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    • 专利摘要:
    CATALYST FOR PURIFICATION OF DISCHARGE GAS AND METHOD OF PURIFICATION OF DISCHARGE GAS USING THIS CATALYST. To provides a means to suppress deterioration of catalytic performance in an exhaust gas purification catalyst until after being exposed to a discharge gas containing a phosphorus compound. An exhaust gas purification catalyst of the invention is a catalyst purifying a discharge gas containing a phosphorus compound, and a catalyst includes a catalyst layer A containing rhodium (Rh), palladium (Pd), and both a complex oxide of ceria-zirconia-lantana or a complex ceria-zirconia-lantana-yttrium oxide as active components of the catalyst. Additionally, an average value of distances between Rh particles and the Pd particles closest to Rh and Pd is between 4000 nm, a weight ratio of Pd to Rh is 0.2 to 4.9, and a rate of Yttria content in the ceria-zirconia-lanthanum-yttrium complex oxide is 19% by weight or less.
    公开号:BR112015018456B1
    申请号:R112015018456-1
    申请日:2014-01-31
    公开日:2020-12-08
    发明作者:Masanori Ikeda；Kazuyoshi KOMATA；Shigekazu MINAMI；Yuji Ogino；Hideki Goto
    申请人:Umicore Shokubai Japan Co., Ltd；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention relates to a technique for purifying an exhaust gas from an internal combustion engine. More specifically, the invention relates to a technique for suppressing deterioration in catalytic performance due to long-term exposure to a discharge gas containing a phosphorus compound. TECHNICAL FUNDAMENTALS
    [002] According to fair regulations on automobile emissions, there has been a demand to maintain exhaust gas purification performance in an exhaust gas treatment device for a long time. This means that a demand for long service life of a catalyst according to an after-treatment device for exhaust gas purification has increased and also means that there is a demand for improving the long-term durability of a catalyst. In order to improve the long-term durability of a catalyst, suppression of sintering of noble metal particles supported on a catalyst or suppression of sulfur poisoning have been studied. On the other hand, it is known that poisoning due to phosphorus contained in a discharge gas (hereinafter referred to as phosphorus poisoning) has a great influence on the deterioration of catalytic performance (Non-Patent Literature 1). In order to follow regulations that will be stricter more and more from now on, it is important to suppress phosphorus poisoning or maintain and improve catalytic performance after phosphorus poisoning.
    [003] Phosphorus poisoning is known to be caused by the accumulation or infiltration, in a catalyst layer, of a phosphorus compound derived from a lubricant additive, such as a dialkyl dithiophosphate, which is contained in the exhaust gas. It is known that occurrence of phosphorus poisoning leads to deterioration of catalytic performance (Non-Patent Literature 1).
    [004] Deterioration of catalytic performance due to phosphorus poisoning is known to be caused by the occurrence of the phenomenon as described below. Diffusional inhibition of the exhaust gas in the catalyst layer is caused by the accumulated or infiltrated phosphorus compound in the catalyst layer. In addition, cerium oxide from an oxygen-release-storage material that is widely used in a three-way catalyst and a phosphorus compound reacts with one another to form cerium phosphate. When cerium phosphate is formed, oxygen is difficult to store or release. However, when the exhaust gas atmosphere is fluctuated to be rich or poor, atmospheric fluctuation is less likely to be relieved. discharge gas purification is deteriorated.
    [005] It is disclosed that, in a catalyst particularly using palladium in order to suppress phosphorus poisoning, performance deterioration can be alleviated by using a complex oxide of ceria and ziconia as an oxygen-releasing-storage material (Patent Literature 1).
    [006] Additionally, it is disclosed that performance deterioration due to phosphorus poisoning is suppressed by providing a region that is not a reactive coating composition like a phosphorus capture zone at a front end of the catalyst structure (Patent Literature 2) . CITATION LIST Patent Literatures
    [007] Patent Literature 1: JP H8-38898A
    [008] Patent Literature 2: JP 2009-501079 W (WO2007 / 011498 A) Non-Patent Literature
    [009] Non-Patent Literature 1: A. Scott et. al., SAE Paper, 96 1898, (1996) SUMMARY OF THE INVENTION Technical problem
    [010] According to Patent Literature 1, it is disclosed that the deterioration of catalytic performance after the duration of phosphorus poisoning is suppressed in the case of using ceria-zirconia complex oxide as compared to the case using only ceria. However, suppressing its effect is not enough.
    [011] Additionally, since a large decomposed amount of phosphorus adheres to an inflow side with respect to an exhaust gas flow direction, performance deterioration in the catalyst according to Patent Literature 2 is considered catalytic can be suppressed by providing a portion in which a catalytic material is not coated on the inflow side. However, there is no description in the Examples of catalytic performance after phosphorus poisoning, and a degree of its effect is unclear. Additionally, depending on a travel distance, the phosphorus compound adheres to the vicinity of a catalyst outlet on a flow side and thus catalytic performance is considered to be deteriorated. However, it is difficult to say that Patent Literature 2 proposes a countermeasure sufficient in terms of long-term durability.
    [012] However, an objective of the invention is to suppress deterioration of catalytic performance even after a catalyst has been exposed to a discharge gas containing a phosphorus compound for a long period, and particularly, to suppress deterioration of the catalytic performance of a catalyst bearing rhodium having high activity as a three-way catalyst. Means to Solve the Problem
    [013] The present inventors conducted intensive studies in order to solve the aforementioned problem, and as a result, they found that deterioration in rhodium performance can be suppressed even when a phosphorus compound in a discharge gas is infiltrated into a layer of catalyst by means of a catalyst in which a certain amount of palladium is disposed close to the rhodium and which uses a complex oxide of ceria-zirconia-lantana or a complex oxide of ceria-zirconia-lantana-yttria containing a certain amount or less of yttria. Thus, the invention was complete.
    [014] That is, according to the present invention, an exhaust gas purification catalyst is provided by purifying an exhaust gas containing a phosphorus compound, and the catalyst includes: a rhodium (Rh) catalyst layer A, palladium (Pd), and either a complex ceria-zirconia-lanthan oxide or a complex ceriazirconia-lanthan-yttrium oxide as active components of the catalyst, in which an average value of the distances between Rh particles and the particles closest to Rh and Pd Pd is within 4000 nm, a weight ratio of Pd to Rh is 0.2 to 4.9, and a ratio of yttria content in the ceria-zirconia-lanthanum-yttrium complex is 19 % by weight or less. Advantageous Effects of the Invention
    [015] According to the invention, a high discharge gas treatment performance can be maintained even if the catalyst of the invention is exposed to a discharge gas containing a phosphorus compound for a long period. BRIEF DESCRIPTION OF THE DRAWINGS
    [016] FIG. 1 shows EPMA images in which Ka ray intensities in a catalyst layer after phosphorus poisoning treatment are compared. DESCRIPTION OF THE MODALITIES
    [017] A discharge gas purification catalyst according to the invention is a catalyst purifying a discharge gas containing a phosphorus compound, and the catalyst includes a catalyst layer A containing rhodium (Rh), palladium (Pd), and either a complex ceria-zirconia-lanthan oxide or a complex ceria-zirconia-lanthan-yttrium oxide as active catalyst components. In addition, the exhaust gas purification catalyst of the invention is characterized in that an average value of the distances between Rh particles and the Pd particles closest to Rh and Pd is within 4000 nm, a weight ratio of Pd to Rh is 0.2 to 4.9, and a ratio of yttria content in the ceria-zirconia-lanthania-yttrium complex oxide is 19% by weight or less. The exhaust gas purification catalyst of the invention having such a configuration has excellent catalytic performance (resistance to poisoning) until after the catalyst is exposed to a discharge gas containing a phosphorus compound and excellent duration at high temperature, and can efficiently purify an exhaust gas from an internal combustion engine, particularly nitrogen oxide (NOx) or carbon monoxide (CO) in the exhaust gas. The reason why the exhaust gas purification catalyst of the invention has the effect as described above in this way is not clear, but the reason is inferred as follows. Incidentally, the invention is not intended to be limited by the following inferences.
