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    • 专利摘要:
    exhaust gas purification catalyst a catalyst for purifying an exhaust gas is provided, the catalyst of excellence in catalytic performance and oxygen storage capacity (osc). the exhaust gas purification catalyst of the present invention is an exhaust gas purification catalyst, comprising a ceria-zirconia composite oxide (a) having a pyrochlor structure and a ceria-composite oxide zirconia (b) having a cubic crystalline structure, in which at least part of the ceria-zirconia composite oxide (a) is composed with the ceria-zirconia composite oxide (b).
    公开号:BR112013019650B1
    申请号:R112013019650
    申请日:2012-01-27
    公开日:2019-12-17
    发明作者:Goto Hideki；Mikita Kosuke；Ikeda Masanori；Sugihara Shinji；Ikegami Takahiro
    申请人:Umicore Shokubai Japan Co Ltd；Umicore Shokubai USA Inc；
    IPC主号:
    专利说明:

    CATALYST AND METHOD FOR EXHAUSTING GAS PURIFICATION
    TECHNICAL FIELD
    The present invention relates to a catalyst for the purification of an exhaust gas. In particular, it refers to a catalyst for the purification of an exhaust gas capable of maintaining excellent catalytic performance.
    BACKGROUND OF THE TECHNIQUE
    As a catalyst for the purification of an exhaust gas generated from a gasoline engine, a three-way catalyst for simultaneous removal of nitrogen oxide (hereinafter also referred to as NOx), carbon monoxide (hereinafter also referred to as as CO), and hydrocarbons (hereinafter also referred to as HC) have been suggested. Specifically, it is a catalyst that has both the functions of oxidizing CO and HC to CO2 and reducing NOx to N2. Many of such catalysts have the oxygen storage capacity (hereinafter also referred to as OSC), that is, the catalyst itself accumulates oxygen when the exhaust gas is in an excess oxygen state (ie, oxidizing atmosphere), while releases oxygen when the exhaust gas is in an oxygen deficient state (ie, reducing atmosphere). A cocatalyst component having such CSOs is referred to as an oxygen storage material (hereinafter also referred to as OSC material), which allows CO and HC to be efficiently oxidized to CO2 even in an oxygen deficient state. Examples of known CSO materials have been known to include cerium oxide (CeO 2 ) and ceria-zirconia composite oxide (CeO2-ZrO2 composite oxide). It has been known that, according to
    Petition 870190040200, of 29/04/2019, p. 14/17
    2/52 with the oxidation and reduction reaction of cerium (Ce) sulfate in cerium oxide and cerium-zirconia composite oxide, oxygen absorption and release occurs, and have excellent OSC performance.
    Ceria-zirconia composite oxide (CeO 2 -ZrO 2 composite oxide) includes a ceria-zirconia composite oxide (A) having a pyrochlor structure (hereinafter also simply referred to as ceria-zirconia composite oxide (A)), a ceria-zirconia composite oxide (B) having a cubic crystal structure (fluorite type) (hereinafter also referred to simply as ceria-zirconia composite oxide (B)), a composite oxide ceria-zirconia (C) having a monoclinic structure, a ceria-zirconia composite oxide (D) having a tetragonal crystalline structure, or the like. Among them, the cerium-zirconia composite oxide (A) has the ability to absorb and release a large amount of oxygen due to its pyrochlor structure (Patent Literature 1). On the other hand, in comparison with the ceria-zirconia composite oxide (A) having a pyrochlor structure, the ceria-zirconia composite oxide (B) has a characteristic that can quickly absorb and release oxygen due to its structure cubic crystal (fluorite type).
    Citation list
    Patent literature
    Patent Literature 1: JP 2005-231,951 A
    SUMMARY OF THE INVENTION
    Technical problem
    However, even if a cerium composite oxide
    3/52 zirconia (A) is used, due to an oxygen absorption and release rate, in particular, an oxygen release rate is slow, the purification performance is poor under the condition that the exhaust gas has atmosphere highly floating. In addition, even if the cerium-zirconia composite oxide (B) is used, because the amount of oxygen absorption and release is small, as above, the purification performance cannot be achieved at sufficient level under the condition in which the exhaust gas has a highly floating atmosphere. In addition, the simple combined use of ceria-zirconia composite oxide (A) and ceria-zirconia composite oxide (B) does not show their merits.
    The present invention was made under the conditions described above, and an object of the present invention is to provide a catalyst for purifying an exhaust gas with excellent catalytic performance and excellent oxygen storage capacity (OSC).
    Another object of the present invention is to provide a catalyst for the purification of an exhaust gas with excellent catalytic performance and an excellent property to absorb and release oxygen, even after being exposed to an exhaust gas at high temperature.
    Solution to the problem
    In order to solve the problems described above, the present inventors carried out intensive studies to discover that, through the use, as a CSO material, of ceria-zirconia composite oxide in which a pyrochlor structure and a cubic crystal structure ( fluorite type) are composite, a catalyst having
    4/52 excellent catalytic performance and oxygen storage capacity (OSC) can be obtained, and thus the present invention has been completed.
    Specifically, the present invention provides a catalyst for the purification of an exhaust gas comprising a ceria-zirconia composite oxide (A), having a pyrochlor structure and a ceria-zirconia composite oxide (B) having a structure cubic crystalline in which at least a part of the ceriazirconia composite oxide (A) is composed with the ceriazirconia oxide compound (B).
    Effects of the present invention
    The catalyst for the purification of an exhaust gas of the present invention has excellent catalytic performance and oxygen storage capacity (OSC).
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1 is a schematic drawing of a catalyst according to the present invention.
    DESCRIPTION OF THE MODALITIES
    The exhaust gas purification catalyst of the present invention (hereinafter also simply referred to as the catalyst of the present invention) contains a ceria-zirconia composite oxide (A) having a pyrochlor structure (hereinafter also simply referred to as ceria-zirconia composite oxide (A)) and a ceria-zirconia composite oxide (B) having a cubic crystalline structure (fluorite type) (hereinafter also referred to simply as ceriazirconia composite oxide (B)), which is composed of at least a part of the cerium-zirconia composite oxide (A).
    5/52
    As used here, composite means that when a ceria-zirconia composite oxide (A), ceria-zirconia composite oxide (B), elements other than those included in ceria-zirconia composite oxide (A) and ceria-zirconia composite oxide (B) are mixed together, ceria-zirconia composite oxide (A) and ceria-zirconia composite oxide (B) are in contact with each other on the contact surface between ceria-zirconia composite oxide (A) and ceria-zirconia composite oxide (B), while elements other than those included in ceria-zirconia composite oxide (A) and ceria-zirconia composite oxide ( B) are not present.
    By a structure in which at least a part of the ceria-zirconia composite oxide (A) is composed with the ceria-zirconia composite oxide (B), an excellent oxygen storage capacity (ie, excellent storage property oxygen and high rate of absorption and release of oxygen) can be achieved. Therefore, the catalyst of the present invention can show excellent catalytic performance.
    Although the reason for achieving the effects described above is not yet clear, it is considered as follows. However, the present invention is not limited to the following assumptions. Specifically, although the cerium-zirconia composite oxide (A) has an ability to absorb and release a large amount of oxygen due to its pyrochlor structure, a low rate of oxygen release absorption, in particular, a rate of release slow. On the other hand, although the composite oxide of
    6/52 ceria-zirconia (B) can quickly absorb and release oxygen, due to its cubic crystalline structure (fluorite type), has a lower amount of oxygen absorption and release compared to the ceria-zirconia composite oxide (A ) having a pyrochlor structure.
    For such reasons, when the catalyst according to the present invention absorbs oxygen, the ceria-zirconia composite oxide (B), rapidly absorbs oxygen due to its cubic crystalline structure (fluorite type). At that time, Ce 3+ becomes Ce 4+ (ie Ce 3+ - »Ce 4+ ) in the ceria-zirconia composite oxide (B), and an oxygen concentration gradient is formed between an oxide of ceria-zirconia composite (A) present as Ce 3+ and ceria-zirconia composite oxide (B). Since the ceria-zirconia composite oxide (B) is composed with the ceria-zirconia composite oxide (A), the absorbed oxygen migrates to the ceria-zirconia composite oxide (A) having a pyrochlorine structure , which is present in contact with the cerium-zirconia composite oxide (B), and is absorbed in it. In such a case, due to the pyrochlor structure, the cerium-zirconia composite oxide (A) can store a large amount of oxygen. Due to the high oxygen absorption rate of the ceria-zirconia composite oxide (B) and the high oxygen storage capacity of the ceria-zirconia composite oxide (A), the catalyst of the present invention can quickly absorb and store a large amount of oxygen compared to a case where each is present alone. Thus, the catalyst of the present invention can also
    7/52 function as an OSC material that exhibits excellent oxygen storage capacity (OSC). On the other hand, when the catalyst of the present invention releases oxygen, the ceria-zirconia composite oxide (B) present in contact with the ceria-zirconia composite oxide (A) quickly releases oxygen, due to its cubic crystalline structure (fluorite type). Accompanying the release, Ce 4+ transforms into Ce 3+ (ie Ce 4+ - »Ce 3 + ), in the ceria-zirconia composite oxide (B), and an oxygen concentration gradient is formed between an oxide of ceria-zirconia composite (A), present as Ce 4+ and the ceria-zirconia composite oxide (B). Because oxygen becomes deficient in the ceria-zirconia composite oxide (B), it receives oxygen from the ceria-zirconia composite oxide (A) that is present in contact with it. Due to the pyrochlor structure, the cerium-zirconia composite oxide (A) has an excellent oxygen storage capacity (that is, it can store a large amount of oxygen). Thus, according to the high oxygen release rate of ceriazirconia composite oxide (B) and high oxygen storage capacity of ceriazirconia composite oxide (A), the catalyst of the present invention can rapidly release a large amount of oxygen compared to a case where each is present in isolation.
