equal to 0.2, and M contains at least three kinds of rare earth elements and alkaline earth metal elements excluding Ce having an ion radius larger than the Ce 4+ ion radius, is a cubic system, and has a crystal lattice constant a Oxygen storage / release material, characterized in that is 534 pm or more.
（２）前記置換元素Ｍの含有量ｙが０．１を超え０．２以下であることを特徴とする上記（１）または（２）記載の酸素吸放出材料。 (2) The oxygen storage / release material according to (1) or (2), wherein the content y of the substitution element M is more than 0.1 and 0.2 or less.
（３）前記置換元素Ｍの含有量ｙが０．１５を超え０．２以下であることを特徴とする上記（１）または（２）記載の酸素吸放出材料。 (3) The oxygen storage / release material as described in (1) or (2) above, wherein the content y of the substitution element M is more than 0.15 and 0.2 or less.
（４）前記置換元素ＭとしてＹ、Ｎｄ、Ｌａのうち少なくとも１元素が置換されている上記（１）〜（３）のいずれかに記載の酸素吸放出材料。 (4) The oxygen storage / release material according to any one of (1) to (3), wherein at least one element of Y, Nd, and La is substituted as the substitution element M.
本発明のＣｅ含有量が３０ｍｏｌ％以上であるセリア・ジルコニア系複合酸化物からなるＣｅ利用率が９０％以上の酸素吸放出材料を自動車排ガス浄化触媒に使用すれば、走行状態に応じて刻々と変化する排ガス雰囲気の変動を緩和し、排ガス雰囲気を理論空燃比に長く保持することが出来、これまで以上に貴金属の有害成分浄化性能が高くなる。 If an oxygen storage / release material having a Ce utilization ratio of 90% or more made of a ceria / zirconia composite oxide having a Ce content of 30 mol% or more according to the present invention is used for an automobile exhaust gas purification catalyst, it is momentarily according to the running state. The fluctuation of the changing exhaust gas atmosphere can be alleviated, and the exhaust gas atmosphere can be maintained at the stoichiometric air-fuel ratio for a long time.
以下本発明を詳細に説明する。 The present invention will be described in detail below.
本発明のセリア・ジルコニア系複合酸化物ＣｅｘＺｒ１−ｘ−ｙＭｙＯ２−ｙ／２とは、Ｃｅ含有量ｘが０．３０以上であって、置換元素Ｍは少なくとも３種類のＣｅを除く希土類元素（Ｙ、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｙｂ等）およびアルカリ土類金属元素（Ｃａ、Ｓｒ等）を含み、置換元素Ｍにより一部置換されていて、立方晶系であって結晶の格子定数ａが５３４ｐｍ以上であるセリア・ジルコニア系複合酸化物である。 The ceria-zirconia-based composite oxide Ce x Zr 1- xy My O 2-y / 2 of the present invention has a Ce content x of 0.30 or more, and the substitution element M includes at least three kinds It contains rare earth elements (Y, La, Pr, Nd, Sm, Yb, etc.) excluding Ce and alkaline earth metal elements (Ca, Sr, etc.), and is partially substituted by the substitution element M, and has a cubic system. This is a ceria / zirconia composite oxide having a crystal lattice constant a of 534 pm or more.