    [018] A gas on the rich side (excess fuel) and a gas on the poor side (excess air) in the air / fuel ratio flow in an exhaust gas purification catalyst for a gasoline vehicle. However, an activated metal such as rhodium is useful in the purification of NOx on the rich side and in the purification of CO and hydrocarbon (hereinafter referred to as HC) on the poor side, and the purification of NO and the purification of CO and HC are in an exchange relationship. For this reason, in order to efficiently purify all of NOx, CO and HC, a method of introducing an exhaust gas having a theoretical air-to-fuel ratio of about 14.6 in a catalyst or a method to increase the frequency of theoretical air-to-fuel ratio is effective. However, during travel, the burning behavior of the internal combustion engine varies depending on acceleration and deceleration, ambient temperature, humidity, and the like, and it is not possible to supply only the exhaust gas having a theoretical air-to-fuel ratio for the catalyst of exhaust gas purification. When an oxygen-releasing-oxygen material in the catalyst stores oxygen on the poor side and releases oxygen on the rich side, various exhaust gas compositions can approximate the theoretical air-fuel ratio. That is, in order to increase the frequency of the theoretical air-fuel ratio, the oxygen-release-storage material is an essential material in the exhaust gas purification catalyst.
    [019] However, it is known that the oxygen-release-storage material forms cerium phosphate (CePO4) when exposed to a discharge gas containing a phosphorus compound and thus does not function as a release-storage material- de-oxygen. In addition, when the catalyst is exposed to the exhaust gas containing a phosphorus compound, the phosphorus compound is accumulated on a catalyst coating surface and infiltrates the catalyst layer, and thus pores of a refractory inorganic oxide are blocked, thereby inhibiting gas diffusion. When gas diffusion is inhibited, the exhaust gas does not reach Rh as an active component, and the like, and thus the exhaust gas purification performance is impaired.
    [020] Additionally, in a related technique catalyst, as a general aspect of the accumulation and infiltration of the phosphorus compound, the phosphorus compound is accumulated and infiltrated from the surface of the catalyst layer towards a three-dimensional structure so that the distribution concentration becomes smaller as it approaches the three-dimensional structure. In other words, the concentration of the phosphorus compound becomes greater towards the vicinity of the surface of the catalyst layer. The technique described in Patent Literature 2 described above focuses on the accumulation and infiltration of the phosphorus compound in the direction of discharge gas flow. However, with respect to the depth direction of the catalyst layer, in the same way as in the case of Patent Literature 1 or similar, it is considered that the phosphorus compound exists so that its concentration becomes greater towards the surface of the catalyst layer. In such an accumulation aspect, the diffusion of gas towards the depth of the catalyst layer is inhibited due to the highly concentrated phosphorus compound in the vicinity of the surface of the catalyst layer.
    [021] When a certain amount of palladium is disposed close to rhodium within a certain distance, and a complex oxide of ceria-zirconia-lantana or a complex oxide of ceria-zirconia-lantana-yttria containing a certain amount or less of yttria is used, it is clear that a high resistance to such phosphorus poisoning is exhibited. So, the invention was complete.
    [022] Palladium is more reactive with phosphorus than compared with rhodium and is prone to form a phosphorus-palladium compound. For this reason, the formation of a rhodium-phosphorus and cerium phosphate compound is considered to be suppressed when palladium is close. rhodium complements the phosphorus compound. In addition, the ceria-zirconia-lanthanate oxide is known to exhibit high stability of the crystal structure even after high temperature duration and the stability of its crystal structure is further improved by still containing a certain amount or less of yttria. This high stability of the crystal structure is considered to suppress the formation of cerium phosphate. With such a configuration, in the catalyst of the invention, the inhibition of gas diffusion is suppressed in the vicinity of the catalyst layer surface on which the adhesion of the phosphorus compound occurs at an earlier stage, and thus it is possible to continuously supply the gas of discharge in the direction of depth of the catalyst layer for a long time when compared to the catalyst of the related technique. For this reason, it is possible to decrease the concentration of the phosphorus compound on the surface of the catalyst layer and thus the phosphorus compound is dispersed well in the depth direction of the catalyst layer as compared to the related technique. In addition, with such a configuration, it is considered that the concentration of the phosphorus compound near rhodium can be decreased. For this reason, although the amount of accumulation of the phosphorus compound in the entire catalyst does not decrease, it is considered that the inhibition of gas diffusion is suppressed and thus high catalytic performance can be maintained.
    [023] Hereinafter, modalities of the invention will be described. However, the invention is not intended to be limited to the following description. Incidentally, in this specification, the term "exhaust gas purification catalyst" is also simply referred to as "catalyst" and the term "ceria-zirconia-lantana oxide or ceria-zirconia-lantana-yttrium complex oxide" is also simply referred to as “ceria-zirconia-lanthanum oxide (-ytria)”. Additionally, in this specification, the phosphorus compound indicates a phosphorus-containing compound, such as CePO4, AlPO4, Ca3 (PO4) 2, Zn (PO4) 2, CaZn2 (PO4) 2, or zinc dialkyl dithiophosphate, and there is no limitation particularly in the ways of combining them.
    [024] Additionally, “A to B” in this specification means “A or more but B or less”, and for example, the description “1% by weight to 30% by weight” or “1 to 30% by weight” in this specification indicates “1% by weight or more but 30% by weight or less”. In addition, "C and / or D" in this specification means either or both of C and D. Further, each physical property exemplified in this specification means, although not specifically mentioned, a value as measured by a method described in the Examples to be described below. follow. (I) Discharge Gas Purification Catalyst
    [025] The catalyst of the invention is characterized by including a catalyst layer A containing rhodium, palladium, and a complex oxide of ceria-zirconia-lanthan (-ytria) which may contain a certain amount or less of yttria, and in which a certain amount of palladium is disposed near the rhodium within a certain distance.
    [026] Here, in the catalyst, rhodium and palladium exist as a particle having an average particle diameter from 1 nm to 300 nm, and the average rhodium particle diameter is preferably 1 nm to 50 nm, more preferably 2 nm to 30 nm nm, and more preferably 2 nm to 15 nm. When the average particle diameter of the particle is 1 nm or more, it is possible to suppress an influence due to an interaction of the ceria-zirconia-lantana (-ytria) oxide. In addition, when the average particle diameter is 50 nm or less, the rhodium surface area that can be brought into contact with a discharge gas is not excessively reduced. Then, when the average rhodium particle diameter is adjusted to be within the above ranges, it is possible to sufficiently exert the catalytic performance. The average particle diameter of palladium is preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, and most preferably 5 nm to 50 nm. When the mean particle diameter is 1 nm or more, it is possible to suppress the influence due to an interaction of the ceriazirconia-lanthanate oxide (-ytria). In addition, when the diameter is 200 nm or less, the palladium surface area that can be contacted with a discharge gas is not excessively reduced. However, when the average particle diameter of palladium is adjusted to be within the above ranges, it is possible to sufficiently exercise the catalytic performance. The average particle diameters of rhodium and palladium are measured, for example, by a co-pulse method.
