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    • 专利摘要:
    Exhaust Gas Purification Catalyst, Method for Its Production, and Exhaust Gas Purification Method Using the Same Objective The aim of the present invention is to provide an exhaust gas purification catalyst which is capable of effectively processing an exhaust gas, particularly carbon monoxide (co) and hydrocarbon (hc) in the exhaust gas at a low temperature, and a method for producing the exhaust gas purification catalyst. the objective is achieved by an exhaust gas purification catalyst which is obtained by having a carrier containing a1203 and one or more metal oxides selected from the group consisting of zirconium oxide (zr02), cerium oxide (ce02), yttrium (y203), neodymium oxide (nd203), silicon oxide (si02) and titanium oxide (thio2) which support one or more catalyst components selected from the group consisting of gold (au), silver (ag), platinum ( pt), palladium (pd), rhodium (rh), iridium (ir), ruthenium (ru) and osmium (os). metal oxides have particle diameters of less than 10 nm.
    公开号:BR112013022519B1
    申请号:R112013022519
    申请日:2012-02-29
    公开日:2019-08-13
    发明作者:Kato Naohiro；Goto Yosuke；ogino Yuji；Akasaka Yuta
    申请人:Umicore Shokubai Japan Co Ltd；Umicore Shokubai USA Inc；
    IPC主号:
    专利说明:

    CATALYST FOR PURIFICATION OF EXHAUST GAS, METHOD FOR ITS PRODUCTION AND METHOD OF PURIFICATION OF EXHAUST GAS USING THE SAME
    TECHNICAL FIELD
    The present invention relates to a catalyst for purifying exhaust gas, a method for producing the catalyst and a method of purifying exhaust gas using the catalyst. In particular, the invention relates to an exhaust gas purification catalyst effective in purifying an exhaust gas, in particular a diesel engine exhaust gas, a method for producing the catalyst and an exhaust gas purification method using the catalyst.
    TECHNICAL FUNDAMENTALS
    Various techniques for purifying an exhaust gas generated by internal combustion have been conventionally proposed. In particular, several techniques for purifying a diesel engine exhaust gas have been proposed in order to reduce the discharge of particulate materials (PM) and N0 x contained in an exhaust gas. For example, catalysts for the purification of an exhaust gas have been proposed, oxidation catalysts that oxidize carbon monoxide (hereinafter also called CO) and hydrocarbon (hereinafter also called HC) in CO2 and H 2 0, catalysts for storage of N0 x which store nitrogen oxides (hereinafter also called N0 x ), three-way catalysts that simultaneously remove NO X , CO and HC, and the like.
    It is necessary that a catalyst for purification of
    2/84 exhaust gas has high thermal durability, as it is exposed to the exhaust gas at a high temperature. For example, Patent Literature 1 discloses fine mixed oxide powder obtained by uniformly dispersing Zr oxide and M metal oxide, which does not form a solid solution with Zr oxide, on the nm scale. Patent Literature 1 discloses that fine mixed oxide powder has a high specific surface area and a high pore volume and therefore, when it supports a precious metal to form a catalyst, the growth of precious metal particles is suppressed after aging at a high temperature.
    Patent Literature 2 discloses an inorganic oxide powder containing secondary particles, containing primary particles made of AI2O3, primary particles made of metal oxides of one or at least two of ZrC> 2, SiO 2 and T1O2, and rare earth elements and / or rare earth oxides. The inorganic oxide powder consists of secondary particles obtained by dispersing primary particles made of AI2O3 and primary particles made of the metal oxides described above in an interference state between them and has thermal durability.
    LIST OF QUOTES
    Patent literature
    Patent Literature 1: JP-A No. 2003-20227
    Patent Literature 2: Japanese Patent No. 4352897
    SUMMARY OF THE INVENTION
    Technical problem
    However, the thermal durability of catalysts was not sufficient with the techniques in the literature described
    3/84 above, and additional enhancements were desired. In addition, the literature described above does not disclose a catalyst capable of effectively purifying carbon monoxide (CO) and hydrocarbon (HC) when an exhaust gas temperature is a low temperature in the purification of an exhaust gas, particularly a gas exhaust from a diesel engine.
    Therefore, an objective of the present invention is to provide a catalyst for purifying exhaust gas with high thermal durability and a method for producing the catalyst. Another objective of the present invention is to provide a catalyst for purifying exhaust gas that is capable of effectively purifying an exhaust gas, particularly carbon monoxide (CO) and hydrocarbon (HC) in the exhaust gas at a low temperature, and a method for catalyst production.
    Solution of the problem
    The present inventors have carried out intensive studies in order to solve the problems described above; as a result, they found that an exhaust gas purification catalyst obtained having a carrier containing A1 2 O 3 and a specific metal oxide supports one or more specific catalyst components, and HC and CO in an exhaust gas can be effectively purified , and with this the present invention has been completed.
    More specifically, the present invention provides an exhaust gas purification catalyst, which is obtained by having a carrier that includes aluminum oxide (A1 2 O 3 ) and one or more metal oxides selected from the group consisting of zirconium oxide (ZrO 2 ), cerium oxide
    4/84 (CeO 2 ), yttrium oxide (Y2O3), neodymium oxide (Nd 2 O 3 ), silicon oxide (SiO 2 ) and titanium oxide (TiO 2 ) which supports one or more catalyst components selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) and osmium (Os), in which the metal oxides have diameters particle size less than 10 nm.
    Advantageous effects of the invention
    In accordance with the present invention, an exhaust gas purification catalyst capable of effectively purifying an exhaust gas, in particular HC and CO in the exhaust gas, is provided, even at a low temperature.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Fig. 1 is a graph showing powder X-ray diffrometry of carriers in Examples 1-1 to 1-5 and n
    Comparative example 1-1.
    Fig. 2 is a graph showing powder X-ray diffrometry measured using carriers in Examples 1-3 to 1-5 and Comparative Example 1-1.
    Fig. 3 is a graph showing ZrO 2 contents and conversion of 50% CO in catalyst carriers in Examples 1-3 to 1-5 and Comparative Examples 1-1 and 1-2.
    Fig. 4 is a graph showing ZrO 2 levels and 50% HC conversion in catalyst carriers in
    Examples 1-3 to 1-5is and Examplesa graph comparative 1-1 and 1-2. THE Fig. 5 what show diffractometry in X ray in powder in carriers we Examples 2-1 to 2-3 and at the Example comparative 2-1. THE Fig. 6 is a graph what show diffractometry in
    5/84 carrier powder X-rays in Examples 2-4 to 2-6 and Comparative Example 2-1.
    Fig. 7 is a graph showing the CO purification ability measured using catalysts in Examples 2-1 to 2-3 and in Comparative Example 2-1.
    Fig. 8 is a graph showing the CO purification ability measured using catalysts in Examples 2-4 to 2-6 and in Comparative Example 2-1.
    DESCRIPTION OF MODALITIES
    The first embodiment of the present invention provides a catalyst for purifying exhaust gas, which is obtained by having a carrier containing AI2O3 and one or more metal oxides selected from the group consisting of zirconium oxide (ZrO 2 ), cerium oxide (CeO 2 ), yttrium oxide (Y2O3), neodymium oxide (Nd 2 C> 3), silicon oxide (SiO 2 ) and titanium oxide (TiO 2 ) supports one or more catalyst components selected from the group consisting of gold ( Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) and osmium (Os), where the metal oxides have particle diameters less than 10 nm (hereinafter, the exhaust gas purification catalyst of the present invention can also be called simply the catalyst).