Ｃｅ含有量ｘの範囲は０．３０以上が好ましい。一般的にＣｅ含有量ｘが０．３０未満のセリア・ジルコニア複合酸化物のＣｅ利用率は１００％程度を示すため、Ｃｅ含有量ｘの範囲は０．３０以上とした。より好ましくは０．３３以上である。Ｃｅ含有量の上限は０．９０以下であるのが望ましい。Ｃｅ含有量が０．９０を超えると、Ｃｅ量が多く、Ｃｅの価数変動が起こりにくくなるためである。特に効果がみられる置換元素として、Ｙ、Ｌａ、Ｎｄが挙げられる。置換元素の選定としてはＣｅ４＋よりもイオン半径が大きい元素である。（例えば、Ｃｅ４＋：９７ｐｍ、Ｙ3＋：１０１．９ｐｍ、Ｌａ3＋：１１６ｐｍ、Ｐｒ3＋：１１２．６ｐｍ、Ｎｄ3＋：１１０．９ｐｍ、Ｓｍ3＋：１０７．９ｐｍ、Ｙｂ3＋：９８．５ｐｍ、Ｃａ2＋：１１２ｐｍ、Ｓｒ2＋：１２６ｐｍ）。Ｃｅ４＋のイオン半径よりも大きい元素を３種類以上置換することによって、セリア・ジルコニア複合酸化物内に各置換元素が一様に分布するため、セリア・ジルコニアの格子が広がる。置換元素の種類数の上限は特に限定するものではないが、効果が飽和するので５種以下とすることが好ましい。置換元素が２種類以下になると置換元素同士で分布してしまうため、置換元素が２種類以下では格子を広げる効果は見られない。したがって、本発明では置換元素を少なくとも３種以上とした。 The range of Ce content x is preferably 0.30 or more. In general, the Ce utilization rate of a ceria-zirconia composite oxide having a Ce content x of less than 0.30 is about 100%, so the range of the Ce content x is 0.30 or more. More preferably, it is 0.33 or more. The upper limit of Ce content is desirably 0.90 or less. This is because when the Ce content exceeds 0.90, the amount of Ce is large and the valence fluctuation of Ce is difficult to occur. Examples of substitution elements that are particularly effective include Y, La, and Nd. The substitution element is selected with an ionic radius larger than that of Ce 4+ . (For example, Ce 4+ : 97 pm, Y 3+ : 101.9 pm, La 3+ : 116 pm, Pr 3+ : 112.6 pm, Nd 3+ : 110.9 pm, Sm 3+ : 107.9 pm, Yb 3+ : 98.5 pm, Ca 2+ : 112 pm, Sr 2+ : 126 pm). By substituting three or more elements larger than the ion radius of Ce 4+ , each substitution element is uniformly distributed in the ceria / zirconia composite oxide, so that the ceria / zirconia lattice is expanded. The upper limit of the number of types of substitution elements is not particularly limited, but is preferably 5 or less because the effect is saturated. When the number of substitution elements is two or less, the substitution elements are distributed with each other. Therefore, when the number of substitution elements is two or less, the effect of expanding the lattice is not observed. Accordingly, in the present invention, at least three or more substitution elements are used.
本発明に関わるＣｅ利用率９０％以上の酸素吸放出材料としてのセリア・ジルコニア系複合酸化物ＣｅｘＺｒ１−ｘ−ｙＭｙＯ２−ｙ／２は、Ｘ線回折装置で測定された（１１１）面の格子定数が５３4ｐｍ以上であることが望ましい。セリア・ジルコニア系複合酸化物の格子定数の上限は特に限定するものではないが、望ましくは５４１ｐｍ以下である。 The ceria-zirconia-based composite oxide Ce x Zr 1- xy My O 2-y / 2 as an oxygen storage / release material having a Ce utilization rate of 90% or more according to the present invention was measured with an X-ray diffractometer. It is desirable that the lattice constant of the (111) plane is 534 pm or more. The upper limit of the lattice constant of the ceria / zirconia composite oxide is not particularly limited, but is desirably 541 pm or less.
Ｃｅ利用率を向上させるためには立方晶系の結晶の格子定数(以下単に格子定数ということがある)を５３４ｐｍ以上にすることが必要で、立方晶系の結晶の格子定数を５３４ｐｍ以上にするためには、置換量は特に限定しないが、セリア・ジルコニア系酸化物の置換元素量ｙは０．１を超え０．２以下が好ましく、置換効果をより大きく得るためには０．１以上０．２以下、より好ましくは０．１５以上０．２以下である。 In order to improve the Ce utilization rate, it is necessary to set the lattice constant of the cubic crystal (hereinafter sometimes simply referred to as “lattice constant”) to 534 pm or more, and to set the lattice constant of the cubic crystal to 534 pm or more. For this purpose, the amount of substitution is not particularly limited, but the amount of substitution element y of the ceria / zirconia oxide is preferably more than 0.1 and not more than 0.2. .2 or less, more preferably 0.15 or more and 0.2 or less.