    Thus, as a whole, the catalyst of the present invention can quickly absorb and release a large amount of oxygen and, therefore, can have excellent catalytic performance.
    8/52
    As shown in Figure 1, catalyst 1 of the present invention contains ceria-zirconia composite oxide (A) 2 having a pyrochlor structure and ceria-zirconia composite oxide (B) 3 having a cubic crystalline structure (type fluorite) which is composed of at least part of the peripheral ceria-zirconia composite oxide (A) 2.
    Here, with regard to the state of the ceria-zirconia composite oxide (A) 2 with the ceria-zirconia composite oxide (B) 3, it is sufficient that at least part of the ceria-zirconia composite oxide (A) 2 is composed with the ceria-zirconia composite oxide (B) 3, and preferably, is coated with the ceria-zirconia composite oxide (B) 3. More specifically, as shown in Figure IA, the same may have a structure in which all the ceria-zirconia composite oxide (A) 2 is composed with the ceria-zirconia composite oxide (B) 3, or, as shown in Figure IB or 1C, a structure in which the ceria-zirconia composite oxide (A) 2 is partially composed with cerium oxide, zirconia composite oxide (B) 3. In addition, the ratio of a ceria-zirconia composite oxide (A) to an oxide of ceria-zirconia composite (B) is not · specifically limited if desired to absorb oxygen and the capacity for liberation can be achieved. However, it is preferably 50 to 100%, and more preferably 75 to 100%, in relation to the surface area of the ceria-zirconia composite oxide (A) and, as shown in Figure 1 A, a structure in which all the ceria-zirconia composite oxide (A) 2 is composed with the ceria-zirconia composite oxide (B) 3 (that is, the ratio of
    9/52 composite = 100%) is particularly preferable. For this reason, the ceria-zirconia composite oxide (B) 3 can absorb oxygen quickly and efficiently, and the absorbed oxygen quickly migrates to the zirconia-ceria (A) 2 composite oxide present in the center. As a result, the catalyst of the present invention can rapidly absorb a large amount of oxygen. Likewise, when oxygen is released from the ceria-zirconia composite oxide (B) 3, a large amount of oxygen migrates from the ceria-zirconia composite oxide (A) 2 present in the center to the composite oxide of ceria-zirconia (B) 3 that accompanies the release, and as a result, oxygen is rapidly released from the cerium-zirconia composite oxide (B) 3. Consequently, the catalyst of the present invention can rapidly release a large amount of oxygen.
    The catalyst of the present invention contains the cerium-zirconia composite oxide (A). Here, the cerium-zirconia composite oxide (A) is not specifically limited, as long as it has a pyrochlorine phase in its crystalline structure. For example, those disclosed in WO 2008/093471 can be used in a similar way. As described here, the pyrochlor structure represents a structure represented by the chemical formula: Ce 2 Zr 2 O 7 , in which Ce and Zr form a network of regular tetrahedra, and is easily present in a reducing atmosphere. Under an oxidizing atmosphere, a separate structure formed by CeZrO 4 / is formed and the two structures are reversibly converted to the other.
    An exhaust gas discharged from the combustion engine
    10/52 has fluctuating oxygen concentration depending on the change in the operating condition. For these reasons, the cerium (Ce) ion in the cerium-zirconia composite oxide that is used for a catalyst to purify an exhaust gas is subjected to a valence change such as Ce 3+ and Ce 4+ . This can cause changes in the crystal structure of a ceria-zirconia composite oxide. However, in many cases, such a modification of the crystalline structure of a ceria-zirconia composite oxide is reversible. It is believed that such a reversible change in the crystalline structure is also the same as that of the cerium-zirconia (A) composite oxide according to the present invention. Thus, even though the cerium-zirconia composite oxide (A) used as a raw material in the present invention may temporarily have a crystalline structure different from the pyrochlor structure in the catalyst composition, it is sufficient to have a pyrochlor structure under a atmosphere in which the oxide is used as a catalyst of the present invention.
    The amount used of the ceriazirconia (A) composite oxide of the present invention is not specifically limited. However, it is preferably from 1 to 100 g, and preferably from 3 to 50 g per liter of catalyst. With such an amount used, the catalyst of the present invention can absorb and release a sufficient amount of oxygen.
    With regard to ceriazirconia (A) composite oxide, as long as Ce and Zr are contained as an essential constitutional element in addition to Ce 2 Zr 2 O 7 consists substantially of Ce / Zr / O only, a part of the elements
    Constituent 11/52 can be replaced with a rare earth metal (rare earth element), a transition metal, an alkali metal, an alkaline earth metal, or the like. Examples of rare earth metal include, although not specifically limited, scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), and neodymium (Nd). However, cerium is not included in rare earth metal. Examples of the transition metal include, although not specifically limited, cobalt (Co), nickel (Ni). Examples of an alkali metal include, although not specifically limited, sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs). Examples of the alkali metal include, although not specifically limited, calcium (Ca), strontium (Sr), and barium (Ba). In addition, a part of the constitutional components of the cerium-zirconia composite oxide (A) can be replaced with a metallic component, such as magnesium (Mg), antimony, hafnium, tantalum, rhenium, bismuth, samarium, gadolinium, holmium, thulium, ytterbium, germanium, selenium, cadmium, indium, scandium, titanium, niobium, chrome, iron, silver, rhodium and platinum. They can be used alone or in combination with two or more. In addition, the other metal described above may be present in the form of a ceriazirconia composite oxide (A). Among them, from the point of view of improved heat resistance of an OSC material, it is preferable to include a rare earth metal, in particular, yttrium and / or lanthanum. The amount of the other metal used is, in terms of oxide, preferably 0.05 to 30% by weight, and more preferably, 0.1 to 20% by weight in relation to the cerium-zirconia composite oxide (A). Beyond
    In addition, the amount of the other metal used is, in terms of oxide, preferably 0.5 to 15 g, and preferably 3 to 10 g, per liter of catalyst.
    The difference in crystalline structure between the OSC material according to the present invention and the ceria-zirconia composite oxide (B) having a cubic crystalline structure can be clearly demonstrated by X-ray diffraction, if it is composed exclusively of a material of CSOs. In the OSC material according to the present invention, from a peak originating from a pyrochlor structure it is detected close to 2θ = 14.5 °. In addition, when the OSC material according to the present invention is added in a catalyst composition, the presence or absence of addition can be characterized by the diffraction pattern by TEM (Transmission Electron Microscope) and also by EDX (Spectroscopy Dispersive Energy X-ray). When a crystalline sample is irradiated with an electronic beam by TEM, the electronic beam is subjected to conversion / diffraction in the sample, and shows the dispersion again. As a result, the specific diffraction pattern for the crystalline structure is formed. Thus, the ceria-zirconia composite oxide (A) and the ceria-zirconia composite oxide (B), each having different structures, form a different diffraction pattern. In addition, according to EDX, a specific X-ray generated after the application of an electronic beam to an object is detected, and from the distribution of energy obtained from the X-ray, the constitutional material in question can be examined. When the OSC material according to the present invention is added, it is confirmed
    13/52 that no other element than the elements derived from a ceria-zirconia composite oxide (A) and a ceria-zirconia composite oxide (B) is present at an interface between the ceria-zirconia composite oxide ( A) and the cerium-zirconia composite oxide (B).
    A weight ratio between cerium and zirconium that are contained in the cerium-zirconia (A) composite oxide or the like is, although not specifically limited, preferably 1: 9 to 9: 1 and more preferably, 2: 3 to 3: 2, in oxide terms. With such a composition, excellent oxygen absorption and release performance and heat resistance can be achieved.
    The shape or similar of the ceriazirconia (A) composite oxide is not specifically limited, if the desired properties such as absorption and release performance and heat resistance are obtained. Examples of the cerium-zirconia (A) composite oxide shape include particle shape, fine particle shape, powder shape, column shape, cone shape, prism shape, cubic shape, shape pyramid, and the amorphous shape. Preferably, the shape of the ceriazirconia composite oxide (A) is particle shape, fine particle shape, powder shape. When having a particle shape, fine particle shape, powder shape, the average diameter of the ceriazirconia composite oxide particles (A) is not specifically limited. The average particle diameter of the cerium-zirconia composite oxide (A) is preferably in the range of 1 to 100 μτη, and more preferably in the range of 1 to 20 μτη. However, the average particle diameter or particle diameter
    14/52 used here means diameter. In addition, although not specifically limited, a specific surface area of the cerium-zirconia composite oxide (A) is generally small. Specifically, the specific surface area of the ceria-zirconia composite oxide (A) is 0.1 to 20 m 2 / g.