    That is, in the first exhaust gas purification catalyst of the invention, AI2O3, a specific metal oxide (hereinafter also can be called simply metal oxide) and a specific catalyst component (hereinafter also can be called simply a catalyst component ) are essentially present. Among these components, the
    6/84 catalyst component is a precious metal, and insofar as a precious metal has an oxidizing activity, it converts nitrogen oxide (NOx), carbon monoxide (CO) and hydrocarbon (HC), which is a non-component burned fuel, such as gasoline or diesel engine fuel, such as light oil and heavy oil, in a carbon dioxide exhaust gas, harmless water, nitrogen, and the like, and purifies a gas exhaustion.
    The first exhaust gas purification catalyst of the present invention can effectively purify carbon monoxide (CO) and hydrocarbon (HC) even at a low temperature and is preferably used particularly as an exhaust gas purification catalyst effective in purifying an exhaust gas from a diesel engine.
    mechanism capable of obtaining the advantage described above is undefined, however, it can be deduced as follows. Furthermore, the present invention is in no way limited to the deduction described below.
    In the present invention, AI2O3 and a metal oxide are a form of a mixture, which is a mixture obtained by mixing primary particles of the respective compounds in nano order. AI2O3 and metal oxide are different in terms of primary particle sizes. When the metal oxide is contained in a specific content in a carrier containing AI2O3 and the metal oxide, the metal oxide has a primary particle diameter less than 10 nm. That is, when a mass ratio of AI2O3 and metallic oxide is 99.5: 0.5 to 60:40, the oxide
    7/84 metal has a primary particle diameter of less than 10 nm and preferably has a very fine crystal structure or an amorphous (non-crystalline) structure. AI2O3 preferably has a primary particle diameter of 10 to 100 nm.
    In the present invention, AI2O3 and the metal oxide do not form a complex oxide and are in the form of a nano-order mixture, as described above. This is because the metal oxide contained with AI2O3 has a property of not forming a complex oxide with AI2O3, primary particles of a complex oxide made of its oxides hardly exist, and primary simple oxide particles of each of the compounds exist. That is, the first exhaust gas purification catalyst of the present invention is a mixture that is obtained by dispersing primary particles of AI2O3 and primary particles of metal oxide. The shape of the mixture is assumed to be one in which primary particles of fine metal oxide are fitted into primary particles of A1 2 O 3 . That is, the mixture is in a form of combining fine metal oxide into primary particles of AI2O3. At that time, the metal oxide, as described above, has a primary particle diameter of less than 10 nm and preferably has a very fine crystal structure or an amorphous (non-crystalline) structure.
    In the first exhaust gas purification catalyst of the present invention, A1 2 O 3 and a metal oxide do not form a complex oxide, primary particles of metal oxide and primary particles of A1 2 O 3 intervene between the respective primary particles, thus considering ,
    8/84 that the progress of the growth of primary particles of a simple oxide is inhibited and the reduction of a surface area and pore capacity are sufficiently inhibited, and the dispersibility of a catalyst component to be supported can, therefore, sufficiently maintained. As a result, it is assumed that the catalyst that has the carrier maintains a catalytic activity, even when used under the condition of an elevated temperature, and the catalyst can purify exhaust gas even at a low temperature.
    As described above, AI2O3 and a metal oxide do not form a complex oxide, AI2O3 and metal oxide that have a primary particle diameter of less than 10 nm form a mixture in a specific mixing ratio (mass ratio) in nano order and, therefore, an excellent exhaust gas purification catalyst is obtained in terms of thermal durability. The oxidation catalyst of the present invention maintains a catalytic activity, even when used under a high temperature condition, and can effectively purify (oxidize) an exhaust gas, even when the thermal history becomes long. That is, a precious metal effectively acts on nitrogen oxide (NOx), carbon monoxide (CO) and hydrocarbon (HC), which is an unburned fuel component, such as gasoline or diesel engine fuel such as , for example, light oil and heavy oil, in particular carbon monoxide (CO) and hydrocarbon (HC), in an exhaust gas, and more successfully purifies an exhaust gas even at a low temperature.
    9/84
    Consequently, the first oxidation catalyst obtained by the method of the present invention has high thermal durability and can effectively purify an exhaust gas, particularly carbon monoxide (CO) and hydrocarbon (HC) in an exhaust gas, even at a temperature low. Therefore, the first oxidation catalyst of the present invention is particularly effective for purifying exhaust gas from the diesel engine under a low temperature, even when used under a high temperature condition.
    The first preferred embodiment of the present invention provides a catalyst for purifying exhaust gas, which is obtained by having a carrier containing A1 2 O 3 and one or more metal oxides selected from the group consisting of zirconium oxide (ZrO 2 ), oxide cerium (CeO 2 ), yttrium oxide (Y 2 O 3 ), neodymium oxide (Nd 2 O 3 ), silicon oxide (SiO 2 ) and titanium oxide (TiO 2 ) that support one or more catalyst components that are selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) and osmium (Os), in which the metal oxides have particle diameters less than 10 nm. In addition, a mass ratio of aluminum oxide and metal oxide is preferably 99.5: 0.5 to 70:30.
    The second embodiment of the present invention provides a catalyst for purifying exhaust gas, which is obtained by having a carrier that is made up of 60 to 99.49 parts per mass of aluminum oxide (A1 2 O 3 ), 0.5 to 20 parts per mass of zirconium oxide (ZrO 2 ), and one or more metal oxides selected from the group consisting of 0.01
    10/84 to 10 parts by mass of silicon oxide (SiO2) and 0.01 to 10 parts by mass of titanium oxide (TIO2) (the total mass of aluminum oxide, zirconium oxide and metal oxides is 100 parts by mass) that support one or more catalyst components that are selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) and osmium (Os).
    That is, in the second exhaust gas purification catalyst of the present invention, Ai 2 O3, ZrC> 2r a specific metal oxide (hereinafter, between metal oxides, S1O2 and / or T1O2 can also be called the second metal oxide) and a specific catalyst component essentially exist. Among these components, the catalyst component is a precious metal, and insofar as a precious metal has an oxidation activity, it converts nitrogen oxide (NOx), carbon monoxide (CO) and hydrocarbon (HC), which is a unburned fuel component such as gasoline or diesel engine fuel, such as light oil and heavy oil, in an exhaust gas in harmless carbon dioxide, water, nitrogen, and the like, and purifies a exhaust gas.
    The second exhaust gas purification catalyst of the present invention can effectively purify carbon monoxide (CO) even at a low temperature, and in addition, the catalyst can effectively purify carbon monoxide (CO) even after poisoning caused by a sulfur component at a low temperature and is therefore preferably used as a
    11/84 oxidation catalyst for exhaust gas purification, which is effective for purifying a diesel engine exhaust gas.
    In addition, the second exhaust gas purification catalyst of the present invention is used in the purification of an exhaust gas containing toxic substances, specifically, for example, carbon monoxide, hydrocarbon and sulfur oxide (SO X ). That is, the present invention provides a method for efficiently purifying an exhaust gas containing toxic substances (e.g., carbon monoxide, hydrocarbon and sulfur oxides (S0 x)). In addition, the second exhaust gas purification catalyst of the present invention inhibits deterioration of the catalytic performance caused by poisoning a sulfur component and is therefore preferably used in the purification of an exhaust gas containing sulfur oxides ( S0 x ), in particular, SO 2 .