    [027] Here, the description “arranged close to rhodium within a certain distance” means that an average value of closer distances between the outer periphery and rhodium particles and the outer periphery and palladium particles (distances between Rh particles and particles closest to Pd) is 0 to 4000 nm. The distance is preferably 0 to 300 nm, more preferably 0 to 200 nm, and most preferably 0 to 80 nm. When palladium exists at a distance greater than 4000 nm, a palladium-phosphorus compound is formed to have no relationship with rhodium particles. Consequently, a palladium rhodium phosphorus poisoning suppression effect is not sufficient. On the other hand, the case of the 0 nm distance means that rhodium particles and palladium particles are merely present in the same portion without forming an alloy. In this case, although an alloy may be formed or not formed, it is preferable that an alloy is formed.
    [028] The distance between palladium particles and rhodium particles is measured, for example, by EDS (energy dispersion spectroscopy) analysis using a scanning transmission electron microscope. In this specification, an average value of the distances between Rh particles and the closest Pd particles is obtained as follows. A point on the outermost periphery of a Pd particle image existing at the shortest distance from a point on the outermost periphery of a Rh particle image determined from EDS analysis is measured to obtain a distance between particles closest to the particle of Rh Rh and the Pd particle. The same measurement is performed on 30 particles in total, and a value, which is obtained by calculating an average value of the distances between the closest particles thus obtained, is used.
    [029] When the active catalyst components are supported in a three-dimensional structure, the supported amount of rhodium is not particularly limited, but is preferably 0.001 to 1g, and more preferably 0.1 to 0.5g, in terms of Rh, for 1 liter (hereinafter, denoted as "L" in some cases) of the three-dimensional structure. In addition, the supported amount of palladium in the catalyst layer A is preferably 0.2 to 4.9 times by weight, and more preferably 0.5 to 4 times by weight with respect to the weight of Rh in the catalyst layer A.
    [030] In other words, when the supported amount of palladium is less than the above ranges, an effect of suppressing phosphorus poisoning may not be sufficient in some cases. On the other hand, when the supported amount then exceeds the quantities in the above ranges , cost performance can be deteriorated by using a large amount of an expensive noble metal and rhodium catalyst purification performance can be impaired in some cases.
    [031] Additionally, the supported amount of palladium is preferably 0.05 to 20g, and more preferably 0.1 to 10g, in terms of Pd per 1L of the three-dimensional structure.
    [032] In addition, other noble metals can be included in the active catalyst component, in addition to rhodium and palladium. Here, as other noble metals, platinum, iridium, and the like are exemplified, and platinum is preferably included. The other noble metals can be used in a form as they are, but it is preferable that other noble metals are supported in a three-dimensional structure. When the active catalyst components are supported in a three-dimensional structure, the supported amount of platinum is not particularly limited, but is preferably 10 g or less, and more preferably 0.01 to 5 g, in terms of platinum, per 1 L of the three-dimensional structure . That is, when the supported amount of platinum is 10g or less, exhaust gas purification efficiency is improved according to an introduced amount, and deterioration in cost performance due to the use of a large amount of expensive noble metal can be prevented. .
    [033] In addition, the catalyst of the invention may include a catalyst layer B other than catalyst layer A. At this time, catalyst layer B is formed by coating as a bottom layer and catalyst layer A is formed by coating as a surface layer. In addition, noble metals such as rhodium and palladium can be contained in the catalyst layer B. For example, palladium-containing catalyst layer B is coated as the bottom layer, and catalyst layer A is coated as a surface layer on catalyst layer B. It is preferable that the catalyst layer A is the outermost surface layer.
    [034] In the catalyst of the invention, when rhodium and palladium described above are supported on the same catalyst layer (the catalyst layer A) together with the complex ceria-zirconia-lanthan oxide (-ytria), which may contain a certain amount or less of yttria, as an oxygen-release-storage material, exhaust gas purification performance is efficiently exerted even in an adhesion state of the phosphorus compound.
    [035] The rate of yttria content in the ceriazirconia-lanthanate oxide (yttria) as an oxygen-release-storage material is 0 to 19% by weight, preferably 0 to 15% by weight, more preferably from 2 to 15%, and more preferably from 5 to 12% by weight. When the rate of yttria content exceeds 19% by weight, the crystal structure becomes strong. However, oxygen release is less likely to occur and catalytic performance is deteriorated. In addition, the rate of ceria content in the ceria-zirconia-lanthanate oxide (yttria) is preferably 5 to 96% by weight, more preferably 5 to 50% by weight, and most preferably 20 to 45% by weight.
    [036] Additionally, rare earth metals other than cerium, lanthanum and yttrium may be contained in the complex ceria-zirconia-lanthan oxide (-ytria) which may contain a certain amount or less of yttria. Rare earth metals can be contained either in merely a physically mixed form or in a form of a complex cerium oxide. Here, rare earth metals (excluding cerium and yttrium) may include neodymium (Nd), scandium (Sc), praseodymium (Pr), or the like and preferably include neodymium, praseodymium, or the like. Incidentally, the other rare earth metals may be in the same metal form or in an oxide form. The content rate of other rare earth metals (excluding cerium, lanthanum, and yttrium) in the complex oxide is not particularly limited, but is preferably 0 to 20%, more preferably 0.5 to 15%, and most preferably 2 to 10% , in terms of an oxide.
    [037] It is preferable that rhodium and palladium as active catalyst components are supported in a three-dimensional structure together with complex ceria-zirconia-lanthan oxide (-ytria) which may contain a certain amount or less of yttrium and is more preferable than rhodium and palladium being supported in a three-dimensional structure together with a refractory inorganic oxide, additionally. Incidentally, it is preferable that refractory inorganic oxide is supported in a three-dimensional structure, but this does not mean that a case where rhodium and palladium as components of active catalyst, and in addition other noble or similar metals are partially supported in refractory inorganic oxide is excluded. For this reason, it is preferable that the catalyst of the invention still contains refractory inorganic oxide, and in particular, it is preferable that the catalyst of the invention contains alumina containing lanthan (Al2O3-La2O3) from the point of view of improving heat resistance.
    [038] When the active components of the catalyst are supported in a three-dimensional structure, the content ratio of the complex ceria-zirconia-lanthan oxide (-ytria) in the refractory inorganic oxide is not particularly limited, but is preferably 3 to 70% by weight, and more preferably 7 to 60% by weight. When the amount of ceria-zirconia-lanthan (oxide) complex is 3% by weight or more, oxygen release-storage performance is satisfactorily exercised and the fluctuation atmosphere of the exhaust gas is effectively alleviated. On the other hand, when the amount of it is 70% by weight or less, the amount of refractory inorganic oxide, such as alumina containing lanthan, which is a base material of a noble metal as an active component, is not relatively much decreased and progression of sintering of the noble metal can be suppressed.
    [039] By the way, the term "sinter" described above means such a state that particles together in the large blocks are being exposed to a high temperature. When metal particles such as rhodium as an active catalyst component cause sintering, the surface areas of the metal particles are decreased and thus the catalytic activity is deteriorated, which is not favorable.