    A method for producing the ceriazirconia (A) composite oxide according to the present invention is not specifically limited. Instead, a known method can be used as is or with appropriate modifications. In the following, preferred embodiments of the method for producing the cerium-zirconia composite oxide (A) according to the present invention will be described. However, the method of producing the cerium-zirconia (A) composite oxide according to the present invention is not limited to the following preferred embodiments.
    Specifically, each raw material for cerium and zirconium is mixed with the other and melts by heating to a predetermined temperature (for example, 2000 ° C or higher). After cooling, a CeO 2 -ZrO 2 composite oxide ingot is prepared, which is then ground.
    Here, the raw material for cerium is not specifically limited and specific examples of these include nitrate, carbonate, sulfate, acetate, chloride, bromide, and cerium oxide. The cerium raw material can be used either alone, in a combination of two or more, or in the form of composite oxide. Among them, considering the melting under heating or the like, cerium oxide (ie cerium) is preferable. Cerium oxide may be an oxide
    15/52 obtained from nitrate, carbonate, sulfate, acetate, chloride, or bromide. However, the purity of the raw material
    of cerium is not specifically limited, but is preferably, highly pure, in particular, has The 99.9% or higher purity. In addition, a raw material zirconium no is
    specifically limited, too. Specific examples of these include zirconium nitrate, carbonate, sulfate, acetate, chloride and bromide, and elemental zirconium material such as badelite, silica zirconia removed, and zirconium oxide. The zirconium raw material can be used either alone, in a combination of two or more, or in the form of composite oxide. Among them, considering the melting under heating or the like, zirconium oxide (for example, zirconia) is preferable. Zirconium oxide can be obtained from an oxide of nitrate, carbonate, sulfate, acetate, chloride or bromide. In addition, the cerium feedstock and the zirconium feedstock can be a mixture of the feedstocks or their composite oxide. However, the purity of the zirconium raw material is not specifically limited, but is preferably highly pure, in particular, it has a purity of 99.9% or greater.
    In addition, in addition to the cerium raw material and the zirconium raw material described above, another component can be used in combination. Here, the other component is not specifically limited, as long as it does not affect the properties of the ceriazirconia (A) composite oxide (in particular, excellent oxygen absorption and release property). Specific examples
    16/52 of these include an alkali metal such as potassium, rubidium, and cesium; magnesium, an alkaline earth metal like calcium, strontium and barium; and a metal component such as hafnium, rhenium, bismuth, yttrium, lanthanum (La), praseodymium, neode, samarium, gadolinium, ytterbium, germanium, selenium, indium, titanium, iron, silver, rhodium, platinum and palladium. As an alternative, the other component also includes those included because they originated from impurities in the cerium raw material or zirconium raw material. In addition, when the other component is used in combination, the amount of it used is not specifically limited, if the characteristics of the cerium-zirconia (A) composite oxide (in particular, excellent oxygen absorption and release properties) do not are harmed. It can be properly selected considering the desired effects.
    The cerium feedstock and the zirconium feedstock are mixed together at a predetermined ratio, added to a melting device, and melting by heating. Here, the mixing ratio between the cerium raw material and the zirconium raw material is not specifically limited, if they exhibit a pyrochlor structure. The mixing ratio between the cerium raw material and the zirconium raw material (that is, the weight ratio in terms of oxide), is preferably 1: 9 to 9: 1, and more preferably, 2: 3 to 3: 2. With such a mixing ratio, excellent oxygen absorption and release properties and heat resistance can be achieved.
    The cerium raw material and the zirconium raw material, and if necessary, other component (s), are
    17/52 mixed together, and the resulting mixture is melted under heating. The melting method is not specifically limited, if at least one of the raw material mix is melting. Specific examples of these include an electrical fusion (arc type) and the high frequency thermal plasma method. Among them, an electrical fusion and, in particular, a fusion method using an electric arc furnace is preferably used.
    For a fusion method using an electric arc furnace, for a mixture containing the raw material of cerium and the raw material of zirconium and, if necessary, other component (s) (ie a mixture of raw material of oxide of ceria-zirconia composite (A)), a conductive material (for example, coke) can be added. In this way, the initial electrical current can be promoted. Here, an addition amount of the conductive material is not specifically limited, and is sufficient if it is an amount to promote the desired initial electrical current. The amount of addition of the conductive material can be selected appropriately taking into account the mixing ratio between the cerium raw material and the zirconium raw material.
    In addition, the condition for melting the mixture of ceria-zirconia (A) composite oxide materials is not specifically limited, if at least one of the mixture of the raw materials is melted. For example, a secondary voltage is preferably 70 to 100 V. An average application source is preferably 80 to 100 kW. In addition, a heating temperature for the mixing of the ceria composite oxide raw material
    18/52 zirconia (A) is not specifically limited. It is sufficient that it allows the merger of at least one. A melting point of an oxide of the raw material is high, for example, cerium oxide has a melting point of 2200 ° C and the melting point of zirconium oxide is 2720 ° C. However, even for such a case, there is an effect of decreasing the melting point and, thus, a melting state can be obtained even when the melting temperature (heating) is lower than the melting point of the oxide. The material can be added with a small amount of nitrate, carbonate, sulfate, chloride, or cerium or zirconium bromide. Therefore, the merger can be promoted during the production process. Considering the above, the heating temperature of the mixture of raw materials of ceriazirconia (A) oxide is preferably 2000 ° C or higher, more preferably 2200 ° C or higher, even more preferably 2400 ° C or higher, and especially preferably 2600 ° C or higher. In addition, the upper limit of the heating temperature for mixing raw material is preferably 3000 ° C or lower, and more preferably 2800 ° C or lower, although not specifically limited thereto. On the other hand, to lower the melting point, a trace amount of flow or the like can be added. When elementary materials are added, the melting point of the raw material mixture varies depending on the molar ratio between zirconia and ceria. Specifically, for a case where CeO 2 / ZrO 2 (molar ratio) = 1/9, it is about 2600 ° C. For a case where the molar ratio is 5/5, it is about 2200 ° C. For a case where the molar ratio is 9/1, it
    19/52 is about 2000 ° C.
    A heating time for the mixture of raw material of ceria-zirconia composite oxide (A) is preferably 0.5 to 3 hours. By holding for 0.5 hours or more after the raw material mixture is returned to the melting state, homogeneous melting can be achieved. However, since the mixture of ceria-zirconia (A) composite oxide raw materials is melted for a predetermined period of time, it can be cooled by itself or kept in the molten state for a predetermined period of time. . For such cases, a maintenance time in the molten state is preferably 1 to 2 hours. In addition, an atmosphere during fusion is not specifically limited, and its examples include air, nitrogen and argon and helium as an inert gas. In addition, a pressure during melting is not specifically limited, and any one of atmospheric pressure, increased pressure and reduced pressure can be used. In general, it is performed under atmospheric pressure.
    When the melting is complete, the molten mixture is cooled to produce a CeO 2 -ZrO 2 composite oxide ingot. For example, by covering an electric oven, with a carbon cover and slow cooling for 20 to 30 hours, an ingot can be obtained. A method for cooling the melt includes, although not specifically limited, cooling naturally in an atmosphere to a temperature of 100 ° C or less, and preferably 50 ° C or less, after ingestion from the apparatus. fusion Consequently, a cerium oxide ingot of
    20/52 zirconium, in which the compound of cerium raw material and zirconium raw material is present is obtained homogeneously.
    The ingot after melting is subsequently pulverized. Conditions for spraying an ingot include, although not specifically limited, spraying until the diameter of the ceriazirconia composite oxide particle (A) is preferably 3 mm or less, and more preferably 1 mm or less. In addition, examples of a sprayer that can be used include, although not specifically limited, a bath crusher and a roller crusher. Considering the handling during the post-treatment processes, it is preferable that the ingot is pulverized until it becomes powder of 1 mm or less and then subjected to a classification. However, impurities or the like can be separated from the powder obtained by magnetic separation, and if desired, suboxides formed during the melting process or crystal deformations caused by cooling can be removed by oxidative calcination in an electric oven or the like. Here, the condition for oxidative calcination is not specifically limited, if this allows the oxidation of an ingot or powder, but the calcination can generally be carried out at 100 ° C to 1000 ° C, and preferably 600 ° C to 800 ° C. In addition, the calcination time is, although not specifically limited, from 0.5 to 5 hours and preferably from 1 to 3 hours.
    The powder obtained by the method described above can be subjected to fine spraying according to the intended use. Although not specifically limited, the
    21/52 fine spraying can be performed for 5 to 30 minutes, using a sprayer such as planetary mill, ball mill or jet mill. The condition for fine spraying includes, although not specifically limited, finely spraying until the average particle diameter of the ceria-zirconia composite oxide is 0.3 to 2.0 pm, and more preferably, 0.5 to 1.5 pm. Although the detailed reasons remain unclear, it is believed that the surface area of the composite oxide is increased by fine spraying and, therefore, large oxygen release can be achieved even in a low temperature region. However, the average particle diameter can be measured by a known method using a laser diffraction and dispersion analyzer or the like.