    The second catalyst of the present invention contains one or more metal oxides selected from the group consisting of silicon oxide (SiO 2 ) and titanium oxide (TiO 2 ) with aluminum oxide (AI2O3) and zirconium oxide (ZrOj) and, therefore, This way, it increases the thermal durability of catalytic performance and can generate a protective effect of catalytic performance due to poisoning caused by a sulfur component in a fuel. The mechanism capable of obtaining the advantage described above is undefined, however, it can be deduced as follows. Furthermore, the present invention is in no way limited to the deduction described below.
    It can be deduced that a carrier's acidity
    12/84 increases by adding silica (SiO 2 ) and / or titania (TiO 2 ) to zirconia-alumina (ZrO 2 -Al 2 O3). Since S0 x , which is the main sulfur component in an exhaust gas, is an acidic gas, the affinity between the carrier and SO X can be reduced by using a carrier that has a relatively high acidity. In this way, the catalyst hardly suffers from poisoning caused by a sulfur component and the catalytic performance is thus maintained. Consequently, it is assumed that a protective effect of catalytic performance can be transmitted by adding silica and / or titania to zirconia-alumina. When an addition of an amount of silica and / or titania is less or exceeds a specific range, large particles of each of titania and silica are generated, which causes deterioration of the catalytic performance.
    In the present invention, AI2O3, ZrO 2 and the second metal oxide are in the form of a mixture, and primary particles of each compound are mixed in nano order to form the mixture. A1 2 O 3 , ZrO 2 and the second metal oxide are different in terms of primary particle sizes. When AI2O3, ZrO 2 and the second metal oxide are contained in specific levels in a carrier containing AI2O3, ZrO 2 and the second metal oxide, ZrO 2 has a primary particle diameter of less than 10 nm and, preferably, has a crystal structure very thin or an amorphous (non-crystalline) structure. The second metal oxide most preferably has a primary particle diameter of less than 10 nm and, particularly preferably, has a very fine crystal structure or an amorphous (non-crystalline) structure. AI2O3
    13/84 preferably has the primary particle diameter from 10 to 100 nm.
    In the present invention, Al 2 0 3 , ZrO 2 and the second metal oxide do not form a complex oxide and are in the form of a mixture in nano order, as described above. This is because ZrO2 and the second metal oxide contained with AI2O3 have a property that it does not form a complex oxide with A1 2 O 3 , primary particles of a complex oxide made of its oxides hardly exist, and primary particles of simple oxide of each one. compounds exist. That is, the exhaust gas purification catalyst of the second embodiment of the present invention is a mixture that is obtained by dispersing primary particles of A1 2 O 3 , primary particles of ZrO 2 and primary particles of the second metal oxide. The shape of the mixture is assumed to be one in which fine primary particles of ZrO 2 and fine primary particles of the second metal oxide are fitted into primary particles of Α1 2 0 3 . That is, the mixture is in the form of a combination of the thin ZrO 2 and the second fine metallic oxide in primary particles of AI2O3. In this form, ZrO 2 , as described above, has a primary particle diameter of less than 10 nm and preferably has a very fine crystal structure or an amorphous (non-crystalline) structure. The second metal oxide most preferably has a primary particle diameter of less than 10 nm and particularly preferably has a very fine crystal structure or an amorphous (non-crystalline) structure.
    In the exhaust gas purification catalyst of the
    14/84 present invention, AI2O3, ZrCk and the second metal oxide do not form a complex oxide, primary particles of the second metal oxide, primary particles of ZrO2 and primary particles of A1 2 O 3 intervene between the respective primary particles considering, therefore, that the progress of the growth of primary particles of a simple oxide is inhibited and the reduction of a surface area and pore capacity are sufficiently inhibited, and the dispersibility of a catalyst component to be supported can therefore be sufficiently maintained . As a result, it is assumed that the catalyst that has the carrier maintains a catalytic activity, even when used under the condition of an elevated temperature, and the catalyst can purify an exhaust gas even at a low temperature.
    As described above, AI2O3, ZrC> 2 and the second metal oxide do not form a complex oxide, AI2O3, ZrC> 2 which have a primary particle diameter of less than 10 nm and the second metal oxide forms a mixture at a specific mixing ratio (mass ratio) in nano order and therefore an excellent exhaust gas purification catalyst in terms of thermal durability can be obtained. The oxidation catalyst of the present invention can maintain used catalytic activity even under a high temperature condition and effectively purifies (oxidizes) an exhaust gas even with a long thermal history and even after sulfur poisoning. That is, the precious metal effectively acts on nitrogen oxide (NOx), carbon monoxide (CO) and hydrocarbon (HC), which is an unburned fuel component, such as
    15/84 example, gasoline or fuel from a diesel engine, for example, light oil and heavy oil, in particular carbon monoxide (CO) and hydrocarbon (HC), in an exhaust gas and thus can successfully purify an exhaust gas even at a low temperature.
    Consequently, the second oxidation catalyst produced by the method of the present invention has high durability and can effectively purify an exhaust gas, in particular carbon monoxide (CO) in the exhaust gas at a low temperature even after sulfur poisoning.
    Therefore, the oxidation catalyst according to the present invention is particularly effective for purifying a diesel engine exhaust gas at a low temperature, even when used under high temperature conditions and when the catalyst is exposed to sulfur poisoning.
    The mixture of the present invention obtained by mixing primary particles of A1 2 O 3 and a metal oxide in nano order can also be called the first oxide mixture hereinafter.
    The mixture of the present invention obtained by mixing primary particles of A1 2 O 3 , ZrO 2 and the second metal oxide in nano order can also be called the second oxide mixture hereinafter.
    The first oxide mixture and the second oxide mixture are also collectively called simply the oxide mixture.
    Modalities of the present invention will be described below. Note that constituent elements and modalities of the present invention will be specifically described at
    16/84, but these are part of examples of embodiments of the invention, and the invention is not limited to those levels.
    First, constituent components of the exhaust gas purification catalyst of the present invention in the first and second embodiments will be described.
    Exhaust gas purification catalyst
    1. First oxide mixture
    The first exhaust gas purification catalyst of the present invention contains the first mixture of oxide made of AI2O3 and a metal oxide. The first mixture of oxide (AI2O3 and metal oxide) is used as a carrier for a catalyst component as a preferable modality. The carrier may contain other components in addition to the first oxide mixture (A1 2 O 3 and metal oxide), but it is preferably constituted only with the first oxide mixture (AI2O3 and metal oxide). The first oxide mixture can be used in combination of two or more types in the present invention.
    The exhaust gas purification catalyst of the present invention contains a metal oxide as the first oxide mixture. The first metal oxide that can be used in the present invention is one or more selected from the group consisting of zirconium oxide (ZrO 2 ), cerium oxide (CeC> 2), yttrium oxide (Y2O3), neodymium oxide (Nd 2 O 3 ), silicon oxide (SiO 2 ) and titanium oxide (TiO 2 ) t and these can be used alone or in combination of two or more. Among these metal oxides, ZrO 2 , Y2O3 is preferable, and ZrO 2 is more preferable from the point of view of ease of formation in mixture of nano order with AI2O3.
    17/84
    As a preferred embodiment of the catalyst of the present invention, zirconium oxide (ZrO 2 ) is essentially contained. That is, the metal oxide is preferably zirconium oxide (ZrO 2 ), or a mixture of zirconium oxide (ZrO 2 ) and one or more selected from the group consisting of cerium oxide (CeO 2 ), yttrium oxide (Y 2 O 3 ), neodymium oxide (Nd 2 O 3 ), silicon oxide (SiO 2 ) and titanium oxide (TiO 2 ).