    [040] Anyone that is generally used as a catalyst support can be used as the refractory inorganic oxide used in the invention other than the complex ceriazirconia-lanthanide oxide (-ytria) and the lanthanum-containing alumina described above. A known refractory inorganic oxide can be used, but an inorganic oxide having a melting point of 1000 ° C or greater is preferably used. Inorganic oxides having a melting point of more preferably 1000 to 3000 ° C, and even more preferably 1500 ° C to 3000 ° C can be used. For example, a-alumina or deactivated alumina such as Y—, 8-, n—, or 0-alumina, zeolite, titania, zirconia, titania, and silicon oxide can be used. In addition, these complex oxides, for example, alumina-titania, aluminazirconia, or titania-zirconia can be used, but an activated alumina powder is preferable. Here, refractory inorganic oxide can be mixed only in a form of a mixture of two or more types. Although refractory inorganic oxide can be used as is, it is preferable that refractory inorganic oxide is supported in a three-dimensional structure. When refractory inorganic oxide is supported in a three-dimensional structure, the amount of refractory inorganic oxide used is not particularly limited, but is generally 10 to 300 g, and preferably 50 to 200 g per 1 L of the three-dimensional structure. When the amount of the same is 10 g or more, it is possible to sufficiently disperse a noble metal and thus sintering the noble metal is suppressed. So, sufficient durability can be obtained. On the other hand, when the amount of the same is 300g or less, the thickness of the catalyst layer is not excessively increased and thus the contact state between the noble metal and the exhaust gas is favorable. Then, catalytic performance can be sufficiently exercised.
    [041] The refractory inorganic oxide to be used in the invention can be in any form, such as in a granule form, a particulate form, a powder form, a cylindrical form, a conical form, a prismatic form, a cubic, pyramidal shape, and irregular shape. A granule form, a particulate formula, and a powder form are preferable, and a powder form is more preferable. When the refractory inorganic oxide is in a granule form, a particulate form, or a powder form, the average primary particle diameter of the refractory inorganic oxide is not particularly limited, but for example, it is in the range of 5 nm to 20 nm. nm, and more preferably 5 nm to 10 nm. Within this range, it is possible to withstand a noble metal in refractory inorganic oxide. Incidentally, the average primary particle shape or diameter of the refractory inorganic oxide in the invention can be measured by a known method such as a transmission electron microscope (TEM).
    [042] A specific BET surface area of refractory inorganic oxide is not particularly limited, but is preferably 50 to 750 m2 / g, and more preferably 150 to 750 m2 / g, from the point of view of the support of an active catalyst component such as a noble metal.
    [043] The method of producing a catalyst of the invention is not particularly limited, and a known method can be used. Preferably, a method is exemplified which includes mixing the active catalyst components as described above in a form that they are, or in another suitable form in a suitable solvent to prepare a paste, coating a three-dimensional structure with the paste, and then drying and calcining the coated structure.
    [044] In the method described above, there is no particular limitation on a source of rhodium (Rh) as the starting material, and raw materials used in the field of purification of a discharge gas can be used. Specific examples thereof include rhodium, halides such as rhodium chloride, inorganic rhodium salts, hexamine salt, carbonate, bicarbonate, nitrate and oxalate; carboxylates such as formate; hydroxides; alkoxides; and oxides. Preferably, nitrate, ammonium, salt, amine salt, and carbonate are exemplified. Among them, nitrate (rhodium nitrate), chloride (rhodium chloride), acetate (rhodium acetate), and hexaamine salt (rhodium hexaamine) are preferable, and rhodium nitrate is more preferable. Here, the amount of rhodium source added is such as an amount to carry the amount of rhodium supported in a three-dimensional structure as described above. By chance, in the invention, the rhodium sources described above can be used solely or as a mixture of two or more types.
    [045] Additionally, there is no particular limitation on a source of palladium (Pd) as a starting material, and raw materials used in the field of purification of a discharge gas can be used. Specific examples of it include palladium; halides such as palladium chloride; inorganic palladium salts, such as nitrate, sulfate, acetate, ammonium salt, amine salt, tetramine salt, carbonate, bicarbonate, nitrite, and oxalate; carboxylates such as format; hydroxide, alkoxide, and oxide. Preferably, nitrate, acetate, ammonium salt, amine salt, tetramine salt, and carbonate are exemplified. Among them, nitrate (palladium nitrate), chloride (palladium chloride), acetate (palladium acetate), tetramine salt (tetramine palladium) are preferable, and palladium nitrate is more preferable. By chance, in the invention, the palladium sources described above can be used alone or as a mixture of two or more types. Here, the amount of palladium source added is such that an amount to lead to the amount of palladium supported in a three-dimensional structure as described above.
    [046] Additionally, in the case where platinum is contained as an active catalyst component, there is no particular limitation on a source of platinum (Pt) as a starting material, and raw materials used in the field of purification of a discharge gas can be used. Specific examples of it include platinum; halides such as platinum bromide and platinum chloride; inorganic platinum salts, such as nitrate, dinitrodiamine salt, tetramine salt, sulfate, ammonium salt, amine salt, bisethanolamine salt, bisacetylacetonate salt, carbonate, bicarbonate, nitrite and oxalate; carboxylates such as formate; hydroxides, alkoxides, and oxides. Among them, nitrate (platinum nitrate), dinitrodiamine salt (dinitrodiamineplatin), chloride (deplatin chloride), tetramine salt (platinum tetraamide), bisethanolamine salt (bisethanolamineplatin), and bisacetyl acetonate salt (platinum bisacetylacetonate) are preferred. Nitrate and dinitrodiamine salt are more preferable. By chance, in the invention, the platinum sources described above can be used alone or as a mixture of two types. Here, the amount of platinum source added is such that an amount to carry the amount of platinum supported in a three-dimensional structure as described above.
    [047] Additionally, there is no particular limitation on a crude ceria material (source of Ce2O) of the ceria-zirconia-lanthanate oxide (-ytria) as a starting material, and crude materials used in the gas purification field discharge can be used. Specific examples thereof include nitrate such as cerium nitrate, carbonate, and sulfate. Among them, nitrate is preferably used. Incidentally, in the invention, the sources of CeO2 described above can be used alone or as a mixture of two or more types. Here, the amount of CeO2 source added is such as an amount to carry the amount of ceria supported in a three-dimensional structure as described above.
    [048] Additionally, there is no particular limitation on a raw material of zirconia (source of ZrO2), and raw materials used in the field of purification of a discharge gas can be used. Specific examples of the same include zirconium oxinitrate, zirconium oxychloride, zirconium nitrate, and basic zirconium sulfate. Among them, zirconium oxinitrate and zirconium nitrate are preferably used. Incidentally, in the invention, the sources of ZrO2 described above can be used alone or as a mixture of two or more types. Here, the amount of the ZrO2 source added is such that an amount to carry the amount of zirconia supported in a three-dimensional structure as described above.
    [049] In addition, there is no particular limitation on a raw lanthan material (La2O3), and raw materials used in the field of purification of a discharge gas can be used. Specific examples thereof include lanthanum hydroxide, lanthanum nitrate, lanthanum acetate or lanthanum hydroxide. Among them, lanthanum nitrate or lanthanum hydroxide is preferable. The sources of La2O3 described above can be used alone or as a mixture of two or more types. Here, the amount of La2O3 source added is such as an amount to lead to the amount of lanthan supported in a three-dimensional structure as described above.
    [050] Still, there is no particular limitation on a raw material of yttria (source of Y2O3), and raw materials used in the field of purification of a discharge gas can be used. Specific examples of it include yttrium hydroxide, yttrium nitrate, yttrium oxalate, and yttrium sulfate. Among them, yttrium hydroxide and yttrium are preferentially used. Incidentally, in the invention, the Y sources described above can be used alone or as a mixture of two or more types. Here, the amount of Y2O3 source added is such an amount as to lead to the amount of yttria supported in a three-dimensional structure as described above.
    [051] Additionally, in a case where the catalyst of the invention contains a refractory inorganic oxide, cerium, a complex ceria-zirconia oxide, a rat earth metal, and an alkaline earth metal, each of these components as a starting material can be used in one form as it is, or in another form, but preferably used in one form as it is. The amount of each of the added components described above is such that an amount to lead to the amount of the component supported in a three-dimensional structure as described above, or to the amount of the component existing in the catalyst as described above.