    Therefore, the cerium-zirconia composite oxide (A) containing cerium and zirconium in a weight ratio preferably from 1: 9 to 9: 1, and more preferably 2: 3 to 3: 2 in terms of oxide (CeO 2 , ZrO 2 ) can be obtained.
    The composite oxide of ceria-zirconia (A) can be subjected to heat durability test, and change in structure, before and after the test can be measured by the X-ray diffractometer (XRD). For example, by confirming an exact overlap of the main peak waveforms (corresponding to Zro, 5Ceo, s0 2 ) after calcination in hot air at 1050 ° C and 1150 ° C, excellent thermal stability can be confirmed. Furthermore, if the peak above is very strong, it is possible to conclude that there is a large crystal structure.
    catalyst of the present invention additionally contains the cerium-zirconia composite oxide (B).
    22/52
    Here, ceria-zirconia composite oxide (B) is ceria-zirconia composite oxide with a cubic crystal and / or tetragonal crystal structure that substantially does not contain a pyrochlor phase, and those disclosed in WO 2008/093471 may be used in a similar way, for example. Therefore, since the structure is different, the ceria-zirconia composite oxide (A) and the ceria-zirconia composite oxide (B) can have the same or different composition (for example, constitutional elements). In addition, the presence or absence of an trace element may be different.
    The amount used of the ceriazirconia composite oxide (B) of the present invention is not specifically limited. However, it is preferably from 5 to 100 g, and preferably from 10 to 80 g, per liter of catalyst. With such an amount used, the catalyst of the present invention can absorb and release oxygen at a sufficient rate.
    In addition, a mixing ratio between the cerium-zirconia composite oxide (A) and the ceria-zirconia composite oxide (B) is not specifically limited, as long as the cerium-zirconium composite oxide (A) is composed with the cerium-zirconia composite oxide (B) to a desired degree. Specifically, the mixing ratio (weight ratio) between the ceriazirconia composite oxide (A) and the ceriazirconia composite oxide (B) is preferably 1: 0.5 to 20, and more preferably 1: 1 to 10. Within the range, the ceriazirconia composite oxide (A) can be sufficiently composed with the ceriazirconia composite oxide (B).
    23/52
    Regarding the ceriazirconia composite oxide (B), it can substantially consist of Ce / Zr / O only. However, since Ce and Zr meet as an essential constitutional element, a part of the constituent elements can be replaced with another metal. Examples of the other metal include a rare earth metal (rare earth element), a transition metal, an alkali metal, an alkaline earth metal, or the like. Here, rare earth metal, transition metal, alkali metal, alkaline earth metal, or the like are not specifically limited and those exemplified above for the cerium-zirconia composite oxide (A) can also be mentioned. Alternatively, a part of the constituent components of the cerium-zirconium composite oxide (B) can be replaced with a metal component such as hafnium, rhenium, bismuth, gadolinium, ytterbium, germanium, selenium, indium, scandium, titanium, iron, silver, rhodium, palladium and platinum. They can be used alone or in combination of two or more. In addition, the other metal described above may be present, in the form of cerium-zirconium composite oxide (B). Among them, in order to further improve the heat resistance of an OSC material, it is preferable to include a rare earth metal, in particular, yttrium and / or lanthanum. The amount used of the other metal is, in terms of oxide, preferably 0.05 to 30% by weight, and more preferably 0.1 to 20% by weight, compared to the cerium-zirconia composite oxide (B). In addition, the amount used of another metal is, in terms of oxide, preferably from 0.5 to 15 g, more preferably from
    24/52 to 8 g, and especially preferably 2 to 5 g, per liter of the catalyst.
    A weight ratio between cerium and zirconium that are contained in the cerium-zirconia composite oxide (B) is, although not specifically limited, preferably 10: 1 to 1:50, more preferably 5: 1 to 1: 40, even more preferably 6: 1 to 1:12, and more preferably 4: 1 to 1: 8, in terms of oxide. With such a composition, excellent rate of oxygen absorption and release and heat resistance can be achieved. In addition, a specific BET surface area of ceria-zirconia composite oxide (B) is not specifically limited, if the oxygen in the exhaust gas can be absorbed (stored) and released at a sufficient rate. Preferably, it is 30 to 500 m 2 / g, more preferably 100 to 300 m 2 / g and especially preferably between 150 and 250 m 2 / g.
    Method for composing ceriazirconia composite oxide (A) with ceriazirconia composite oxide (B) is not specifically limited. Below, a preferred embodiment of the method for composing the ceriazirconia composite oxide (A) with the ceriazirconia composite oxide (B), will be explained. However, the present invention is not limited to the preferred embodiment described below.
    Specifically, the ceriazirconia composite oxide (A) is produced in the manner described above. The cerium-zirconia composite oxide thus obtained (A) is added and mixed with an aqueous solution of raw materials that contain the cerium raw material, the zirconium raw material, and if desired, another metal, such as
    25/52 described above (for example, yttrium and lanthanum) and the like. Here, the cerium raw material and the zirconium raw material are not specifically limited, and those previously exemplified for the production method of the cerium-zirconia composite oxide (A) can be used in a similar way. In addition, raw materials, such as another metal that are added as desired are not specifically limited, and those exemplified earlier for the production method of ceria-zirconia composite oxide (A) can be used in a similar way.
    Then, the mixture is added with ammonia or with an aqueous ammonia solution for the coprecipitation of cerium hydroxide and zirconium hydroxide. The amount of ammonia addition is, although not specifically limited, an amount to give a liquid mixture of pH 8 to 12, considering it easy to coprecipitate cerium hydroxide and zirconium hydroxide. The mixture is filtered by suction and washed with pure water. The resultant is dried and calcined again. Here, drying and calcination conditions are not specifically limited and, in general, those that are well known in the catalyst field can be used in a similar way. For example, it is preferable that the drying conditions include 1 to 5 hours at a temperature of 50 to 200 ° C and the calcination conditions include 1 to 5 hours at a temperature of 200 and 700 ° C. In addition, drying and calcination are preferably carried out under an air flow.
    For this reason, a structural body having the cerium-zirconia composite oxide (A) composed with the oxide of
    26/52 ceria-zirconia composite (B), in which the ratio of cerium weight, zirconium, in terms of oxide (CeO 2 , ZrO 2 ) is as described above, can be obtained (hereinafter also referred to as an OSC material of the present invention).
    The catalyst of the present invention essentially contains OSC material of the present invention having the ceria-zirconia composite oxide (A) compounded with the ceria-zirconia composite oxide (B). Here, the amount of OSC material used in the present invention is not particularly limited, if the desired properties including excellent oxygen storage capacity (OSC), oxygen absorption and release rate, catalytic performance, or the like can be exhibited. The amount used of the OSC material of the present invention is preferably 5 to 100 g, and more preferably 10 to 80 g, per liter of the catalyst. With such an amount used, the OSC material of the present invention can exhibit excellent oxygen storage capacity (OSC) and oxygen absorption and release rate and, therefore, the catalyst of the present invention can exhibit excellent catalytic performance.
    The catalyst of the present invention essentially contains OSC material of the present invention, but it can additionally contain another component. For example, the catalyst of the present invention preferably still contains a catalytically active component directly to catalyze a chemical reaction for the purification of exhaust gases (for example, oxidation and reaction reduction). Here, considering catalytic or similar activity, the preferred examples of
    27/52 catalytically active components include a noble metal, although it is not specifically limited to them.
    Preferred examples of the noble metal that is used as a catalytically active component include, although not specifically limited, platinum, palladium and rhodium. Noble metal can be used alone or in combination with two or more types. The amount of noble metal used is not specifically limited. For example, the amount of platinum used is preferably 0.01 to 5 g, and more preferably 0.5 to 3 g, per liter of the catalyst. The amount of palladium used is preferably 0.1 to 20 g, and more preferably 0.5 to 10 g, per liter of catalyst. The amount of rhodium used is preferably 0.01 to 3 g, and more preferably 0.03 to 1.5 g per liter of the catalyst. However, when two or more types of noble metal are used, the use of noble metal amount means the total amount of noble metal. In addition, when the catalyst of the present invention has a layered structure with two or more layers, the amount of noble metal used means the amount of each layer of catalyst. In addition to the noble metal or as a substitute for the noble metal, the catalyst of the present invention may also contain, as other components, at least one member selected from the group consisting of a refractory inorganic oxide, and a refractory inorganic oxide including a metal of rare earth (excluding cerium), a transition metal (excluding zirconium), and an alkaline earth metal. Refractory inorganic oxide can be used as a carrier to support a catalytically active component such as
    28/52 noble metal, rare earth metal, and another metal element of it. Refractory inorganic oxide is not specifically limited, if it is generally used as a carrier for the catalyst. Specifically, preferred examples thereof include aluminum oxide (A1 2 O 3 ) as an a-alumina, and γ, δ, η, Θ active alumina, silicon oxide (SiO 2 ), titanium oxide (titania) (TiO 2 ), zirconium oxide (ZrO 2 ), phosphorus oxide (P 2 O 5 ), - phosphoric acid zeolite, or composite oxide thereof including alumina-titania composite oxide, alumina-zirconia composite oxide, titanium-zirconia composite oxide and ceria-zirconia composite oxide. Among them, aluminum oxide, silicon oxide (silica), phosphorus oxide, titanium oxide, zirconium oxide, cerium oxide and cerium-zirconia composite oxide are preferable. Silicon oxide (silica), zirconium oxide, aluminum oxide and ceriazirconia composite oxide are more preferable. Zirconium oxide, aluminum oxide, ceria-zirconia composite oxide, and active alumina powder are even more preferable. Refractory inorganic oxide can be used either alone or in combination with two or more. In addition, it can be used in the form of oxide, as described above, but those capable of forming heating oxide can also be used. For the latter, hydroxide, nitrate, halide such as chloride, acetate, sulfate and carbonate, or the like, aluminum, silicon, titanium, zirconium, and phosphorus can be used. For the latter, refractory inorganic oxide may contain other metals. Examples of other metals include, but are not limited to,
    29/52 rare earth, such as scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), and neodymium (Nd) (with the proviso that cerium is excluded; as the case may be) , the transition metal such as cobalt (Co), nickel (Ni), (with the proviso that iron and zirconium are excluded, as the case may be) and alkaline earth metal such as magnesium (Mg) and barium ( Ba). Other metals can be used alone or in combination with two or more. Among them, it is preferable that yttrium and / or lanthanum are included in the refractory inorganic oxide. In addition, when the refractory inorganic oxide contains the other metal, the amount of it used is, in terms of oxide, preferably 0.5 to 10 g, and more preferably 2 to 5 g, relative to 100 g of the oxide refractory inorganic. However, when two or more of the other metals are used, the amount of use of the other metal means the total amount of them. In addition, when the catalyst of the present invention has a layered structure with two or more layers, the amount used of the other metal means the amount in each layer of catalyst.