    As another preferred embodiment of the catalyst of the present invention, one or more metal oxides selected from the group consisting of yttrium oxide (Y 2 O 3 ) neodymium oxide (Nd 2 O 3 ), silicon oxide (SiO 2 ) and oxide of titanium (TiO 2 ) are contained with zirconium oxide (ZrO 2 ). According to the modality, the thermal durability of the catalytic performance can be increased, a protective effect of the catalytic performance due to poisoning caused by a sulfur component in the fuel can be transmitted.
    In the exhaust gas purification catalyst of the present invention, a mass ratio of AI2O3 of the metal oxide in the first oxide mixture (Α1 2 Ο 3 and metal oxide) is preferably
    99.5: 0.5
    60:40, more preferably
    99.5: 0.5
    70:30, even more preferably
    99: 1
    80:20, particularly preferably
    98: 2 to
    85:15 and, even more preferably,
    95: 5 to 90:10, based on an oxide. When the metal oxide is less than 0.5% by mass, it can hardly be an effect of improving the catalytic performance and, when the metal oxide exceeds 30% by mass, an amount of the metal oxide does not contribute to improvement
    18/84 of catalytic performance and, therefore, not being economical. Because it contains each oxide in such a proportion, there is a tendency that primary particles of each oxide are hardly adjacent.
    In the first exhaust gas purification catalyst of the present invention, the metal oxide in the first oxide mixture has a particle diameter of less than 10 nm, preferably less than 9 nm, more preferably less than 7 nm, even more preferably less than 6 nm nm and, particularly preferably, less than 5 nm. The lower limit of the metal oxide particle diameter is preferably 0.3 nm. When the particle diameter is less than 10 nm, the dispersibility of the metal oxide between primary particles of A1 2 O 3 is increased and the thermal durability is thereby increased.
    In addition, in the specification, the particle diameter of the metal oxide can be found by powder X-ray diffraction (XRD) in examples described below using the Scherrer equation. Here, being less than 5 nm of particle diameter means a size that cannot be seen by powder X-ray diffrometry (XRD).
    In the first exhaust gas purification catalyst of the present invention, as a preferred embodiment, a metal oxide is less than 5 nm, and metal oxides that are greater than or equal to 5 nm are not contained. That is, it is particularly preferable that a peak derived from metal oxide is not observed in powder X-ray diffraction.
    19/84
    As described above, in the first oxide mixture, a metal oxide is one in which a metal is not substituted or does not penetrate into primary particles of AI2O3, in other words, it is a metal oxide that does not form a complex oxide with A1 2 O 3 . Consequently, since the metal oxide of the present invention forms primary particles separate from primary particles of AI2O3, the metal oxide never forms primary particles of an oxide complex with AI2O3.
    In the exhaust gas purification catalyst of the present invention, a particle diameter of primary particles of AI2O3 in the first oxide mixture (hereinafter, also called primary particle diameter) is preferably 10 to 100 nm, more preferably 10 to 70 nm. nm, even more preferably 10 to 50 nm and, particularly preferably, 10 to 30 nm. It is preferable in the present invention that, when the primary particle diameter is 10 to 100 nm, gaps between primary particles of AI2O3 are present where the metal oxide can exist in a sufficient amount. In addition, the particle diameter of AI2O3 can be measured with the electronically transmitted microscope.
    In the first exhaust gas purification catalyst of the present invention, as a preferable embodiment,
    AI2O3 and metal oxide form secondary particles by a proportion of levels. As the metal oxide is very thin in the present invention, the secondary particle diameter of the oxide mixture (AI2O3 and metal oxide) is preferably 10 to 100 nm, more preferably 10 to 70 nm, even more preferably 10 to nm and, particularly preferably , 10 to 30 nm.
    20/84
    A specific surface area of Brunauer-Emmett-
    Teller (from here on hereinafter called BET) gives first mixture of oxide (A1 2 O 3 and oxide metallic) gives gift invention is preferably 10 at 500 m 2 / g more
    preferably 50 to 400 m 2 / g, even more preferably 80 to 380 m 2 / g, particularly preferably 100 to 350 m 2 / g.
    A use amount (supported amount) of the first oxide mixture is not particularly limited, and can be appropriately selected according to a concentration of a toxic component to be purified (removed). Specifically, the amount of use of the first oxide mixture (supported amount; conversion of oxide) can be used in an amount of preferably 0.1 to 500 g, more preferably 1 to 300 g, and even more preferably 10 to 200 g, per liter of the catalyst (three-dimensional structure). As long as the amount of use is within these ranges, a toxic component can be sufficiently purified (removed). In addition, when the first oxide mixture is used in combination of two or more types, the total amount of the first oxide mixture is preferably within the range described above.
    As described later, the first mixture of oxide (AI2O3 and metal oxide) is obtained by adding an alkaline solution to a solution containing a water-soluble compound of Al and a water-soluble compound of one or more metals selected from the group consisting of Zr , Ce, Y, Nd, Si and Ti (for example, a water-soluble compound of Zr when the metal oxide is ZrO 2 ) to be mixed and deposited
    21/84 (coprecipitates) to obtain a coprecipitated product (precursor to the oxide mixture) which is a precipitate made of a precursor of AI2O3 and a precursor of metal oxide (coprecipitation step).
    2. Second oxide mixture Second exhaust gas purification catalyst of the present invention contains the second oxide mixture made of AI2O3, ZrO 2 and the second metal oxide. The second oxide mixture (AI2O3, ZrO 2 and the second metallic oxide) is used as a carrier for a catalyst component as a preferable modality. The carrier may contain other components in addition to the second oxide mixture (AI2O3, ZrO 2 and the second metal oxide), but is preferably made up only of the second oxide mixture (A1 2 O 3 , ZrO 2 and the second metal oxide). In addition, the second oxide mixture can be used in combination of two or more types in the present invention.
    second exhaust gas purification catalyst of the present invention contains one or more second metal oxides selected from the group consisting of silicon oxide (SiO 2 ) and titanium oxide (TiO 2 ) as the second oxide mixture, these can be used alone or in combination of two or more.
    When SiO 2 or TiO 2 is used alone in a carrier constituted by A1 2 O3,
    ZrO 2 and the second metal oxide, SiO 2 or TiO 2 can be used in an amount of 0.01 to 10 parts by mass, and when SiO 2 and TiO 2 are used in combination, each of them can be contained in an amount from 0.01 to 10 parts by mass.
    In the second catalyst for purifying gas
    22/84 exhaustion of the present invention, for each content in the second oxide mixture (AI2O3, ZrO 2 and the second metallic oxide), A1 2 O 3 is 60 to 99.49 parts by mass, ZrO 2 is 0.5 to 20 parts by mass, the second metal oxide is 0.01 to 20 parts by mass (SiO 2 is 0.01 to 10 parts by mass and / or TiO 2 is 0.01 to 10 parts by mass) based on oxides with respect to to 100 parts by mass of the oxide mixture, and the total amount of A1 2 O 3 , ZrO 2 and the second metal oxide is 100 parts by mass. In function of containing the respective oxides in these proportions, there is a tendency that primary particles of the respective oxides are hardly adjacent.
    In addition, a preferable content of each oxide is described below.