格子定数を５３４ｐｍ以上とするとＣｅ利用率が向上する理由は完全には解明されていないが、以下のように推定している。すなわち、セリア・ジルコニア複合酸化物ではＣｅが４価から３価に変化することにより、酸素が放出される。Ｃｅのイオン半径はＣｅ３＋とＣｅ４＋で異なり、Ｃｅ３＋の方が大きく、酸素を放出する際はＣｅのイオン半径は大きくなる。Ｃｅのイオン半径が大きくなるためには格子内にスペースが必要だが、従来のセリア・ジルコニア複合酸化物ではＣｅ４＋がＣｅ３＋となるための十分なスペースがない。 The reason why the Ce utilization rate is improved when the lattice constant is 534 pm or more has not been completely clarified, but is estimated as follows. That is, in the ceria-zirconia composite oxide, oxygen is released by changing Ce from tetravalent to trivalent. The ionic radius of Ce is different between Ce 3+ and Ce 4+ . Ce 3+ is larger, and when oxygen is released, the ionic radius of Ce is larger. In order to increase the ion radius of Ce, a space is required in the lattice. However, in the conventional ceria / zirconia composite oxide, there is not enough space for Ce 4+ to become Ce 3+ .
その理由としてはＺｒ４＋のイオン半径はＣｅ４＋よりも小さく、主にＣｅとＺｒで構成されるセリア・ジルコニア複合酸化物の格子の大きさ（格子定数）はＣｅ４＋にとって小さいためである。Ｃｅ３＋と比較して小さいＣｅ４＋にとっても小さい格子のなかでさらに大きなＣｅ３＋への変化は難しくその結果、従来のセリア・ジルコニア複合酸化物においてすべてのセリアが価数変動できないため、ＯＳＣ理論量で発揮できるセリア・ジルコニアが存在しないと推定される。ここで、セリア・ジルコニア系複合酸化物の格子定数を５３４ｐｍ以上とすると、パイロクロア構造のセリア・ジルコニア系複合酸化物の（２２２）面から計算される格子定数の大きさとほぼ等しくなる。セリア・ジルコニア系複合酸化物の格子定数をパイロクロア構造のセリア・ジルコニア系複合酸化物と同等以上の格子にすることで、粒子内のＣｅの価数変動が容易となり配合されたほぼ全てのＣｅが価数変化できるようになり、Ｃｅ利用率が高まる。 This is because the ion radius of Zr 4+ is smaller than that of Ce 4+ and the lattice size (lattice constant) of the ceria / zirconia composite oxide mainly composed of Ce and Zr is small for Ce 4+ . Change in addition to a large Ce 3+ among very small lattice small ce 4+ compared to Ce 3+ is difficult as a result, since all the ceria in the conventional ceria-zirconia composite oxide is not a valence, OSC theory It is estimated that there is no ceria or zirconia that can be exhibited in Here, when the lattice constant of the ceria / zirconia composite oxide is 534 pm or more, the lattice constant is approximately equal to the size of the lattice constant calculated from the (222) plane of the ceria / zirconia composite oxide having a pyrochlore structure. By making the lattice constant of the ceria-zirconia composite oxide to be equal to or greater than that of the pyrochlore-structured ceria-zirconia composite oxide, the valence change of Ce in the particles is facilitated and almost all of the blended Ce is contained. The valence can be changed, and the Ce utilization rate is increased.
格子定数を高めるためにＣｅ、Ｚｒ以外の元素Ｍを置換するが、置換元素Ｍを増やした量だけ酸素吸放出を行うＣｅイオン量が減ることや第三成分が多いと格子歪みが生じ、蛍石構造を保つことが難しくなる問題があり、格子定数は５４１ｐｍ程度より大きくする必要はない。格子定数が５３４ｐｍ未満の場合、セリウムの価数変動が起こりにくく、Ｃｅ利用率が大きくならない。したがって、本発明では立方晶系であって結晶の格子定数ａが５３４ｐｍ以上と規定した。 In order to increase the lattice constant, elements M other than Ce and Zr are substituted. However, when the amount of Ce ions that absorb and release oxygen is reduced by the increased amount of the substituted element M or when the third component is large, lattice distortion occurs and There is a problem that it is difficult to maintain the stone structure, and the lattice constant does not need to be larger than about 541 pm. When the lattice constant is less than 534 pm, the valence change of cerium hardly occurs and the Ce utilization rate does not increase. Therefore, in the present invention, the crystal system is cubic and the crystal lattice constant a is defined to be 534 pm or more.
本発明のセリア・ジルコニア系複合酸化物でＯＳＣ量が高い自動車排ガス浄化触媒に使用すれば、変化する排ガス雰囲気を理論空燃比に長く保持することが出来る。 If the ceria / zirconia composite oxide of the present invention is used for an automobile exhaust gas purification catalyst having a high OSC amount, the changing exhaust gas atmosphere can be maintained at a stoichiometric air-fuel ratio for a long time.