    When the catalyst of the present invention also contains refractory inorganic oxide, the amount of refractory inorganic oxide used is, although not specifically limited, preferably from 10 to 300 g, and more preferably 30 to 150 g, per liter of catalyst. However, when two or more types of refractory inorganic oxide are used, the amount of refractory inorganic oxide used means their total amount. In addition, when the catalyst of the present invention has a layered structure with two or more
    30/52 layers, the amount of refractory inorganic oxide used means the amount of each layer of catalyst. When it is the same or greater than 10 g, and not only can the catalytically active component such as a noble metal be sufficiently dispersed, but the entire durability can also be achieved at a sufficient level. On the other hand, when it is the same or less than 300 g, the catalytically active component as a noble metal can be properly in contact with the exhaust gas to induce an easy temperature rise. As a result, the oxidation and reduction reaction can be desirably carried out. In addition, a specific BET surface area of refractory inorganic oxide is preferably 50 to 750 m 2 / g, and more preferably 150 to 750 m 2 / g, from the point of view of supporting the catalytically active component as a noble metal. Furthermore, in relation to a refractory inorganic oxide size, although not specifically limited, an average particle diameter is preferably 0.5 to 150 pm, and more preferably from 1 to 100 pm if it is in powder form, for example .
    As for refractory inorganic oxide for a case where the catalyst of the present invention still contains refractory inorganic oxide, containing a rare earth metal (excluding cerium), a transition metal (excluding zirconium), and an alkaline earth metal, those specifically described above can be used with the amount of use described above. Examples of rare earth metal (excluding cerium) include scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), and neodymium (Nd), although not specifically limited to them. 0 metal
    31/52 of rare earth is generally used in the form of oxide. The amount of rare earth metal used (excluding cerium) is, in terms of oxide, preferably 0.5 to 10 g, and more preferably 2 to 5 g per liter of catalyst. Examples of alkaline earth metals include calcium (Ca) and barium (Ba), although not specifically limited to them. Alkaline earth metal is generally used in the form of oxide. The amount of alkaline earth metal used is, in terms of oxide, preferably 0.5 to 20 g, and more preferably 2 to 10 g, per liter of catalyst. Examples of the transition metal include cobalt (Co) and nickel (Ni) although not specifically limited to them. The transition metal is generally used in the form of oxide. The amount of the transition metal used is, in terms of oxide, preferably 0.01 to 20 g, and more preferably, 0.1 to 10 g per liter of the catalyst.
    Alternatively, the catalyst of the present invention may further contain, as a substitute for the above component or in addition to at least one of the above components, a cocatalyst component. The cocatalyst component is not specifically limited, and any cocatalyst components well known in the catalyst field can be used. Examples of these include a rare earth metal, an alkaline earth metal, and other transition metals. The cocatalyst component is generally present as an oxide in the catalyst. Examples of rare earth metal (excluding cerium) include scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), and neodymium (Nd), although not specifically limited to
    32/52 same. The rare earth metal is generally used in the form of oxide. The amount of rare earth metal used (excluding cerium) is, in terms of oxide, preferably from 0.5 to 10 g, and more preferably from 2 to 5 g, per liter of catalyst. Examples of alkaline earth metal include magnesium (Mg) and barium (Ba). Alkaline earth metal is generally used in the form of oxide, but it can be used in the form of carbonate or sulfate. The amount of alkaline earth metal used is, in terms of oxide, preferably 0.5 to 20 g, and more preferably 2 to 10 g, per liter of catalyst. Examples of other transition metals include cobalt (Co) and nickel (Ni), although not specifically limited to them. The transition metal is generally used in the form of oxide. The amount of transition metal used is, in terms of oxide, preferably 0.01 to 20 g, and more preferably, 0.1 to 10 g per liter of the catalyst. The cocatalyst component can be dispersed alone in a layer of catalyst, or it can be supported on the composite oxide of ceria-zirconia (A) or refractory inorganic oxide. However, when two or more of the cocatalysts are used, the amount used of the cocatalyst means the total amount of them. In addition, when the catalyst of the present invention has a layered structure with two or more layers, the amount of cocatalyst used means the amount of each layer of catalyst.
    Alternatively, the catalyst of the present invention may further contain, as a substitute for the above component or in addition to at least one of the above components,
    33/52 an OSC material. The OSC material is not specifically limited, and any OSC material well known in the catalyst field can be used. Specific examples thereof include ceria-zirconia composite oxide (CeO 2 -ZrO 2 composite oxide) having only a pyrochlor structure, cerium oxide (CeO 2 ) with only a cubic crystalline structure (fluorite type) only, zirconium oxide (ZrO 2 ) having a cubic crystalline structure (fluorite type) only, and ceria-zirconia composite oxide (CeO 2 -ZrO 2 composite oxide) with only a cubic crystalline structure (fluorite). The amount of OSC material used is, although not specifically limited, preferably from 5 to 150 g, and more preferably from 10 to 120 g, per liter of the catalyst.
    The catalyst of the present invention can be used on its own, but is preferably supported on a carrier. Any conveyor that has been generally used in the field can be used without limitation, but a three-dimensional structural body is used preferably. Examples of a three-dimensional structural body include a refractory conveyor such as a honeycomb conveyor. In addition, the three-dimensional structural body is preferably an integrally molded body (i.e., an integrally structured body), and examples of which can be used include preferably a monolithic carrier, a metal honeycomb carrier, a honeycomb carrier honey plugged as a diesel particulate filter, and a drilling metal. In addition, the use of a body is not necessarily required
    34/52 integral three-dimensional structural, and a pellet carrier or the like can also be used, for example.
    As for the monolithic support, those commonly referred to as ceramic honeycomb carrier can be used. In particular, those made from cordierite, mullite, a-alumina, silicon carbide, silicon nitride, or the like are preferable. Among them, those made from cordierite (ie cordierite transporters) are particularly preferable. In addition, an integral structural body obtained using refractory metal having resistance to oxidation, including stainless steel, Fe-Cr-Al alloy or the like can be used.
    Monolithic conveyor is produced by an extrusion molding method or by rolling a sheet-like element, followed by hardening. The form of gas air inlet (cell shape) can be any one of hexagonal, rectangular, triangular, or corrugation. This can be used sufficiently when the cell density (Number of cells / unit area) is 100 to 1200 cells / square inch. It is preferably 200 to 900 cells / square inch, and more preferably 250 to 500 cells / square inch. A method for supporting the catalyst of the present invention on a three-dimensional structural body is not specifically limited, and a wash coating or the like can be used, for example.
    In the following, preferred embodiments of the method for producing the catalyst of the present invention will be explained. However, it should be noted that this
    The invention is not limited to the preferred embodiments.
    Specifically, the OSC material according to the present invention and, if desired, other components described above, for example, a noble metal raw material, refractory inorganic oxide, refractory inorganic oxide, including at least one selected from the group consisting of a rare earth metal (excluding cerium), a transition metal (excluding zirconium), and an alkaline earth metal and cocatalyst component, or the like, are suitably weighed and mixed according to the desired composition, stirred for 0 , 5 to 24 hours at 5 to 95 ° C, and subject to wet grinding, to generate a paste. The paste is placed in contact with a carrier, as described above (for example, a three-dimensional structural body), and air-dried at a temperature of 50 to 300 ° C, and preferably 80 to 200 ° C for 5 minutes at 10 hours and, preferably, 5 minutes to 8 hours. Then, it is calcined at a temperature of 300 to 1200 ° C, and preferably from 400 to 800 ° C for 30 minutes to 10 hours, and preferably 1 hour to 5 hours. Subsequently, the paste (B) is placed in contact with the conveyor coated with the paste (A), and air-dried at a temperature of 50 to 300 ° C, and preferably, 80 to 200 ° C for 5 minutes to 10 hours. and, preferably, from 5 minutes to 8 hours. Then, it was calcined at a temperature between 300 and 1200 ° C, and preferably 400 to 800 ° C for 30 minutes to 10 hours, and preferably, 1 hour to 5 hours and, as a result, the catalyst of the present invention is obtained.