    A content of AI2O3 in the second oxide mixture (AI2O3, ZrO 2 and metal oxide) is 60 to 99.49 parts by mass, preferably 69 to 99.5 parts by mass, more preferably 70 to 99 parts by mass, even more preferably 79 to 97 parts by mass, particularly preferably 84 to 95 parts by mass and, more preferably still, 89 to 94.9 parts by mass, based on oxides with respect to 100 parts by mass of the oxide mixture. When AI2O3 is less than 60 parts by mass, the contents of zirconia and the second metal oxide are very large and, therefore, they are hardly allowed to exist in fine particles or an amorphous state, and when A1 2 O 3 is greater than 99.49 parts by mass, a sufficient amount of zirconia cannot be contained and the thermal durability is thus reduced.
    A content of ZrO 2 in the second oxide mixture (AI2O3, ZrO 2 and metallic oxide) is 0.5 to 20 parts by mass,
    23/84 preferably 1 to 18 parts by mass, more preferably 2 to 15 parts by mass, even more preferably 3 to 12 parts by mass and, particularly preferably, 5 to 10 parts by mass, based on oxides with respect to 100 parts by mass of the oxide mixture. When ZrO 2 is less than 0.5 parts by mass, it can hardly be achieved sufficiently to improve the catalytic performance, and when ZrO 2 exceeds 20% by mass, the amount of ZrO 2 does not contribute to the improvement of catalytic performance. thus being economical.
    A SiO 2 content in the second oxide mixture (A1 2 O 3 ,
    ZrO 2 and metal oxide) is 0.01 to 10 parts by mass,
    preferably 0.03 to 8 parts per pasta, more preferably 0.05 to 7 parts per pasta, still more preferably 0, 08 6 parts per pasta and,
    particularly preferably,
    0.1 to 5 parts by mass, based on oxides with respect to
    100 parts by mass of the oxide mixture.
    A content of TiO 2 in the second oxide mixture (AI2O3,
    ZrO 2 and metal oxide) is 0.01 to 10 parts by mass, preferably 0.05 to 9 pieces by mass, more preferably 0, 1 to 7 parts by pasta, still more preferably 0.25 a 5 pieces per pasta and, particularly preferably 0.5 to 2.5 parts per mass, based in oxides with respect to 100 parts per mixture mass of oxide.
    When the second metal oxide (SiO 2 ,
    TiO 2 ) is less than
    0.01 part by mass, respectively, an effect of
    24/84 improves catalytic performance, and when the second metal oxide exceeds 10 parts by mass, the amount of metal oxide does not contribute to the improvement of catalytic performance and is therefore not economical. In function of containing the respective oxides in these proportions, there is a tendency that primary particles of the respective oxides are hardly adjacent.
    Furthermore, when SiO2 and TiO2 are used in combination in the second oxide mixture of the present invention, the total amount of the contents is preferably 0.02 to 20 parts by mass, more preferably 0.03 to 15 parts by mass, even more preferably 0.05 to 12 parts by mass, particularly preferably 0.08 to 10 parts by mass, with respect to 100 parts by mass of the oxide mixture.
    In the second exhaust gas purification catalyst of the present invention, ZrO 2 in the second oxide mixture has a particle diameter of less than 10 nm. The particle diameter is preferably less than 9 nm, more preferably less than 7 nm, even more preferably less than 6 nm and, particularly preferably, less than 5 nm. The lower limit of the particle diameter of the second metal oxide is preferably 0.3 nm. When the particle diameter is less than 10 nm, the dispersibility of metal oxides between primary AI2O3 particles is increased and the thermal durability is increased.
    In the second exhaust gas purification catalyst of the present invention, the second metal oxide (SiO2, TiO 2 ) in the second oxide mixture has the diameter
    25/84 of particle less than 10 nm. The particle diameter is preferably less than 9 nm, more preferably less than 7 nm, even more preferably less than 6 nm and, particularly preferably, less than 5 nm. The lower limit of the particle diameter of the second metal oxide is preferably 0.3 nm. When the particle diameter is less than 10 nm, dispersibility of the metal oxide between primary particles of AI2O3 is increased and the thermal durability is increased.
    In addition, the particle diameters of ZrO 2 and the second metal oxide can be found by powder X-ray diffractometry (XRD) from the examples described below using the Scherrer equation. Here, being less than 5 nm of a particle diameter means a size that cannot be observed by powder X-ray diffrometry (XRD).
    In the second exhaust gas purification catalyst of the present invention, as a preferable embodiment, the particle diameter of ZrO 2 is less than 5 nm or the particle diameter of the second metal oxide is less than 5 nm, more preferably, the diameters particle size of ZrO 2 and the second metal oxide are both less than 5 nm, and ZrO 2 and the second metal oxide, which are greater than or equal to 5 nm, are not contained. That is, it is particularly preferable that peaks derived from ZrO 2 and the second metal oxide are not seen in powder X-ray diffractometry.
    As described above, in the second oxide mixture, ZrO 2 and the second metallic oxide are those in which a metal is not replaced or does not penetrate into primary particles of
    26/84
    ΑΙ2Ο3, in other words, they do not form a complex oxide with A1 2 Ü3. Consequently, since ZrO 2 and the second metal oxide of the present invention form primary particles separated from primary particles of A1 2 C> 3, ZrO 2 and the second metal oxide never form primary particles of an oxide complex with AI2O3, respectively. In the specification, being less than 10 nm of metal oxide particle diameters in the second oxide mixture means that at least one of ZrO 2 , SiO 2 or TiO 2 has a particle diameter of less than 10 nm. ZrO 2 is preferably less than 10 nm, and the metal oxides (ZrO 2 , and at least one or more selected from the group consisting of SiO 2 and TiO 2 ), which are contained, are more preferably less than 10 nm.
    In the second exhaust gas purification catalyst of the present invention, a particle diameter of a primary AI2O3 particle in the second oxide mixture (hereinafter also referred to as the primary particle diameter) is preferably 10 to 100 nm, more preferably 10 at 70 nm, even more preferably 10 to 50 nm and, particularly preferably, 10 to 30 nm. It is preferable that, when the primary particle diameter is 10 to 100 nm in the present invention, there may be gaps between primary particles of A1 2 O3 when the second metal oxide is present in a sufficient amount. In addition, the particle diameter of AI2O3 can be measured by an electronically transmitted microscope.
    In the second exhaust gas purification catalyst of the present invention, as a preferred embodiment, A1 2 O3, ZrO 2 and the second metal oxide form
    27/84 secondary particles by a proportion of contents. Since ZrO 2 and the second metal oxide are very thin in the present invention, the secondary particle diameter of the second oxide mixture (AI2O3, ZrO 2 and the second metal oxide) is preferably 10 to 100 nm, more preferably 10 to 70 nm, even more preferably 10 to 50 nm and, particularly preferably, 10 to 30 nm.
    A specific surface area of Brunauer-EmmettTeller (hereinafter referred to as BET) of the second oxide mixture of the present invention (AI2O3, ZrO 2 and the second metallic oxide) is preferably 10 to 500 m 2 / g, more preferably 50 to 400 m 2 / g, even more preferably 80 to 380 m 2 / g, particularly preferably 100 to 350 m 2 / g.
    A use amount (supported amount) of the second oxide mixture is not particularly limited, and can be appropriately selected according to a concentration of a toxic component to be purified (removed). Specifically, the amount of use of the second oxide mixture {amount supported; oxide conversion) can be used in an amount of preferably 0.1 to 500 g, more preferably 1 to 300 g and, even more preferably, 10 to 200 g, per liter of the catalyst (three-dimensional structure). As long as the amount of use is within these ranges, a toxic component can be sufficiently purified (removed). In addition, when the second oxide mixture is used in combination of two or more types, the total amount of the oxide mixture is preferably within the range described above.