以下に実施例（発明例）、比較例を用いて本発明の作用効果を具体的に説明するが、本発明はこれらに限定されるものではない。 Although the effect of this invention is concretely demonstrated using an Example (invention example) and a comparative example below, this invention is not limited to these.
まず、ＯＳＣ量(μｍｏｌ％−Ｏ２／ｇ)、Ｃｅ利用率（％）および格子定数ａ(pm)の算出方法について説明する。 First, a method for calculating the OSC amount (μmol% −O 2 / g), the Ce utilization rate (%), and the lattice constant a (pm) will be described.
ＯＳＣ量は以下のように測定される。アルミナパンに試料（セリア・ジルコニア系複合酸化物）を２０ｍｇ程度充填し、熱重量分析計にセットする。試料を５％Ｈ２／Ａｒ流通下、８００℃で１時間還元処理を行う。還元処理前後における重量変化を試料のＯＳＣ量として算出した。 The amount of OSC is measured as follows. About 20 mg of a sample (ceria / zirconia composite oxide) is filled in an alumina pan and set in a thermogravimetric analyzer. The sample is subjected to reduction treatment at 800 ° C. for 1 hour under 5% H2 / Ar flow. The change in weight before and after the reduction treatment was calculated as the OSC amount of the sample.
また、Ｃｅ利用率（％）は、下記のように算出する。セリア・ジルコニア系複合酸化物内のセリアの価数変動は下記式（１）のように起こる。 Further, the Ce utilization rate (%) is calculated as follows. Ceria valence fluctuation in the ceria-zirconia composite oxide occurs as shown in the following formula (1).
４ＣｅＯ２ ⇔ 2Ｃｅ２Ｏ３+Ｏ２ ・・・（１）
式（１）よりＣｅが４ｍｏｌに対して、酸素は１ｍｏｌ放出される。ＣＺが１ｇで放出されるＯＳＣ量は下記式（２）のように表される。
4CeO 2 ⇔ 2Ce 2 O 3 + O 2 (1)
From the formula (1), 1 mol of oxygen is released with respect to 4 mol of Ce. The amount of OSC released by 1 g of CZ is expressed as the following formula (2).
ＯＳＣ量＝ＣＣｅ÷（ＭＣｅ＋２×ＭＯ）÷４÷１００・・・（２）
ここで、ＣＣｅ：試料内のＣｅ含有量（ｍａｓｓ％）、ＭＣｅ：Ｃｅ原子量（１４０．１１６ｇ／ｍｏｌ）、ＭＯ：Ｏ原子量（１６．０００ｇ／ｍｏｌ）
OSC amount = C Ce ÷ (M Ce + 2 × M O ) ÷ 4 ÷ 100 (2)
Here, C Ce : Ce content (mass%) in the sample, M Ce : Ce atomic weight (140.116 g / mol), M O : O atomic weight (16.000 g / mol)
実測したＯＳＣ量を式（２）より算出したＯＳＣ量で割り、パーセント表記にした値をＣｅ利用率とした。まとめると、下記式（３）のようになる。 The measured OSC amount was divided by the OSC amount calculated from the equation (2), and the value expressed in percent was used as the Ce utilization rate. In summary, the following equation (3) is obtained.
Ｃｅ利用率(％)＝A(μmol-O2/g）/｛Cce÷(140.116+32)÷4÷100×106｝・・・（３）
ここで、Ａ：試料のＯＳＣ量（μｍｏｌ−Ｏ２／％）、ＣＣｅ：試料内のＣｅ含有量（ｍａｓｓ％）
Ce utilization rate (%) = A (μmol-O 2 / g) / {C ce ÷ (140.116 + 32) ÷ 4 ÷ 100 × 10 6 } (3)
Here, A: OSC amount of sample (μmol-O 2 /%), C Ce : Ce content in sample (mass%)
また、格子定数は以下のように測定される。リガク製ＲＩＮＴ２０００を使用、Ｘ線源としてＣｕＫαを用い、管電流４０ｍＡ、管電圧３０ｋＶ、２θ＝１０．００°〜７０．０９°、ステップ幅：０．０３°、計測速度：０．１１１°／ｓｅｃｏｎｄの条件でＸ線回折パターンを測定した。得られたＸ線回折パターンにおいて２θ＝２８〜３０°付近に現れるセリア・ジルコニア系酸化物のミラー指数（１１１）面のピークを用いて、結晶の格子定数ａ（ｐｍ）を算出した。格子定数ａを算出するために、下記の数式（４）のブラッグの式より結晶面の間隔ｄを算出した。
The lattice constant is measured as follows. Rigaku RINT2000 is used, CuKα is used as the X-ray source, tube current 40 mA,
ｄ＝ｎλ／２ｓｉｎθ ・・・（４）
ここで、ｄ：結晶面の間隔、θ：結晶面とＸ線が成す角度、λ：Ｘ線の波長（１５４．１８ｐｍ＝１．５４１８Å）、ｎ：整数
d = nλ / 2 sin θ (4)
Here, d: crystal plane spacing, θ: angle formed by the crystal plane and X-ray, λ: wavelength of X-ray (154.18 pm = 1.5418Å), n: integer
得られるセリア・ジルコニア系複合酸化物は立方晶系であるため、下記式（５）より格子定数ａを算出した。 Since the obtained ceria / zirconia composite oxide is cubic, the lattice constant a was calculated from the following formula (5).