    However, since the CSO material according to
    36/52 the present invention is contained, the catalyst of the present invention can have a single layer of the catalyst layer or can have a multilayer structure in which two or more layers of catalysts are laminated. For a case where the catalyst of the present invention has a multilayer structure in which two or more layers of catalysts are laminated, the OSC material according to the present invention can be arranged on any catalyst layer. Preferably, the OSC material according to the present invention is arranged in a layer that contains at least palladium. According to this provision, the OSC material according to the present invention can show its maximum level of performance. In addition, another layer of catalyst that does not contain the OSC material according to the present invention is not specifically limited, and may be any layer of catalyst known in the catalyst field. For example, except that the CSO material according to the present invention is not used, the same constitution (component) as described above can be used. In addition, the constitution (components) in each catalyst layer may be the same, but a different constitution is preferable. For example, for a noble metal, preferred examples of the noble metal in two layers of catalyst (ie described as a combination of noble metals in the lower catalyst layer and a noble metal in the upper catalyst layer) include, but are not limited to them, a combination of platinum and rhodium, a combination of palladium and rhodium, a combination of platinum, palladium and rhodium, a combination of platinum, rhodium
    37/52 and palladium, and a combination of palladium, rhodium and platinum. With such a combination, the exhaust gas can be purified efficiently. Among them, a combination of platinum and rhodium and a combination of palladium and rhodium are more preferable. However, although it is not necessary to include a noble metal in each layer of catalyst, it is preferable to have it in each layer of catalyst. Thus, catalytic performance can be improved.
    The OSC material according to the present invention can have excellent oxygen storage capacity (OSC), that is, an excellent oxygen storage performance and a high oxygen absorption and release rate. In addition, even after being exposed to a high temperature of 700 ° C or higher, the OSC material according to the present invention can have excellent oxygen storage capacity (OSC), that is, an excellent oxygen storage performance and high rate of absorption and release of oxygen. For these reasons, the catalyst of the present invention can have excellent catalytic performance, even after being exposed to high temperatures. In this way, the catalyst of the present invention can desirably be used for the purification of exhaust gases from a combustion engine, in particular the gasoline engine and the diesel engine. However, the condition for using the catalyst of the present invention is not specifically limited. For example, a space velocity (SV) is 10,000 to 120,000 h ' 1 , preferably 30,000 to 100,000 h' 1 . The catalyst of the present invention has excellent A / F flotation absorption and, even when the flotation width is + 1.0 or
    38/52 superior, excellent catalytic performance can be displayed.
    In addition, a catalyst inlet temperature during acceleration is preferably 0 ° C to 1200 ° C, more preferably 0 ° C to 800 ° C, and even more preferably 200 ° C to 800 ° C. In particular, the catalyst of the present invention can maintain excellent catalytic performance, even after being exposed to high temperature such as 800 ° C or higher. The effect is more significant, in a case where it is exposed to high temperatures, such as 900 ° C or higher. Hydrocarbons discharged from a combustion engine vary depending on use. However, it is preferably the fuel that can be used for an MPI engine. Preferably, it is gasoline, E10, E30, E100, or CNG, and even when it is diesel oil, dimethyl ether, or biodiesel, the catalyst of the present invention is effective if the A / F value is less than
    14.7.
    The catalyst of the present invention can exhibit a unique catalytic activity at the sufficient level. However, in the front stage (introduction side) or in the rear stage (discharge side) of the catalyst of the present invention, the same catalyst or a different catalyst for the purification of an exhaust gas can also be arranged. Preferably, the catalyst of the present invention can be arranged individually, the catalyst of the present invention can be arranged on both sides of the front stage (introduction side) and the rear stage (discharge side), or the catalyst of the present invention is placed on either the front stage (introduction side) or the rear stage (discharge side) and a
    39/52 catalyst conventionally known for the purification of an exhaust gas is placed on the other side. More preferably, the catalyst of the present invention is
    separately arranged or the catalyst for gift invention is placed in both the sides of the stage from the front (introduction side) it's the internship posterior (side of discharge). EXAMPLES Next, the effect of the present invention will be explained
    based on the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples.
    Synthesis Example 1
    First, each of highly pure zirconia (86 g) and highly pure ceria (114 g) was weighed and mixed with each other. The mixture was melted at a temperature of 2250 ° C or higher, applying a secondary voltage of 85 V, an average application power of 99.5 kw, a residence time of 2 hours, and a total amount of electricity of 182 kWh per using an electric arc type oven.
    However, to promote the initial electrical current, 10 g of coke was used. Once the melting is completed, the electric oven is covered with a carbon cap and slowly cooled in air over 24 hours to generate an ingot. The resulting ingot was sprayed with a bath crusher and a roller crusher until it was 3 mm or less, and the powder of 1 mm or less was collected with a sieve. In addition, to remove suboxides formed during the melting process or deformations in the crystal caused by supercooling, the
    40/52 calcination was carried out at 800 ° C in air for 3 hours in an electric oven followed by spraying for 10 minutes, using a planetary mill, to give a ceria-zirconia (Al) composite oxide, which has an average particle diameter 3.4 qm and a specific surface area of 2.0 m 2 / g. However, the average particle diameter was measured by a diffraction and laser scattering analyzer. In addition, as a result of the analysis of the ceriazirconia (Al) composite oxide using an X-ray diffractometer (XRD), it was confirmed that the ceriazirconia (Al) composite oxide contains only one pyrochlor phase in the structure crystalline. Thus, ceriazirconia (Al) composite oxide is CeO 2 ZrO 2 composite oxide that has a pyrochlor structure and composition of ceria and zirconia (CeO 2 : ZrO 2 ) of 57: 43 (weight ratio).
    Ion exchange water (500 g) containing cerium-zirconia (Al) composite oxide having a pyrochlor structure obtained from above (average particle diameter = 3.4 pm, specific surface area = 2.0 m 2 / g cerium oxide (CeO 2 ): zirconia (ZrO 2 ) = 57: 43 (weight ratio)) (100 g), cerium nitrate (purity of
    99.0%) (317 g), zirconium oxynitrate (degree of purity
    99.0%) (301.1 g) and lanthanum nitrate hexahydrate (107.2 g) was prepared. For the aqueous solution, 5% by weight of water in ammonia was added in order to give a final pH of 10.2, to induce the coprecipitation of cerium hydroxide and zirconium hydroxide. Then, the mixture was filtered with suction and washed with pure water. The resultant was dried at 150 ° C for 3 hours, calcined at 500 ° C for 2 hours, and sprayed for 10 minutes using a mill
    41/52 planetary, to give an OSC material that has an average particle diameter of 2.1 pm and a specific surface area of 53.7 m 2 / g. The OSC 1 material was subjected to diffraction and EDX analysis using TEM, to verify that the ceria-zirconia (Al) composite oxide is composed with CeO 2 -ZrO 2 -La 2 O 3 as a composite oxide. ceria-zirconia (Bl), and the ceria-zirconia composite oxide portion (Bl) contains only one cubic crystal, in its crystalline structure. Specifically, the OSC material obtained 1 is an OSC material in which CeO 2 -ZrO 2 (CeO 2 : ZrO 2 = 57: 43 (weight ratio)) having a pyrochlor structure is composed of CeO 2 -ZrO 2 - La 2 O 3 having a cubic crystalline structure, where the composition is as follows; CeO 2 : ZrO 2 : La 2 O3 = 45: 45: 10 (weight ratio). In addition, in the OSC 1 material thus obtained, all of the ceriazirconia composite oxide (Al) is composed (coated) with the ceriazirconia composite oxide (Bl).
    Synthesis example 2
    Ion exchange water (500 g) containing cerium nitrate (99.0% purity) (579.9 g), zirconium oxinitrate (99.0% purity) (455.5 g) and hexahydrate lanthanum nitrate (133.0 g) was prepared. To the aqueous solution, 5% by weight of water in ammonia was added in order to give a final pH of 10.2, to induce the coprecipitation of cerium hydroxide and zirconium hydroxide. Then, the mixture was filtered with suction and washed with pure water. The resultant was calcined at 500 ° C for 2 hours, and sprayed for 10 minutes, using a planetary mill, to give the ceria-zirconia (B2) composite oxide, which has an average particle diameter of 2.2 pm and area
    42/52 specific surface of 70.0 m 2 / g. The ceria-zirconia composite oxide (B2) was analyzed by X-ray diffractometer (XRD), to verify that the ceria-zirconia composite oxide (B2), has only one cubic crystal in the crystalline structure. In addition, the composition is as follows; CeO 2 : ZrO 2 : La 2 O 3 = 45: 45: 10 (weight ratio).