    As described later, the second oxide mixture
    28/84 (ΑΙ2Ο3, ZrO 2 and the second metal oxide) is obtained by adding a solution containing a water-soluble compound of Al and a water-soluble compound of Zr, or a solution containing a water-soluble compound of Al, a water-soluble compound of Al Zr and a water-soluble Ti compound, to an alkaline solution or an alkaline solution containing a water-soluble Si compound to be mixed and deposited (coprecipitated) to obtain a coprecipitated product (precursor to the second oxide mixture), which is a precipitate made of an AI2O3 precursor, a ZrO 2 precursor, and a second metal oxide precursor (coprecipitation step).
    3. Catalyst component
    The exhaust gas purification catalyst of the present invention contains a catalyst component. Hereinafter, the catalyst component can also be termed as a precious metal.
    catalyst component used in the present invention is one or more selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) and osmium (Os). These catalyst components can be used alone or in combination of two or more. Among these components, platinum, palladium, rhodium and iridium are preferably used, and platinum, palladium and rhodium are more preferable. Among them, it is preferable that the catalyst component is platinum or that the catalyst components are platinum and palladium, and a mass ratio of platinum and palladium is 1: 0 to 1: 1. In addition, a combination of platinum and palladium is most preferably used, as the performance
    High catalytic 29/84 can be obtained even when an expensive amount of platinum is reduced. When platinum and palladium are used in combination, a mass ratio of platinum and palladium is preferably 1: 1 to 40: 1. The mass ratio is more preferably 1: 1 to 30: 1 and, even more preferably, 1: 1 to 20: 1. The mass ratio is particularly preferably 1: 1 to 4: 1 and, most preferably, 1: 1 to 2: 1. When palladium is less than the range described above, an addition effect is hardly obtainable, and when beyond the range, more effects can hardly be obtained.
    When platinum and palladium are used in combination, a component obtained by producing an alloy of platinum and palladium is preferable. Here, production of an alloy means that platinum and palladium are present on the same particle under an electron microscope. A method of producing alloys is not particularly limited and, for example, a component obtained by mixing a compound containing platinum and a compound containing palladium to have a ratio within the range described above can be used. That is, a catalyst component prepared in a method in the examples described below is preferable; the catalyst component is obtained by impregnating a carrier with a solution containing platinum and palladium, thereby supporting a component obtained by producing an alloy of platinum and palladium in the carrier,
    An amount of use (supported amount) of a catalyst component is not particularly limited and can be appropriately selected according to a concentration of a toxic component to be purified
    30/84 (removed). Specifically, the amount of use (supported amount; precious metal conversion) of the catalyst component can be used in an amount of preferably 0.01 to 10 g, more preferably 0.3 to 10 5 g, per liter of a catalyst (structure three-dimensional).
    When the amount of use is within a range as a session, a toxic component can be sufficiently removed (purified). In addition, when two or more catalyst components are used in combination, the total amount of the catalyst components is preferably within the range described above.
    4. Other components first and second exhaust gas purification catalysts of the present invention may contain 15 components in addition to the AI2O3, metal oxide and catalyst component compounds (precious metals) described above, or AI2O3, ZrO2, the second metal oxide and compounds of catalyst components (precious metals). These components are not particularly limited, and examples of these include alkali metals, alkaline earth metals, rare earth elements and manganese, iron, copper, silicon, titanium, zirconium and oxides thereof, beta type zeolites, type ZSM-5 and type Y and compounds obtained by ion exchange of these zeolites with iron, copper, cerium, or the like. In addition, a supported amount of the component described above is not particularly limited. Specifically, a usage amount of each component (supported amount; oxide conversion) can be used in an amount of preferably 0.1 to 250 g, more preferably 0.1 to 200 g and, even more preferably, 1 to 100 g , per liter of
    31/84 catalyst (three-dimensional structure).
    In particular, in the exhaust gas purification oxidation catalyst of the present invention, a refractory inorganic oxide is preferably further supported on the catalyst (three-dimensional structure) in a direct manner. Hereinafter, a refractory inorganic oxide that is directly supported on the catalyst (three-dimensional structure) is called a refractory inorganic oxide (supported component). A moment of support for refractory inorganic oxide (supported component) is not particularly limited, and is preferable after support of a metal oxide and is more preferable after support of a catalyst component. For example, for refractory inorganic oxide (supported component), any component used as a carrier catalyst can be used, and examples of these include active alumina, for example, a-alumina, γ-alumina, δ-alumina, η-alumina and θ-alumina, simple oxides such as titania, zirconia and silicon oxide (silica), complex oxides or fine mixtures such as alumina-titania, zirconia-alumina, titania-zirconia, zeolite, silica-silica- zirconia, silica-alumina, and lanthanumalumina, and mixtures of these compounds. Among them, simple oxides such as, for example, zeolite, γ-alumina, silica, titania, zirconia and ceria, complex oxides or fine mixtures such as, for example, silica-alumina, lanthanum-alumina, zirconia-alumina and ceriazirconia are used , and mixtures of these compounds. Zeolite is more preferable, and β-zeolite is even more preferable. Zeolite is a hydrocarbon adsorbent and can absorb
    32/84 heavy hydrocarbon (HC) which is adsorbed at a low temperature before the catalyst is activated. In that case, when β-zeolite is used, a molar ratio of silica and alumina (silica / alumina ratio) is not particularly limited, preferably 15 to 500, more preferably 20 to 250 and, even more preferably, 25 to 200. . The refractory inorganic oxide described above can be used alone or in a form of a mixture of two or more types.
    One form of refractory inorganic oxide (supported component) is not particularly limited and the following form is preferable. For example, a specific surface area of BET (Brunauer-Emmett-Teller) of refractory inorganic oxide (supported component) is not particularly limited and is preferably large. The specific surface area of BET is preferably 100 to 650 m 2 / g, more preferably 150 to 600 m 2 / g, even more preferably 200 to 550 m 2 / g. The average particle diameter of the refractory inorganic oxide powder is also not particularly limited and is preferably 0.1 to 10 pm, more preferably 0.2 to 5 pm and, even more preferably, 0.3 to 3 pm, considering the uniformity of a mud.
    When supported) supported)
    O oxide i it is contained, of oxide i
    norwegian refractory an amount of refractory use (component (quantity (supported component) preferably 1 to 250 g, more preferably 150 g, even more preferably 15 to 100 g, per liter of the catalyst (eg three-dimensional structure). refractory inorganic oxide
    33/84 (supported component) is contained within the range, performance and cost are suitable as a heavy hydrocarbon adsorbent. In addition, a supported amount of refractory inorganic oxide (supported component) does not include a supported amount of the first or second oxide mixture as the carrier described above, and is an amount of a refractory inorganic oxide that is supported separately in a three-dimensional structure .
    Method for producing catalyst for purification of exhaust gas
    A method of producing the exhaust gas purification catalyst of the present invention is not particularly limited and, for example, the following example is included.
    A method of producing the exhaust gas purification catalyst of the present invention includes a step of adding a solution containing a water-soluble compound of Al and a water-soluble compound of one or more metals selected from the group consisting of Zr, Ce, Y , Nd, Si and Ti to an alkaline solution to be mixed and coprecipitated to obtain a coprecipitated product, and then the calcination of the coprecipitated product to obtain, in this way, a carrier containing the aluminum oxide and metal oxide described above.
    The production method of the exhaust gas purification catalyst of the present invention may further include a step of impregnating the carrier containing AI2O3 and the metal oxide with an aqueous solution of a compound of a catalyst component, and then calcining the carrier obtained by impregnation to obtain a carrier with
    34/84 supported catalyst component.