ａ＝（ｈ2+ｊ2+ｌ2）1/2×ｄ＝31/2×ｄ ・・・ （５）
ここで、ｄ：結晶面の間隔、θ：結晶面とＸ線が成す角度、ミラー指数（ｈｋｌ）：（１１１）
a = (h 2 + j 2 + l 2 ) 1/2 × d = 3 1/2 × d (5)
Where d: crystal plane spacing, θ: angle between crystal plane and X-ray, Miller index (hkl): (111)
式（４）を式（５）に代入すると、格子定数ａ（ｐｍ）は下記式（６）のようになる。 Substituting equation (4) into equation (5), the lattice constant a (pm) is as shown in equation (6) below.
ａ（ｐｍ）＝154.18×31/2／2ｓｉｎθ ・・・ （６）
ここで、θ：結晶面とX線が成す角度
a (pm) = 154.18 × 3 1/2 / 2 sin θ (6)
Where θ is the angle formed by the crystal plane and the X-ray
（実施例１）
塩化セリウム溶液、オキシ塩化ジルコニウム溶液、塩化プラセオジム溶液と純水を混合し、モル比でＣｅＯ２：ＺｒＯ２：Ｌａ２Ｏ３：Ｙ２Ｏ３：Ｎｄ２Ｏ３＝５７．９：２６．０：１０．２：４．０：１．９、０．４ｍｏｌ／ｌとなるような溶液１ｌ（リットル）を得た。得られた混合溶液にペルオキソ二硫酸アンモニウムを１５ｇ添加し、撹拌しながら９５℃まで加熱し、セリウム・ジルコニウム複合硫酸塩を得た。得られた硫酸塩スラリーを６０℃まで冷却後、アンモニア水を加えて中和し水酸化物を含むスラリーを得た。得られた水酸化物スラリーに対して濾過−洗浄操作を４回繰り返してセリウム・ジルコニウム複合水酸化物ケーキを得た。得られた複合水酸化物ケーキを１２０℃で乾燥して複合水酸化物粉末を得、これを坩堝につめ電気炉で７００℃にて３時間焼成し、セリア・ジルコニア系複合酸化物粉末を得た。
Example 1
A cerium chloride solution, a zirconium oxychloride solution, a praseodymium chloride solution and pure water are mixed, and CeO 2 : ZrO 2 : La 2 O 3 : Y 2 O 3 : Nd 2 O 3 = 57.9: 26.0 in a molar ratio. A solution of 1 l (liter) was obtained that had a ratio of 10.2: 4.0: 1.9 and 0.4 mol / l. 15 g of ammonium peroxodisulfate was added to the obtained mixed solution and heated to 95 ° C. with stirring to obtain a cerium-zirconium composite sulfate. The obtained sulfate slurry was cooled to 60 ° C. and neutralized by adding ammonia water to obtain a slurry containing hydroxide. Filtration-washing operation was repeated 4 times for the obtained hydroxide slurry to obtain a cerium-zirconium composite hydroxide cake. The obtained composite hydroxide cake was dried at 120 ° C. to obtain a composite hydroxide powder, which was put into a crucible and fired at 700 ° C. for 3 hours in an electric furnace to obtain a ceria / zirconia composite oxide powder. It was.
得られた粉末を前述のＸ線回折方法で格子定数を測定したところ、５４１ｐｍであった。 When the lattice constant of the obtained powder was measured by the aforementioned X-ray diffraction method, it was 541 pm.