    Synthesis Example 3
    First, each of highly pure zirconia (235 g) and highly pure zirconia (265 g) was weighed and mixed together. The mixture was melted at a temperature of 2250 ° C or higher, applying a secondary voltage of 85 V, an average application power of 99.5 kW, a residence time of 2 hours, and a total amount of electricity of 182 kWh through of an electric arc type oven.
    However, to promote the initial electrical current, 25 g of coke was used. Once the melting is completed, the electric oven is covered with a carbon cap and cooled slowly in air over 24 hours to give an ingot. The resulting ingot was sprayed with a bath crusher and a roller crusher until it was 3 mm or less, and the powder of 1 mm or less was collected with a sieve. In addition, to remove suboxides formed during the melting process or deformations in the crystal caused by cooling, calcination was carried out at 800 ° C in air for 3 hours, followed by spraying for 10 minutes, using a planetary mill, to give an oxide of ceria-zirconia composite (A2), which has an average particle diameter of 3.4 pm and a specific surface area of 2.0 m 2 / g. However, the average particle diameter was measured by a diffraction and
    43/52 laser scattering. Furthermore, as a result of the analysis of the ceria-zirconia composite oxide (A2) using X-ray diffractometer (XRD), it was confirmed that the ceria-zirconia composite oxide (A2) contains only one pyrochlor phase in the structure crystal. In addition, the composition is as follows; CeO 2 : ZrO 2 ξ 57: 4 3 (weight ratio).
    Synthesis Example 4
    Ion exchange water (500 g) containing cerium nitrate (99.0¾ purity) (317 g), zirconium oxinitrate (99.0% purity) (301.1 g) and lanthanum nitrate hexahydrate (107.2 g) was prepared. To the aqueous solution, 5% by weight of water in ammonia was added in order to give a final pH of 10.2, to induce the coprecipitation of cerium hydroxide and zirconium hydroxide. Then, the mixture was filtered with suction and washed with pure water. The resultant was calcined at 500 ° C for 2 hours, and sprayed for 10 minutes, using a planetary mill, to give the cerium-zirconia composite oxide (B3), which has an average particle diameter of 2.2 pm and surface area of 70.0 m 2 / g. The ceria-zirconia composite oxide (B3) was analyzed by X-ray diffractometer (XRD), to verify that the ceria-zirconia composite oxide (B3) contains only one cubic crystal (tetragonal crystal) in the crystalline structure . In addition, the composition is as follows; CeO 2 : ZrO 2 : La 2 O 3 ~ 41: 45.7: 13.3 (weight ratio).
    Example 1
    Each raw material, including palladium nitrate as a source of palladium, alumina (A1 2 O 3 ), and the OSC 1 material obtained from Synthesis Example 1 above [that is, the
    44/52 OSC material in which CeO 2 -ZrO 2 (CeO 2 : ZrO 2 = 57: 43 (weight ratio)) having a pyrochlor structure is composed of CeO 2 -ZrO 2 -La 2 O 3 having a structure cubic crystalline, wherein the composition is as follows; CeO 2 : ZrO 2 : La 2 O 3 = 45: 45: 10 (weight ratio)] was weighed to give a ratio of Pd: A1 2 O 3 : OSC material 1 = 3: 52: 60 (ratio by weight). Then, the raw materials were mixed with each other, stirred for 1 hour and then subjected to wet spraying, to prepare a paste (A).
    In addition, each raw material including rhodium nitrate as a rhodium source, powdered zirconia, CeO 2 -ZrO 2 -Y 2 O 3 composite oxide (= 30: 60: 10 (weight ratio)) and alumina (A1 2 O 3 ) was weighed to give a ratio of Rh: ZrO 2 : CeO 2 -ZrO 2 -Y 2 O 3 : A1 2 O 3 = 0.2: 20: 30: 30 (weight ratio). Then, the raw materials were mixed with each other, stirred for 1 hour and then subjected to wet spraying, to prepare a paste (B).
    The obtained paste (A) was coated by washing on a honeycomb support made of cordierite with a volume of 0.7 L (99.2 mm in diameter x 90 mm in length), dried at 150 ° C, and calcined for 1 hour at 500 ° C. The total amount of each catalyst component derived from the paste (A) was 115 g after calcination. Each catalyst component derived from the suspension (A) that is contained per liter of the carrier, was as follows; Pd was 3 g, A1 2 O 3 was 52 g, and the OSC 1 material was 60 g.
    Then, the paste (B) was coated by washing in the conveyor coated with the paste (A), dried at 150 ° C and calcined for one hour at 500 ° C, to obtain a
    45/52 catalyst 1. The total amount of each catalyst component derived from the paste (B) was 80.2 g after calcination. Each catalyst component derived from the paste (B), which is contained per liter of the carrier, was as follows; Rh was 0.2 g, ZrO 2 was 20 g, Ce O2 -ZrO 2 -Y 2 O 3 was 30 g, and A1 2 O 3 was 30 g.
    Comparative Example 1
    Except that the cerium-zirconia (B2) composite oxide obtained from Synthesis Example 2 [ie, an OSC material having a cubic crystalline structure only, where CeO 2 : ZrO 2 : La 2 O 3 = 45 : 45: 10 (weight ratio)] is used in an amount of 60 g per liter of carrier instead of the OSC material 1 of Example 1, a catalyst 2 was obtained in the same way as in Example 1.
    Comparative Example 2
    Each raw material including palladium nitrate as a source of palladium, alumina (A1 2 O 3 ), and the cerium-zirconia composite oxide (A2) obtained from Synthesis Example 3 above [That is, OSC material that it has a pyrochlor structure only, where CeO 2 : ZrO 2 - 57: 43 (weight ratio)] was weighed to give a ratio of Pd: A1 2 O 3 ; OSC material 3 = 3: 65: 47 (weight ratio). Then, the raw materials were mixed with each other, stirred for 1 hour and then subjected to wet spraying, to prepare a paste (C).
    The obtained paste (C) was coated by washing on a honeycomb support made of cordierite with a volume of 0.7 L, dried at 150 ° C and calcined for 1 hour at 500 ° C. The total amount of each catalyst component derived from the paste (C) was 115 g, after calcination. Each
    46/52 paste catalyst component (C), which is contained per liter of the carrier, was as follows; Pd was 3 g, A1 2 O 3 was 65 g, and the OSC 3 material was 47 9 ·
    Then, the paste (B) was coated by washing in the conveyor coated with the paste (C), in the same way as in Example 1, dried at 150 ° C and calcined for one hour at 500 ° C, to obtain a catalyst 3.
    Comparative Example 3
    A catalyst 4 was obtained in the same manner as in Example 1 except that a mixture containing the cerium-zirconia composite oxide (B3), which was obtained from Synthesis Example 4, in an amount of 45 g per liter of carrier , and the ceriazirconia (Al) composite oxide, which was obtained from Synthesis Example 1 in an amount of 15 g per liter of carrier, was used instead of the OSC 1 material of Example 1. However, the The mixture was prepared by physically mixing the ceria-zirconia composite oxide (B3), which has only a cubic crystalline structure and has the same composition as the ceria-zirconia composite oxide (Bl) of Synthesis Example 1, with the oxide of ceria-zirconia (Al) composite, which has only a pyrochlor structure, so as to have the same composition as the OSC 1 material of Synthesis Example 1.
    Example 2
    Each raw material including palladium nitrate as a source of palladium, alumina (A1 2 O 3 ), and the OSC 1 material obtained from Synthesis Example 1 above [ie, the OSC material in which CeO 2 -ZrO 2 (CeO 2 : ZrO 2 = 57: 43
    47/52 (weight ratio)) having a pyrochlor structure is composed of CeO 2 -ZrO 2 -La 2 O 3 having a cubic crystalline structure, where the composition is as follows; CeO 2 : ZrO 2 : La 2 O 3 - 45: 45: 10 (weight ratio)] was weighed to give a ratio of Pd: A1 2 O 3 : OSC material 1 = 3: 52: 60 (ratio by weight). Then, the raw materials were mixed with each other, stirred for 1 hour and then subjected to wet spray to prepare a paste (D).
    In addition, each raw material, including rhodium nitrate as a rhodium source, zirconia powder, CeO 2 composite oxide -ZrO 2 -Y 2 O 3 (= 30: 60: 10 (weight ratio)) and alumina (A1 2 O 3 ) was weighed so as to give a ratio of Rh: ZrO 2 : ZrO 2 -CeO 2 -Y 2 O 3 : A1 2 O 3 = 0.15, 20: 30: 30 (weight ratio ). Then, the raw materials were mixed with each other, stirred for 1 hour and then subjected to wet spraying to prepare a paste (E).
    The obtained paste (D) was coated by washing on a honeycomb support made of cordierite with a volume of 0.9 L (103 mm in diameter x 105 mm in length), dried at 150 ° C, and calcined for 1 hour at 500 ° C. The total amount of each catalyst component derived from the paste (D) was 119.5 g, after calcination. Each catalyst component derived from the paste (D), which is contained per liter of the carrier, was as follows; Pd was 2.5 g, A1 2 O 3 was 52 g, and the OSC 1 material was 60 g.