    [052] The active catalyst components as described above are mixed in an appropriate solvent to prepare a paste. There is no particular limitation on a solvent to be used to prepare paste. Any solvent used in the purification field of a discharge gas can be properly employed, but an aqueous medium is preferable. Examples of such an aqueous medium include water, low alcohols such as ethanol and 2-propanol, and aqueous organic alkali solutions. Water and a low alcohol are preferably used, and water is particularly preferably used. At this time, the concentration of the active catalyst component in the solvent is not particularly limited as long as a desired amount of it can be supported in a three-dimensional structure. The amount thereof is such that the concentration of the active catalyst component in the solvent is preferably 20 to 60% by weight and more preferably 25 to 50% by weight. In addition, after mixing the active catalyst compound in the solvent, it is preferably that the mixture is ground wet. At this time, a wet grinding method is generally carried out according to a well-known method, and there is no particular limitation thereon. For example, wet grinding is carried out using a ball crusher or the like.
    [053] Then, the catalyst of the invention can be prepared by coating the paste as described above in a three-dimensional structure, followed by drying and calcination, so that the active components of the catalyst are supported in the three-dimensional structure.
    [054] There is no particular limitation on a three-dimensional structure that is covered by the active components of the catalyst, and materials generally used in the field of purification of a discharge gas can be used appropriately, but a refractory three-dimensional structure is preferable. Such a refractory three-dimensional structure (a refractory monolithic three-dimensional structure) may include a heat resistant support such as a honeycomb support. A monolithic honeycomb structure is preferable. Examples of it include a monolithic honeycomb support, a metal honeycomb support, and a socket honeycomb support. Alternatively, a pellet holder or the like can be used although it is not a monolithic three-dimensional structure.
    [055] As a monolithic support, generally, a so-called ceramic honeycomb support is acceptable. In particular, a honeycomb support using cordierite, silicone carbide, or silicone nitride as a raw material is preferable. Among them, a cordierite honeycomb support is particularly preferable. Alternatively, a monolithic structure formed using an oxidation resistant heat resistant metal such as stainless steel and an Fe-Cr-Al alloy can be used.
    [056] These monolithic supports can be produced by an extrusion molding method, a method of strongly rolling a sheet-like element, or the like. The shape of the gas passage orifice (cell shape) can have any hexagonal, rectangular, triangular shape, and corrugation shapes. In view of usability, the cell density (cell number / unit of the cross-sectional area) from 100 to 1200 cells / in2 (0.15 to 1.86 cells / mm2) is satisfactory, and 200 to 900 cells / in2 (0.31 to 1.39 cells / mm2) is preferable.
    [057] There is no particular limitation in the conditions of drying and calcination after coating in a three-dimensional structure, and conditions used in the field of purification of a discharge gas can be appropriately employed. For example, after contacting (coating) a paste with a three-dimensional structure, the three-dimensional structure is pushed out of the paste to remove excess paste. After that, the structure is dried in air at a temperature of 50 to 300 ° C, preferably from 80 to 200 ° C, for 5 minutes to 10 hours, preferably 30 minutes to 8 hours. Subsequently, the structure is calcined at a temperature of 300 to 1200 ° C, preferably from 400 to 700 ° C, for 10 minutes to 10 hours, preferably 30 minutes to 5 hours.
    [058] By the way, in the method described above, the catalyst of the invention is produced by mixing desired active catalyst components to prepare a paste, coating the paste in a three-dimensional structure, and drying and calcining the structure. Alternatively, the catalyst of the invention can be produced as follows, for example. The catalyst of the invention can be produced by preparing two or more pastes of active catalyst components, sequentially coating each paste in a three-dimensional structure, and drying and calcining the structure. In other words, one of the pastes for each active catalyst component described above is brought into contact with a three-dimensional structure support, and then air-dried at a temperature of 50 to 300 ° C, preferably from 80 to 200 ° C, for example. 5 minutes to 10 hours, preferably 30 minutes to 8 hours. Subsequently, the structure is calcined at a temperature of 300 to 1200 ° C, preferably 400 to 700 ° C, for 10 minutes to 10 hours, preferably 30 minutes to 5 hours. Accordingly, a catalyst layer B which is a bottom layer is formed. Then, another paste of active catalyst components is similarly supported on a three-dimensional structure support, and yet as needed, yet another paste of active catalyst components is similarly supported on a three-dimensional structure support to form a catalyst layer A which is a surface layer, to render a complete catalyst.
    [059] In the catalyst of the invention as described above or the catalyst produced by the method as described above, provided that a certain amount of palladium is disposed close to rhodium within a certain distance and is supported in the complex oxide of ceria-zirconia-lantana ( -ytria) which may contain a certain amount or less of yttria, high purification performance can be maintained for a long time even in the case where a phosphorus compound is contained in the exhaust gas. For this reason, the catalyst according to the invention can preferably be used in the purification of an exhaust gas containing a phosphorus compound from an internal combustion engine.
    [060] So, the invention is also to provide a method for purifying a discharge gas, the method characterized by purifying a discharge gas containing a phosphorus compound from an internal combustion engine using the catalyst of the invention. The method includes a step of bringing the catalyst of the invention into contact with the exhaust gas containing a phosphorus compound from the internal combustion engine. (II) Catalyst usage condition
    [061] After the exhaust gas purification catalyst of the invention is exposed to a exhaust gas having a temperature of 800 ° C to 1200 ° C from an internal combustion engine, it is preferable that rhodium particles are arranged close to the particles palladium and be supported on the ceria-zirconia-lanthanate oxide which may contain a certain amount or less of yttria. That is, in this case, even when the catalyst is exposed to the highest temperature that the temperature of the catalyst bed can reach, since rhodium particles are disposed close to the palladium particles and are supported, NOx, CO, or HC in the gas. discharge can be purified even in a case where the catalyst is exposed to a discharge gas containing a phosphorus compound. Then, even after exposure to a high temperature exhaust gas, the exhaust gas containing a phosphorus compound can be effectively purified by the exhaust gas purification catalyst of the invention. (III) Discharge Gas Purification Method
    [062] The catalyst of the invention as described above or the catalyst produced by the method as described above has high purification performance not only in a state where the phosphorus compound is not accumulated but also in a state where the phosphorus compound is accumulated as phosphorus oxide (P2O5) in an amount of preferably 1 g to 50 g, more preferably 1 g to 30 g, even more preferably 3 g to 50 g, more preferably 5 g to 10 g per 1 L of the three-dimensional structure. The state where 1 g or more of the phosphorus compound is included is a state that can occur after a long period of use, and it is necessary to consider a case where 1 g or more of the phosphorus compound is included in order to improve long-term durability . On the other hand, a case where 50 g or more of the phosphorus compound is accumulated corresponds to a malfunction in an engine oil or combustion system, and this is a state that may not occur in a normal start. Consequently, this state is not considered.