    The production method of the exhaust gas purification catalyst of the present invention may also include a step of preparing a slurry containing the carrier with supported catalyst component, or the carrier with supported catalyst component and supported inorganic refractory oxide) (preferably zeolite ), and mud coating a three-dimensional structure.
    1. Production method of the first or second oxide mixture
    First, the method of producing the oxide mixture of the present invention will be described.
    A preferred production method of the oxide mixture in the present invention is a embodiment in which the production method includes a step of adding a solution containing a water-soluble compound of Al and a water-soluble compound of one or more metals selected from the group consisting of in Zr, Ce, Y, Nd, Si and Ti to an alkaline solution to be mixed and after coprecipitation to obtain a coprecipitate product (that is, after coprecipitation of a precursor to the oxide mixture), and calcination of the coprecipitate product (precursor) to obtain a mixture of oxide (a carrier containing aluminum oxide and metal oxide).
    The first oxide mixture of the present invention may contain A1 2 O 3 , and one or more metal oxides selected from the group consisting of zirconium oxide (ZrO 2 ), cerium oxide (CeO 2 ), yttrium oxide (Y2O3), neodymium oxide (Nd 2 O 3 ), silicon oxide (SiO 2 ) and titanium oxide (TiO 2 ).
    35/84
    A production method is not particularly limited and includes a zol-gel method, a method of mixing the suns, a method of mechanical grinding, and the like. However, in order to form a mixture obtained by mixing primary particles in nano order as described above, the oxide mixture is preferably produced in a coprecipitation method.
    That is, the oxide mixture of the present invention is obtained by adding a solution containing a water-soluble compound of Al and a water-soluble compound of one or more metals selected from the group consisting of Zr, Ce, Y, Nd, Si and Ti (for example, a water-soluble Zr compound when the metal oxide is ZrO 2 ) to an alkaline solution to be mixed and deposition (coprecipitation) of a coprecipitated product, which is a precipitate made of an AI2O3 precursor and a metal oxide precursor (precursors to the oxide mixture) (coprecipitation step).
    The second oxide mixture of the present invention may contain A1 2 C> 3, ZrO 2 , and one or more metal oxides selected from the group consisting of SiO 2 and TiO 2 . For production, Al, Zr, Ti and Si can be simultaneously coprecipitated in a coprecipitation method, or Al and Zr can be deposited in the coprecipitation method and then impregnated with an aqueous solution of a water-soluble compound of Ti and / or However, in order to allow Ti and / or Si to exist in fine particles or in an amorphous form, it is preferably produced simultaneously in the coprecipitation method.
    That is, the second oxide mixture of the present invention is obtained by adding a solution that contains a
    36/84 water-soluble compound of Al and water-soluble compound of Zr, or a solution containing water-soluble compound of Al, water-soluble compound of Zr and water-soluble compound of Ti (hereinafter also simply called a salt solution) to an alkaline solution or an alkaline solution containing a water-soluble Si compound to be mixed and deposited (coprecipitated) to obtain a coprecipitated product, which is a precipitate made of an AI2O3 precursor, a ZrO 2 precursor and an oxide precursor metal (precursor to the oxide mixture) (coprecipitation step).
    In addition, a water-soluble Si compound (eg sodium metasilicate) does not exist stably in an acidic solution, but it does exist stably in an alkaline solution. Therefore, when a water-soluble Si compound is used, it is preferable that the water-soluble Si compound is dissolved in an alkaline solution before adding a salt solution to the alkaline solution, or a solution of Al and Zr salt or a solution of Al, Zr and Ti salt is added to an alkaline solution to be mixed and the water-soluble Si compound is then added.
    For a water-soluble Al compound (Al salt), aluminum sulfate (sulfate), aluminum nitrate (nitrate), aluminum hydrochloride (hydrochloride), aluminum acetate (acetate), and the like can be used, and aluminum nitrate it's preferable. In addition, for example, as materials of aluminum nitrate, aluminum hydroxide, nitric acid and water can be mixed to be used. In addition, the water-soluble Al compounds described above can be used alone or in combination with
    37/84 mixture of two or more of them can be used in the present invention.
    Examples of water-soluble metal compounds selected from the group consisting of Zr, Ce, Y, Nd, Si and Ti (metal salts), which can be used, include Zr salts such as zirconyl sulfate (sulfate), zirconyl nitrate (nitrate), zirconyl hydrochloride (hydrochloride), zirconyl acetate (acetate), zirconyl carbonate (carbonate), zirconyl chloride (chloride) and zirconyl hydroxide (hydroxide); Ce salts such as cerium sulphate (sulphate), cerium nitrate (nitrate), cerium hydrochloride (hydrochloride), cerium acetate (acetate), cerium carbonate (carbonate), cerium chloride (chloride) and cerium hydroxide (hydroxide); Y salts such as yttrium sulfate (sulfate), yttrium nitrate (nitrate), yttrium hydrochloride (hydrochloride), yttrium acetate (acetate), yttrium carbonate (carbonate), yttrium chloride (chloride) and yttrium hydroxide (hydroxide); salts of
    Nd as, for example, neodymium sulfate (sulfate), neodymium nitrate neodymium hydrochloride neodymium acetate (acetate), neodymium carbonate (carbonate), neodymium chloride (chloride) neodymium hydroxide silicates (salts of
    Si), for example, sodium orthosilicate (NaíSiOJ, potassium orthosilicate (K2SÍO4), sodium metasilicate (K 2 SiO 3 ), sodium disilicate (Na 2 Si 2 O 5 ), sodium tetrasilicate disilicate (Na 2 SiO9), potassium tetrassilicato (2 SiOg K), sodium sesquisilicate (2 O.2SiO 3Na 2) and potassium sesquisilicate (3K 2 0.2SiO 2), and Ti salts
    38/84 such as, for example, titanium sulfate (sulfate), titanium chloride (chloride) and titanium alkoxide. Among these, a water-soluble compound of Zr metal (metal salt) is preferably zirconyl nitrate, a water-soluble compound of a Si metal (metal salt) is preferably sodium metasilicate and a water-soluble compound of a Ti metal (salt metal) is preferably titanium sulfate. In addition, the water-soluble compounds described above of metals can be used alone, or a mixture of two or more can be used in the present invention.
    For a solvent to uniformly dissolve the water-soluble compound of Al and the water-soluble compound of a metal (e.g., a water-soluble compound of Zr, a water-soluble compound of Ti) described above, water, an alcohol and a mixture of these can be used. For alcohol, ethanol, 1propanol or 2-propanol can be used. The concentrations (contents) of the water-soluble compound of Al and the water-soluble compound of a metal in a solvent are not particularly limited, and can be suitably adjusted according to quantities to have Al (Ai 2 O3) and a metal support (metal oxide ). For example, each of the contents of the water-soluble Al compound and the water-soluble compound of a metal is preferably 0.01 to 80% by weight.
    Next, a solution containing a water-soluble compound of Al and a water-soluble compound of one or more metals selected from the group consisting of Zr, Ce, Y, Nd, Si and Ti (hereinafter also simply called a salt solution) is added to a
    39/84 alkaline solution and, thus, a precipitate of a precursor of the oxide mixture is deposited.
    For example, a solution containing a water-soluble compound of Al and a water-soluble compound of Zr, or a solution containing a water-soluble compound of Al, a water-soluble compound of Zr and a water-soluble compound of Ti (salt solution) is added to a solution alkaline or an alkaline solution containing a water-soluble Si compound and, thus, a precipitate from a precursor of the second oxide mixture is deposited.