    Then, the paste (E) was coated by washing in the conveyor coated with the paste (D), dried at 150 ° C and calcined for one hour at 500 ° C, to obtain a
    48/52 catalyst 5. The total amount of each catalyst component derived from the paste (E) was 80.15 g, after calcination. Each catalyst component derived from the slurry (E), which is contained per liter of the carrier, was as follows; Rh was 0.15 g, ZrO 2 was 20 g, CeO 2 -ZrO 2 Y 2 O 3 was 30 g, and A1 2 O 3 was 30 g.
    Comparative Example 4
    A catalyst 6 was obtained in the same manner as in Example 1, except that the ceriazirconia composite oxide (B2) obtained from Synthesis Example 2 [ie, an OSC material having only a cubic crystalline structure, where CeO 2 : ZrO 2 : La 2 O 3 = 45: 45: 10 (weight ratio)] was used in an amount of 60 g per liter of carrier instead of the OSC 1 material of Example 2.
    <Assessment of A / F purification property and CSO property>
    As described below, the A / F purification property and the OSC property were evaluated for catalysts 1 to 6 which were obtained from Example 1 and 2 and Comparative Example 1 to 4.
    1. Resistance treatment
    Each of the 1 to 4 (0.7 liter) catalysts that was obtained from Example 1 and Comparative Examples 1 to 3 was fitted in a catalyst converter, which was then placed in the downstream position in relation to a port exhaust from a 3.0 liter MPI engine, and then the exhaust gas was allowed to flow through the catalyst. The exhaust gas used was a gas discharged from an engine operated for 80 hours according to a mode in which a cycle consisting of the stoichiometric ratio (A / F
    49/52
    14.6) 50 seconds and rich (A / F - 13.5) 5 seconds and 5 seconds fuel cut was repeated periodically, such that the catalyst bed temperature was 1000 ° C, at maximum.
    In addition, for catalysts 5 and 6 (0.7 liters) that were obtained from Example 2 and in Comparative Example 4, the catalyst (0.7 liters) that was obtained from Example 1 was adjusted in a converter of catalyst, which was then placed in the downstream position in relation to a 3.0 liter MPI engine discharge port. In addition, the downstream position in relation to the catalyst converter, a catalyst converter fitted with catalysts 5 and 6, respectively, obtained from Example 2 or Comparative Example 4 was discarded and then the exhaust gas was allowed to flow through the catalyst. The exhaust gas used was a gas discharged from an engine operated for 80 hours in accordance with a mode in which a cycle consisting of a stoichiometric ratio (A / F = 14.6) of 50 seconds and a rich one (A / F = 13.5) of 5 seconds and, in a 5 second fuel cut, it was repeated periodically, in such a way that the temperature of the catalyst BED (catalyst 1) was 1000 ° C at the most, and the temperature of the catalyst BED posterior stage (catalyst 5 or 6), was 930 ° C, at most.
    2. Evaluation of the purification property of the A / F converter set with each catalyst obtained after the resistance treatment in section 1 above was placed on the downstream side of a 2.4 liter MPI engine. In a state where the inlet temperature of the catalyst is set at 500 ° C and a range of + 1.0 is applied with a
    50/52 frequency of 1 Hz, the engine was operated during the A / F change from 14.1 to 15.1, and the exhaust gas was allowed to flow through the catalyst. At that time, the spatial speed (VS) was adjusted to 100,000 h ' 1 . The concentration of CO, HC and NOx was recorded during an A / F change, and from a graph where the longitudinal axis is the conversion rate and the horizontal axis is an A / F value, a crossing point identifiable between CO-NOx and HC-NOx was obtained (ie, COP, a crossing point between CO or HC with NOx). Here, the upper crossing point (COPj means better performance of the catalyst. The results are shown in Table 1 below. However, for catalyst 1 arranged on the upstream side of catalyst 5 or 6, no evaluation was carried out.
    3. Assessment of CSO ownership
    The converter set with each catalyst obtained after the resistance treatment in section 1 above was placed on the downstream side of a 2.4 liter MPI engine. The inlet temperature of the catalyst was set at 500 ° C and the operation was carried out with A / F of 15.1, which later changed to 14.3. Maintenance time of the stoichiometric A / F ratio (from 14.7 to 14.5) at the catalyst outlet when the change is made from 15.1 to 14.3 was obtained. The results are shown in the following Table 2. However, for catalyst 1 arranged on the upstream side of catalyst 5 or 6, no evaluation was performed.
    [Table 1]
    Table 1: A / F purification property
    Catalyst
    CO-NOx
    HC-NOx
    51/52
    Catalyst 1 95.3 95.4 Catalyst 2 94.6 94.8 Catalyst 3 90.4 94.1 Catalyst 4 89.1 93.7 Catalyst 5 99.0 98.7 Catalyst 6 98.6 98.5
    [Table 2]
    Table 2: Ownership of OSC
    Catalyst Maintenance time of the stoichiometric ratio (from 14.7 to 14.5) Catalyst 1 3.50 Catalyst 2 2.92 Catalyst 3 2.40 Catalyst 4 2.23 Catalyst 5 3.60 Catalyst 6 1.70
    From the results of Table 1, it should be noted that catalyst 1 of the present invention has a significantly higher crossover point of CO-NOx and HC-NOx compared to catalyst 2 when using the OSC material having a crystalline structure cubic only, the catalyst using the OSC material having a pyrochlorine structure only, and also catalyst 4 using a mixture of 10 OSC material having only a cubic crystalline structure and the OSC material having only a pyrochlor structure. Likewise, it is noted that the catalyst of the present invention has a crossing point of CO-NOx and
    52/52
    Significantly higher HC-NOx, compared to catalyst 6 using the OSC material having only a cubic crystalline structure. Based on these results, it was considered that the catalyst of the present invention can have excellent purification performance of an exhaust gas with fluctuating oxygen concentration, even after the resistance treatment at 1000 ° C.
    In addition, from the results of Table 2, it should also be noted that catalyst 1 of the present invention has a significantly extended stoichiometric ratio maintenance time (from 14.7 to 14.5), compared to catalyst 2, using the OSC material having only a cubic crystalline structure, catalyst 3 using the OSC material having only one pyrochlor structure, and catalyst 4 using a mixture of OSC material having only one cubic crystalline structure and the OSC material having just a pyrochlor structure. Likewise, it is noted that catalyst 5 of the present invention significantly prolonged the maintenance time of a stoichiometric ratio (from 14.7 to 14.5), compared to catalyst 6, using the OSC material having a structure cubic crystalline only. Based on these results, the catalyst of the present invention is considered to have an excellent oxygen storage capacity (OSC).
    The present application is based on Japanese Patent Application no. 2011-019896, which was approved on February 1, 2011, and its disclosure is incorporated herein by reference in its entirety.
    权利要求:
    Claims (6)
    [1]
    1. Catalyst for the purification of an exhaust gas characterized by the fact that it comprises:
    an oxygen storage material comprising a ceria-zirconia composite oxide (A) having a pyrochlor structure; and a ceriazirconia composite oxide (B) having a cubic crystalline structure, in which at least part of the ceriazirconia composite oxide (A) is composed with the ceriazirconia composite oxide (B), and in which at least a part of the ceria-zirconia composite oxide (A) is coated with the ceria-zirconia composite oxide (B).
    [2]
    2. Catalyst according to claim 1,
    featured by the fact that what the totality of oxide in composite in ceria-zirconia (THE) is composed with the oxide in composite in ceria-zirconia (B).
    [3]
    3. Catalyst according to claim 1 or 2, characterized by the fact that it also comprises at least one noble metal selected from the group consisting of platinum, palladium and rhodium.
    [4]
    4. Catalyst according to any one of claims 1 to 3, characterized in that it further comprises at least one member selected from the group consisting of a refractory inorganic oxide and a refractory inorganic oxide including a rare earth metal (excluding cerium) , a transition metal (excluding zirconium), and an alkaline earth metal.
    [5]
    5. Catalyst according to any one of claims 1 to 4, characterized by the fact that 50 to
    Petition 870190040200, of 29/04/2019, p. 15/17
    2/2
    100% of surface area of cerium oxide composite zirconia (A) is composed with cerium oxide composite zirconia (B) .
    [6]
    6. Method for purifying an exhaust gas,
    5 characterized by the fact that it comprises a step of exposing catalyst, as defined in any one of claims 1 to 5, to the exhaust gas discharged from the combustion engine.
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    同族专利:
    公开号 | 公开日
    CN103442804A|2013-12-11|
    CN103442804B|2016-12-14|
    BR112013019650A2|2016-10-04|
    EP2671638A4|2017-04-12|
    US20140037524A1|2014-02-06|
    WO2012105454A1|2012-08-09|
    EP2671638A1|2013-12-11|
    US9539542B2|2017-01-10|
    JP6120309B2|2017-04-26|
    EP2671638B1|2018-06-27|
    JPWO2012105454A1|2014-07-03|
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    法律状态:
    2019-01-29| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-11-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-12-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/01/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-08-24| B25G| Requested change of headquarter approved|Owner name: UMICORE SHOKUBAI JAPAN CO., LTD. (JP) ; UMICORE SHOKUBAI USA INC. (US) |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011019896|2011-02-01|
    PCT/JP2012/051851|WO2012105454A1|2011-02-01|2012-01-27|Catalyst for cleaning exhaust gas|
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