    [063] Additionally, when the catalyst is coated in a three-dimensional structure and used, in the catalyst of the related technique, generally the phosphorus compound is accumulated in a high concentration on the surface of the catalyst layer and the concentration distribution of the phosphorus compound inside the catalyst layer in the depth direction is uneven. On the other hand, as compared to the prior art catalyst, in the catalyst of the invention, the phosphorus compound is not intensively accumulated in the same portion but is dispersed in the catalyst layer. The concentration distribution of the phosphorus compound within the catalyst layer in the depth direction is obtained by analyzing the mapping image that is obtained by performing analysis on the spectrum belonging to the Ka ray of P (phosphorus) according to EPMA analysis (microanalyzer of electron probe). When the mapping image is organized based on the X-ray intensity, in the catalyst of the related technique, portions in which a highly concentrated phosphorus compound (high intensity) adheres are detected much more than portions in which a poorly concentrated phosphorus compound (low intensity) adheres. On the other hand, in the catalyst of the invention, portions to which a poorly concentrated (low intensity) phosphorus compound adheres are much more detected than portions to which a highly concentrated (high intensity) phosphorus compound adheres. More specifically, the catalyst of the invention is characterized in that, as described in the Examples below, a cross section in a detection portion at 0 to 10% of the maximum intensity of phosphorus Ka ray in analysis EPMA (electron probe microanalyzer) is greater than a cross section in a detection portion in 10 to 54% of it. Here, with respect to the amount of phosphorus compound contained in the catalyst as measured by XRF (X-ray fluorescence analysis), the related technique and the invention is the same. Accordingly, it can be said that, in the catalyst of the invention, the phosphorus compound is infiltrated while being in an additional dispersed state.
    [064] For this reason, the catalyst according to the invention can preferably be used in the purification of the exhaust gas containing a phosphorus compound from the internal combustion engine, and in particular, it exhibits an excellent effect in the purification of nitrogen oxide, carbon monoxide, and hydrocarbon that are contained in an exhaust gas from an internal combustion engine such as a gasoline engine.
    [065] However, the invention is also to provide a method for purifying an exhaust gas, the method characterized by purifying an exhaust gas using an exhaust gas purification catalyst described above. More specifically, the method of the invention is a method of purifying a discharge gas, the method characterized by purifying nitrogen oxide, carbon monoxide, and hydrocarbon into a discharge gas containing a phosphorus compound from an internal combustion engine using the catalyst, that is, a method to purify nitrogen oxide, carbon monoxide, and hydrocarbon in a discharge gas using the exhaust gas purification catalyst until the amount of phosphorus compound accumulation in the exhaust gas of the engine internal combustion is 1g to 30g per 1L of the three-dimensional structure.
    [066] The method includes a step of exposing the catalyst of the invention to a discharge gas containing a phosphorus compound from an internal combustion engine. Here, in this specification, the description “expose to a gas” means that the exhaust gas purification catalyst is brought into contact with the gas, and includes not only a case where all of the catalyst's surface is brought into contact with gas but also a case where a part of the catalyst surface is placed in contact with the gas.
    [067] A method for exposing the exhaust gas purification catalyst to the exhaust gas is not particularly limited, and for example, the exhaust gas purification catalyst can be exposed to the exhaust gas in such a way that the catalyst The exhaust gas purification system is placed in the exhaust gas path of an exhaust port of the internal combustion engine, and the exhaust gas is allowed to flow into the exhaust gas path.
    [068] The gas described above is not particularly limited as it is an exhaust gas from the internal combustion engine. Examples of the same include nitrogen oxide (eg, NO, NO2, or N2O), carbon monoxide, carbon dioxide, oxygen, hydrogen, ammonia, water, sulfur dioxide, and various hydrocarbons.
    [069] The internal combustion engine is not particularly limited. For example, a gasoline engine, a hybrid engine, or an engine using a fuel such as natural gas, ethanol, or dimethyl ether can be used. Among them, an engine using gasoline is preferably used as the internal combustion engine.
    [070] The timing for exposing the exhaust gas purification catalyst to the exhaust gas is not particularly limited, but it is sufficient to hold a time during which at least part of the exhaust gas purification catalyst can be brought into contact with discharge gas.
    [071] The exhaust gas temperature is not particularly limited, but is preferably 0 ° C to 800 ° C, that is, in a range of the exhaust gas temperature during normal activation. Here, an air / fuel ratio of the exhaust gas having a temperature of 0 ° C to 800 ° C of the internal combustion engine is 10 or more but less than 30, and preferably 11 to 14.7.
    [072] The catalyst of the invention as described above or catalyst produced by the method as described above can be exposed to a discharge gas having a temperature of 800 to 1200 ° C. Here, the air / fuel ratio of the exhaust gas having a temperature of 800 to 1200 ° C is preferably 10 to 18.6. In addition, the time to expose the exhaust gas purification catalyst to an exhaust gas with excess oxygen having a temperature of 800 ° C to 1200 ° C is not particularly limited, but for example, it can be 5 to 500 hours .
    [073] Additionally, the temperature of a catalyst inlet part in a case where a phosphorus compound adheres to the catalyst inlet part is preferably 200 ° C to 1200 ° C, and preferably 500 ° C to 1000 ° C. The exhaust gas emitted from the internal combustion engine varies depending on a fuel, a lubricant, and a lubricant additive to be used, but a fuel, a lubricant, and a lubricant additive that are suitable for an MPI engine. multi-point) are preferably used.
    [074] Incidentally, it is preferable that the temperature of the exhaust gas be at a temperature of the exhaust gas at the inlet part of the catalyst. Here, the term “catalyst inlet part” is a part of a discharge pipe, the part of which has a space provided between a catalyst end face and a discharge gas inflow side provided with the gas purification catalyst discharge and a portion 20 cm away from the end face towards the side of the internal combustion engine, and in a center with respect to the vertical direction of the discharge pipe. In addition, the term "catalyst bed part" is a part in a middle position between the end face and the discharge gas flow side and the other end face to the discharge gas flow side, and in the center with respect to the vertical direction of the discharge pipe (in a case where the discharge pipe has a shape other than a circular shape, the part is positioned in a center of gravity with respect to the cross section in the vertical direction of the discharge pipe discharge).