さらに得られた粉末に対してＰｄを０．５ｍａｓｓ％の割合で含浸担持し、ＯＳＣ量の測定を行ったところ、ＯＳＣ量が９０９μｍｏｌ−Ｏ２／ｇ、Ｃｅ利用率が９８％との結果が得られた。 Furthermore, Pd was impregnated and supported on the obtained powder at a ratio of 0.5 mass%, and the amount of OSC was measured. As a result, the OSC amount was 909 μmol-O 2 / g, and the Ce utilization rate was 98%. Obtained.
（実施例２）
表１に示すように、配合組成をＣｅＯ２：ＺｒＯ２：Ｌａ２Ｏ３：Ｙ２Ｏ３：Ｎｄ２Ｏ３＝４９．６：３４．７：８．７：５．３：１．７とした以外は、実施例１と同様にしてセリア・ジルコニア系複合酸化物粉末を得た。
(Example 2)
As shown in Table 1, the composition was changed to CeO 2 : ZrO 2 : La 2 O 3 : Y 2 O 3 : Nd 2 O 3 = 49.6: 34.7: 8.7: 5.3: 1.7 A ceria / zirconia composite oxide powder was obtained in the same manner as in Example 1 except that.
得られた粉末を前述のＸ線回折方法で格子定数を測定したところ、５３８ｐｍであった。 When the lattice constant of the obtained powder was measured by the aforementioned X-ray diffraction method, it was 538 pm.
さらに得られた粉末に対してＰｄを０．５ｍａｓｓ％の割合で含浸担持し、ＯＳＣ量の測定を行ったところ、ＯＳＣ量が８０１μｍｏｌ−Ｏ２／ｇ、Ｃｅ利用率が９８％との結果が得られた。
（実施例３〜１０）
表１に示すように、配合組成を変化させて実施例１と同様に実施し、得られたＯＳＣ量及びＣｅ利用率を表１に併記した。
Furthermore, Pd was impregnated and supported on the obtained powder at a ratio of 0.5 mass%, and the amount of OSC was measured. As a result, the OSC amount was 801 μmol-O 2 / g, and the Ce utilization rate was 98%. Obtained.
(Examples 3 to 10)
As shown in Table 1, the composition was changed and the same procedure as in Example 1 was carried out. The obtained OSC amount and Ce utilization were also shown in Table 1.
（比較例１）
表１に示すように、配合組成をＣｅＯ２：ＺｒＯ２＝５０．０：５０．０とした以外は、実施例１と同様にしてセリア・ジルコニア系複合酸化物粉末を得た。得られた粉末を前述の方法で格子定数を測定したところ、５２６ｐｍであった。
(Comparative Example 1)
As shown in Table 1, ceria / zirconia composite oxide powder was obtained in the same manner as in Example 1 except that the composition was CeO 2 : ZrO 2 = 50.0: 50.0. When the lattice constant of the obtained powder was measured by the method described above, it was 526 pm.
さらに得られた粉末に対してＰｄを０．５ｍａｓｓ％の割合で含浸担持し、ＯＳＣ量の測定を行ったところ、ＯＳＣ量が５７３μｍｏｌ−Ｏ２／ｇ、Ｃｅ利用率が６８％との結果が得られた。 Furthermore, Pd was impregnated and supported on the obtained powder at a ratio of 0.5 mass%, and the amount of OSC was measured. As a result, the OSC amount was 573 μmol-O 2 / g and the Ce utilization rate was 68%. Obtained.
（比較例２）
表１に示すように、配合組成をＣｅＯ２：ＺｒＯ２：Ｌａ２Ｏ３＝５０．０：３７．５：１２．５とした以外は、実施例１と同様にしてセリア・ジルコニア系複合酸化物粉末を得た。
(Comparative Example 2)
As shown in Table 1, ceria and zirconia composite oxidation was carried out in the same manner as in Example 1 except that the composition was CeO 2 : ZrO 2 : La 2 O 3 = 50.0: 37.5: 12.5. A product powder was obtained.
得られた粉末を前述の方法で格子定数を測定したところ、５３３ｐｍであった。 When the lattice constant of the obtained powder was measured by the method described above, it was 533 pm.