    [075] Additionally, a similar or different exhaust gas purification catalyst can be arranged downstream (flow side) of the catalyst of the invention, but as long as a large amount of phosphorus compound adheres upstream rather than downstream, the catalyst of the invention is preferably disposed downstream. EXAMPLES
    [076] The effect of the invention will be described by means of the following Examples and Comparative Examples. However, the technical scope of the invention is not intended to be limited only by the following Examples. By the way, in this specification, exposing the catalyst to a discharge gas containing a phosphorus compound is referred to as “phosphorus poisoning treatment” and exposing the catalyst to a high temperature of 800 ° C to 1200 ° C is referred to as “ heat resistant treatment ”. [Example 1] (Catalyst Layer B formation)
    [077] Each of an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2 (CeO2: ZrO2 = 30:70, the same applied hereinafter), alumina containing lanthanum (Al2O3-La2O3), and barium hydroxide were weighed so that a weight ratio of palladium (Pd): complex CeO2-ZrO2 oxide: Al2O3-La2O3: barium oxide (BaO) would be 3.625: 60: 30: 10, and then was ground wet in a spherical crusher , to prepare a paste (a1). The prepared paste (a1) was reactively coated in an amount in which the total amount of each component described above was 103.625 g / L (hereinafter, a weight per 1L of cordierite support is denoted as g / L), in a 0.8L cordierite support having a cell density of 600 cells / in2 (0.93 cells / mm2) (the same applied hereinafter), dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour. (Catalyst Layer A formation)
    [078] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 59: 4: 12, and Al2O3-La2O3 was weighed so that a weight ratio of rhodium (Rh): Palladium (Pd): complex oxide of CeO2-ZrO2-La2O3-Y2O3: Al2O3-La2O3 could be 0.35: 0.175: 60: 40, and then it was crushed wet in a spherical crusher, to prepare a paste (a2). The prepared paste (a2) was reactively coated in an amount in which the total amount of each component described above was 100.525 g / L, on the cordierite support that has been coated with the paste (a1) in advance, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield a catalyst A which was coated with 3.8 g / L of palladium and 0.35 g / L of rhodium. [Example 2] (Catalyst Layer B formation)
    [079] Each of an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2, Al2O3-La2O3, and barium hydroxide was weighed as a weight ratio of palladium (Pd): complex oxide of CeO2-ZrO2: Al2O3-La2O3: BaO is 3.36: 60: 30: 10, and then it was crushed in a spherical crusher, to prepare a paste (b1). The prepared paste (b1) was reactively coated in an amount of 103.36 g / L in 0.8 L of a cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour . (Catalyst Layer A formation)
    [080] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 59: 4: 12, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 0.44: 60 : 40, and then it was ground in a spherical grinder to make a paste (b2). The prepared paste (b2) was reactively coated in an amount of 100.79 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield a catalyst B that was coated with 3.8 g / L of palladium and 0.35 g / L of rhodium. [Example 3] (Catalyst Layer B formation)
    [081] Each of an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2, Al2O3-La2O3, and barium hydroxide was weighed as a weight ratio of palladium (Pd): complex CeO2-ZrO2 oxide: Al2O3-La2O3: BaO is 2.925: 60: 30: 10, and then it was ground in a spherical grinder to prepare a paste (b1). The prepared paste (b1) was similarly reactively coated in an amount of 102.925 g / L in 0.8 L of a cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour. (Catalyst Layer A formation)
    [082] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 59: 4: 12, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 0.875: 60: 40 , and then it was crushed in a spherical crusher, to prepare a paste (c2). The prepared paste (c2) was reactively coated in an amount of 101.225 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield a catalyst B that was coated with 3.8 g / L of palladium and 0.35 g / L of rhodium. [Example 4] (Catalyst Layer B formation)
    [083] Each of an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2, Al2O3-La2O3, and barium hydroxide was weighed as a weight ratio of palladium (Pd): complex CeO2-ZrO2 oxide: Al2O3-La2O3: BaO is 2.4: 60: 30: 10, and then it was ground in a spherical crusher, to prepare a paste (d1). The prepared paste (d1) was similarly reactively coated in an amount of 102.4 g / L in 0.8 L of a cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour . (Catalyst Layer A formation)
    [084] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 59: 4: 12, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 1.4: 60 : 40, and then it was crushed in a spherical crusher, to prepare a paste (d2). The prepared paste (d2) was reactively coated in an amount of 101.75 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield a catalyst B that was coated with 3.8 g / L of palladium and 0.35 g / L of rhodium. [Comparative Example 1] (Catalyst Layer B formation)
    [085] Each of an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2, Al2O3-La2O3, and barium hydroxide was weighed as a weight ratio of palladium (Pd): complex oxide of CeO2-ZrO2: Al2O3-La2O3: BaO is 3.8: 60: 30: 10, and then it was ground in a spherical crusher to prepare a paste (e1). The prepared paste (e1) was similarly reactively coated in an amount of 103.8 g / L in 0.8 L of a cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour . (Catalyst Layer A formation)
    [086] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 59: 4: 12, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: CeO2-rO2-La2O3-Y2O3: Al2O3-La2O3, oxide would be 0.35: 60: 40, and then it was crushed in a spherical crusher, to prepare a paste (e2). The prepared paste (e2) was reactively coated in an amount of 100.385 g / L on the cordierite support that was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield a catalyst B that was coated with 3.8 g / L of palladium and 0.35 g / L of rhodium. [Comparative Example 2] (Catalyst Layer B formation)
    [087] Each of an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2, Al2O3-La2O3, and barium hydroxide was weighed as a weight ratio of palladium (Pd): complex CeO2-ZrO2 oxide: Al2O3-La2O3: BaO is 3.765: 60: 30: 10, and then it was ground in a spherical grinder to prepare a paste (f1). The prepared paste (f1) was similarly reactively coated in an amount of 103.765 g / L in 0.8 L of a cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour. (Catalyst Layer A formation)
    [088] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 59: 4: 12, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 0.035: 60: 40 , and then it was crushed in a spherical crusher, to prepare a paste (f2). The prepared paste (f2) was reactively coated in an amount of 101.75 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield a catalyst B that was coated with 3.8 g / L of palladium and 0.35 g / L of rhodium. [Comparative Example 3] (Catalyst Layer B formation)
    [089] Each of an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2, Al2O3-La2O3, and barium hydroxide was weighed as a weight ratio of palladium (Pd): complex CeO2-ZrO2 oxide: Al2O3-La2O3: BaO is 2.05: 60: 30: 10, and then it was ground in a spherical crusher, to prepare a paste (g1). The prepared paste (g1) was reactively coated in an amount of 102.05 g / L in 0.8 L of a cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour . (Catalyst Layer A formation)
    [090] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 59: 4: 12, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 1.75: 60 : 40, and then it was crushed in a spherical crusher, to prepare a paste (g2). The prepared paste (g2) was reactively coated in an amount of 100.79 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield a catalyst B that was coated with 3.8 g / L of palladium and 0.35 g / L of rhodium. [Example 5] (Catalyst Layer B formation)
    [091] The paste (b1) used in Example 2 was reactively coated in an amount of 103.36 g / L in 0.8 L of cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour. (Catalyst Layer A formation)
    [092] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 69: 4: 2, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 0.44: 60 : 40, and then it was crushed in a spherical crusher, to prepare a paste (h2). The prepared paste (h2) was reactively coated in an amount of 100.79 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield an L catalyst that was coated with 3.8 g / L palladium and 0.35 g / L rhodium. [Example 6] (Catalyst Layer B formation)
    [093] The paste (b1) used in Example 2 was reactively coated in an amount of 103.36 g / L in 0.8 L of cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour. (Catalyst Layer A formation)
    [094] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 66: 4: 5, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 0.44: 60 : 40, and then it was ground in a spherical grinder to prepare a paste (i2). The prepared paste (i2) was reactively coated in an amount of 100.79 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield an L catalyst that was coated with 3.8 g / L palladium and 0.35 g / L rhodium. [Example 7] (Catalyst Layer B formation)
    [095] The paste (b1) used in Example 2 was reactively coated in an amount of 103.36 g / L in 0.8 L of cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour. (Catalyst Layer A formation)