さらに得られた粉末に対してＰｄを０．５ｍａｓｓ％の割合で含浸担持し、ＯＳＣ量の測定を行ったところ、ＯＳＣ量が６０７μｍｏｌ−Ｏ２／ｇ、Ｃｅ利用率が７４％との結果が得られた。 Furthermore, Pd was impregnated and supported on the obtained powder at a ratio of 0.5 mass%, and the amount of OSC was measured. As a result, the OSC amount was 607 μmol-O 2 / g, and the Ce utilization rate was 74%. Obtained.
（比較例３、４）
表１に示すように、配合組成を変化させて実施例１と同様に実施し、得られた格子定数、ＯＳＣ量及びＣｅ利用率を表１に併記した。
(Comparative Examples 3 and 4)
As shown in Table 1, the composition was changed and the same procedure as in Example 1 was performed. The obtained lattice constant, OSC amount, and Ce utilization were also shown in Table 1.
図１に比較例と実施例のＸ線回折パターンを示す。図１より実施例１におけるＸ線回折パターンにおいて（１１１）面のピークは２８．７°付近に見られた。比較例１におけるＸ線回折パターンにおいて（１１１）面のピークは２９．４°付近に見られた。式（２）を用いて格子定数を算出すると、実施例１の格子定数は５３９ｐｍ、比較例の格子定数は５２６ｐｍであった。比較例２〜４に関しても比較例１と同様な傾向を示し、格子定数は５２６〜５３１ｐｍであった。実施例２〜１０に関しても実施例１と同様な傾向を示し、格子定数は５３５〜５４１ｐｍであった。実施例の格子定数は比較例より高い値を示している。 FIG. 1 shows X-ray diffraction patterns of the comparative example and the example. As shown in FIG. 1, in the X-ray diffraction pattern of Example 1, the peak of the (111) plane was found near 28.7 °. In the X-ray diffraction pattern of Comparative Example 1, the peak of the (111) plane was found near 29.4 °. When the lattice constant was calculated using Equation (2), the lattice constant of Example 1 was 539 pm, and the lattice constant of the comparative example was 526 pm. Regarding Comparative Examples 2 to 4, the same tendency as Comparative Example 1 was exhibited, and the lattice constant was 526 to 531 pm. Examples 2 to 10 also showed the same tendency as Example 1, and the lattice constant was 535 to 541 pm. The lattice constant of the example is higher than that of the comparative example.
表１より実施例１〜１０で得られたセリア・ジルコニア系複合酸化物は、４価未満の価数を有する金属イオンが含まれ、格子定数が５３４ｐｍ以上である酸素吸放出材料となっていて、ＯＳＣ量、Ｃｅ利用率に優れた特性を満たしていた。 The ceria / zirconia composite oxides obtained in Examples 1 to 10 from Table 1 contain oxygen ions having a valence of less than 4 and are oxygen storage / release materials having a lattice constant of 534 pm or more. , OSC amount and Ce utilization ratio were satisfied.
一方で、比較例１〜４で得られたセリア・ジルコニア系複合酸化物の格子定数が５３３ｐｍ以下であり、ＯＳＣ量、Ｃｅ利用率が低い値を示しており、ＯＳＣ能は実施例よりも劣っていた。図２に格子定数とＣｅ利用率の関係を示した。 On the other hand, the ceria / zirconia composite oxides obtained in Comparative Examples 1 to 4 have a lattice constant of 533 pm or less, the OSC amount and Ce utilization are low, and the OSC ability is inferior to that of the examples. It was. FIG. 2 shows the relationship between the lattice constant and the Ce utilization rate.
以上の通り、本発明によれば、格子定数が５３５ｐｍ以上、ＯＳＣ量が６２８μｍｏｌ−Ｏ２／ｇ以上と高く、Ｃｅ利用率９０％以上のセリア・ジルコニア系複合酸化物が得られていることが確認できた。 As described above, according to the present invention, a ceria / zirconia composite oxide having a lattice constant of 535 pm or more, an OSC amount of 628 μmol-O 2 / g or more, and a Ce utilization rate of 90% or more is obtained. It could be confirmed.
本発明のＯＳＣ材料を自動車排ガス浄化触媒の助触媒として使用すれば、排ガス雰囲気変動を緩和し、これまで以上に貴金属の有害成分浄化性能の向上が図れる。 If the OSC material of the present invention is used as a promoter for an automobile exhaust gas purification catalyst, fluctuations in the exhaust gas atmosphere can be mitigated, and the noble metal purification performance can be improved more than ever.
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