    [096] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 56: 4: 15, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 0.44: 60 : 40, and then it was crushed in a spherical crusher, to prepare a paste (j2). The prepared paste (j2) was reactively coated in an amount of 100.79 g / L on the cordierite support that was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield an L catalyst that was coated with 3.8 g / L palladium and 0.35 g / L rhodium. [Comparative Example 4] (Catalyst Layer B Formation)
    [097] The paste (b1) used in Example 2 was reactively coated in an amount of 103.36 g / L in 0.8 L of cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour. (Catalyst Layer A Formation)
    [098] Then, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 51: 4: 20, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 0.44: 60 : 40, and then it was crushed in a spherical crusher, to prepare a paste (k2). The prepared paste (k2) was reactively coated in an amount of 100.79 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield an L catalyst that was coated with 3.8 g / L palladium and 0.35 g / L rhodium. [Comparative Example 5] (Catalyst Layer B formation)
    [099] The paste (b1) used in Example 2 was reactively coated in an amount of 103.36 g / L in 0.8 L of cordierite support, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour. (Catalyst Layer A formation)
    [100] Next, each of an aqueous solution of rhodium nitrate, an aqueous solution of palladium nitrate, a complex oxide of CeO2-ZrO2-La2O3-Y2O3 formed in a ratio of CeO2: ZrO2: La2O3: Y2O3 = 25: 41: 4: 30, and Al2O3-La2O3 was weighed so that a weight ratio of Rh: Pd: CeO2-ZrO2-La2O3-Y2O3 oxide: Al2O3-La2O3, would be 0.35: 0.44: 60 : 40, and then it was crushed in a spherical crusher, to prepare a paste (l2). The prepared paste (l2) was reactively coated in an amount of 100.79 g / L on the cordierite support which was coated with the paste (b1) previously, dried at 150 ° C for 15 minutes, and then calcined at 500 ° C for 1 hour, to yield an L catalyst that was coated with 3.8 g / L palladium and 0.35 g / L rhodium. <Heat Resistance and Phosphorus Poisoning Treatment>
    [101] Each of the catalysts A to D and H to J obtained in Examples 1 to 7 and catalysts E to G, K and L obtained in Comparative Examples 1 to 5 was placed 25 cm on the downstream side of an engine discharge port. 3.0 liter six-cylinder type V and subjected to heat resistance treatment and phosphorus poisoning using an oil having a phosphorus (P) concentration of 3000 ppm in an engine oil. At this time, the temperature of part of the catalytic bed was adjusted to 14.6, and a cycle in which the engine was operated for 25 seconds, and subsequently, the engine was operated for 3 seconds while the fuel supply was stopped was repeated and the operation was carried out for 100 hours in total. It was found that 7.4 g or more of the phosphorus compound per 1 L of three-dimensional structure was contained as phosphorus oxide (P2O5) in the catalyst by analyzing the phosphorus content in each catalyst supported in this way with XRF (X-ray fluorescence analysis) X). <Distances between closest Rh particles and Pd particles and Rh particle diameters and Pd particles>
    [102] After the heat resistant treatment and the phosphorus poisoning treatment are carried out on catalysts A to D and H to J obtained in Examples 1 to 7 and catalysts E to G, K and L obtained in Comparative Examples 1 to 5 , distances between Rh particles and the closest Pd particles were measured by TEM-EDS (energy dispersive X-ray spectroscopy by electron transmission microscope). The measurement results are shown in Table 1. Additionally, at this time, the particle diameter of each of the particles in which Rh was detected by TEM-EDS analysis was 50 nm or less in all catalysts, and the particle diameter of each of the particles in which Pd was detected was 200 nm or less in all of the catalysts. [Table 1] Table 1: Amount of phosphorus adhesion in each catalyst after treatment of phosphorus poisoning
    <EPMA image after Phosphorus Poisoning Treatment>
    [103] Fig. 1 shows EPMA images in which catalysts A to E that have been subjected to phosphorus poisoning treatment are rated 0 to 10%, 10% to 54%, and 54% to 100% of the maximum intensities in the phosphorus Ka radius. From this drawing, it is found that catalysts A to D of the Examples are different from catalyst E of the Comparative Example and portions of 0 to 10% are more than portions of 10 to 54%. Starting from the fact that the adherent amount of the phosphorus compound in all catalysts is the same (Table 1), the results in Fig. 1 show that a portion where a poorly concentrated phosphorus compound is present is widely present in the catalyst layer of the catalysts of the Examples as compared to the catalyst of the Comparative Example. This means that the phosphorus compound in the catalyst layer is more dispersed in the catalysts of the Examples as compared to the catalyst of the Comparative Example. <Performance Evaluation of the Discharge Gas Purification Catalyst>
    [104] Each of the catalysts that have been subjected to heat resistance treatment before and after phosphorus poisoning has been placed 30 cm downstream of a 2.0-liter straight six-cylinder engine discharge port. , the temperature of part of the catalytic bed was increased at a rate of 50 ° C / min while an A / F was adjusted to 14.6 and was changed at an A / F amplitude of ± 0.5 and at a frequency of 0 , 5 Hz, the gas emitted from a catalyst outlet was sampled, and each of the purification efficiency of CO, THC, and NOx was calculated. The temperature at which each purification efficiency reaches 50% is denoted as T50, and the results are shown in Table 2. As T50 after phosphorus poisoning treatment is lower, higher exhaust gas purification performance is displayed even after treatment of phosphorus poisoning. In addition, AT50 was calculated by subtracting T50 before phosphorus poisoning (after heat duration) from T50 after phosphorus poisoning. It can be said that, in this AT50 is less, the catalytic performance is also not deteriorated by the treatment of phosphorus poisoning. Furthermore, it can be said that, in a catalyst having a low AT50 but a high T50, the catalytic performance in the initial stage or before the treatment of phosphorus poisoning is low. Therefore, a catalyst having a low AT50 and a low T50 is preferable.
    [105] From the results of Table 2, it is found that, in the catalysts of the Examples of the invention, T50 after phosphorus poisoning treatment is low and AT50 is also low. This means that the catalyst of the invention exhibits high catalytic performance even in a state where the phosphorus compound adheres. [Table 2] Table 2: Engine evaluation results on the test bench


    [106] By the way, this application is based on Japanese Patent Application No. 2013-017202 filed on January 31, 2013, and the disclosure of which is incorporated herein by reference in its entirety.
    权利要求:
    Claims (7)
    [0001]
    1.Discharge gas purification catalyst purifying a discharge gas containing a phosphorus compound, the catalyst characterized by the fact that it comprises: a catalyst layer A containing rhodium (Rh), palladium (Pd), and or a complex oxide ceria-zirconia-lantana or a complex ceria-zirconia-lanthania-oxide as active components of the catalyst; wherein an average value of the distances between Rh particles and the Pd particles closest to Rh and Pd is 0 to 4000 nm; a weight ratio of Pd to Rh is 0.2 to 4.9; and a ratio of yttria content in the ceriazirconia-lanthania-yttria complex oxide is 19% by weight or less.
    [0002]
    2. Discharge gas purification catalyst according to claim 1, characterized by the fact that it still comprises alumina containing lanthanum.
    [0003]
    3. Discharge gas purification catalyst according to claim 1 or 2, characterized in that it comprises: a catalyst layer B in which the catalyst layer B comprises noble metals selected from the group consisting of rhodium and palladium , a complex oxide of CeO2-ZrO2 and alumina containing lanthanum (Al2O3-La2O3); wherein the catalyst layer B is formed by coating as a bottom layer, and the catalyst layer A is formed by coating as a surface layer.
    [0004]
    Discharge gas purification catalyst according to any one of claims 1 to 3, characterized in that it comprises a phosphorus compound.
    [0005]
    Discharge gas purification catalyst according to any one of claims 1 to 4, characterized by the fact that: the active components of the catalyst are supported in a three-dimensional structure; and the phosphorus compound is contained as phosphorus oxide in an amount of 1 to 50g per 1L of the three-dimensional structure.
    [0006]
    6. Discharge gas purification catalyst, according to claim 4 or 5, characterized by the fact that a cross section in a detection portion at 0 to 10% of the maximum intensity of the phosphorus Ka ray under analysis EPMA (microanalyzer) electron probe) is greater than the cross section in a detection portion in 10 to 54% of it.
    [0007]
    7. Method for purifying a discharge gas, the method characterized in that it comprises purifying a discharge gas using the exhaust gas purification catalyst as defined in any one of claims 1 to 6.
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    JPWO2014119749A1|2017-01-26|
    CN104968430A|2015-10-07|
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    法律状态:
    2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-30| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-08| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2013-017202|2013-01-31|
    JP2013017202|2013-01-31|
    PCT/JP2014/052323|WO2014119749A1|2013-01-31|2014-01-31|Exhaust-gas purification catalyst and exhaust-gas purification method using said catalyst|
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