    For the alkaline solution, an aqueous solution or an alcoholic solution obtained by dissolving ammonium, ammonium carbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, or the like, can be used. Among alkaline solutions, an aqueous solution or an alcoholic solution obtained by dissolving ammonium or ammonium carbonate, which is volatilized on burning, is more preferable. An alkaline solution pH is preferably 9 or more in order to promote a deposition reaction of a precursor of each oxide. A precursor to each oxide is hydroxide, carbonate or nitrate from different oxygen elements, which make up each oxide. A content of a water-soluble Si compound in an alkaline solution is preferably 0.01 to 80% by weight.
    An alkaline solution is added to adjust the pH from 7 to 10 in the coprecipitation step, if necessary. The amount of the addition of the alkaline solution is an amount at a level at which the pH is adjusted to be 7 to 10. In the coprecipitation step, the pH is preferably 8 to 10, and more preferably 9 to 10. In addition, when a compound
    40/84 water-soluble Si is used, the pH of the solution is finally adjusted to around a neutral pH (preferably from pH 5 to 8, more preferably from 6 to 8) using nitric acid, or the like thereby depositing a precursor of oxide.
    An alkaline solution or an alkaline solution containing a water-soluble Si compound (hereinafter also simply called an alkaline solution) is added with the salt solution described above and mixed at high speed in a short time to form a precursor to a oxide mixture. With rapid mixing, gaps are dissolved between rates of deposition of precursors of the respective oxides as a function of small gaps between pHs in the solution. Then, both a precursor of an easily soluble oxide and a precursor of an hardly soluble oxide are deposited at the same time and, thus, a precursor of the oxide mixture can be formed in which the respective elements are dispersed with a uniform composition. The mixing is preferably carried out at 5 to 50 ° C. In addition, an alkaline solution containing a water-soluble Si compound is used, a salt solution is added and the pH of the solution is then adjusted to around neutral pH (preferably pH 5 to 8, more preferably 6 to 8) using nitric acid, or the like, to thereby deposit an oxide precursor. When a water-soluble Si compound is added to an alkaline solution, a salt solution is added to an alkaline solution, and the pH of the solution obtained is adjusted to around neutral pH (preferably pH 5 to 8, more preferably 6 to 8 ) using nitric acid, or the like
    41/84 to deposit an oxide precursor.
    The precursor of the oxide mixture obtained by coprecipitation is collected from a solution of a precursor and sufficiently washed, and then dried at 50 to 250 ° C, preferably 70 to 200 ° C, more preferably 80 to 150 ° C, for 10 minutes at 20 hours, preferably for 3 to 15 hours, and the product obtained is further burned in the atmosphere at 100 to 1,200 ° C, preferably 200 to 1,100 ° C, more preferably 300 to 1,000 ° C, for 10 minutes to 20 hours, preferably for 3 to 15 hours to obtain an oxide mixture. Burning can be carried out in a flow of inert gas, such as nitrogen gas, before burning in the atmosphere.
    As described above, the precursor (a water-soluble compound of Al and a water-soluble compound of a metal) are co-precipitated and the co-precipitated product is burned, thereby obtaining the mixture of A1 2 O 3 oxide and metal oxide. The method can be used as long as the metal oxide hardly forms a solid solution with AI2O3.
    Furthermore, like the oxide mixture obtained as described above, it is considered that there are several oxide mixtures, for example, mixtures of two compounds, for example, Al 2 O3 / ZrO 2 , Al 2 O3 / CeO2, AI2O3 / Y2O3, Al 2 O 3 / Nd 2 O 3 , AI2O3 / S1O2 and Α1 2 Ο 3 / ΤίΟ 2 , mixtures of three compounds such as Al 2 O 3 / ZrO2 / CeO2, Α1 2 θ3 / Ζηθ 2 / Υ 2 θ31 Al 2 O 3 / ZrO 2 / Nd 2 O 3 , Al 2 O3 / ZrO 2 / SiO 2 and Al 2 O3 / ZrO 2 / TiO 2 , and mixtures of four compounds, for example, Al 2 O3 / ZrO2 / SiO 2 / TiO 2 .
    The oxide mixture can be used as a carrier to support a catalyst component in the present invention.
    42/84
    2. Catalyst production method for exhaust gas purification
    Next, the exhaust gas purification catalyst of the present invention is prepared using the oxide mixture obtained as described above.
    A preferable production method of the exhaust gas purification catalyst in the present invention includes a step of impregnating a carrier containing AI2O3 and metal oxide with an aqueous solution of a compound of a catalyst component, thereby burning the carrier obtained by impregnation to obtain a carrier with supported catalyst component.
    A preferred production method of the exhaust gas purification catalyst in the present invention further includes a step of preparing a slurry containing a carrier with supported catalyst component, or a carrier with supported catalyst component and a fire resistant inorganic oxide ( supported component) (preferably zeolite), and coating the mud on a three-dimensional structure.
    That is, in one embodiment of the present invention, one or more catalyst components (precious metals) selected from the group consisting of Au, Ag, Pt, Pd, Rh, Ir, Ru and Os are supported in the oxide mixture to obtain 25 the exhaust gas purification catalyst of the present invention.
    In addition, as another embodiment, a carrier on which a catalyst component is supported (a carrier with supported catalyst component) and a fire resistant inorganic oxide (supported component) (preferably
    43/84 zeolite) can be supported on the exhaust gas purification catalyst of the present invention. In addition, at least one or more alkali metals, alkaline earth metals and rare earth elements can be supported in the exhaust gas purification catalyst of the present invention.
    The following methods are exemplified as the method of producing a catalyst for purifying exhaust gas.
    (1) A method in which a mixture of oxide (carrier) is added to an aqueous solution of a compound (raw material) of a catalyst component (precious metal) and sufficiently mixed, then drying and burning, as desired, to do so obtain the powder from a carrier with supported catalyst component (the oxide mixture). The powder is formed in an aqueous slurry and the aqueous sludge is coated in a three-dimensional structure and then dried and burned, as desired, to thereby prepare a complete catalyst.
    (1 ') A method in which a mixture of oxide (carrier) is added to an aqueous solution of a compound (raw material) of a catalyst component (precious metal) and sufficiently mixed, then drying and burning, as desired , in order to obtain the powder from a carrier with supported catalyst component (the oxide mixture). A fire resistant inorganic oxide (supported component) is further mixed in the carrier powder with supported catalyst component, and the mixture was sprayed with moisture to form an aqueous slurry, the aqueous sludge is coated in a three-dimensional structure and then
    44/84 dried and burnt, as desired to thereby prepare a complete catalyst.
    (2) A method in which a compound (raw material) of a catalyst component (precious metal) and a mixture of oxide are combined to form an aqueous slurry, and the aqueous sludge is coated in a three-dimensional structure and then dried and burned , as desired to thereby prepare a complete catalyst.
    (2 ') A method in which a compound (raw material) of a catalyst component (precious metal) and a mixture of oxide are combined and a fire resistant inorganic oxide (supported component) is further mixed in, as desired, to form an aqueous slurry, and the aqueous sludge is coated in a three-dimensional structure and then dried and burned, as necessary, to thereby prepare a complete catalyst.
    (3) A method in which a compound (raw material) of a catalyst component (precious metal) and a mixture of oxide are combined to form an aqueous slurry, and the aqueous sludge is coated in a three-dimensional structure and then dried and burned , as desired, and the three-dimensional structure is further immersed in an aqueous solution of a compound (raw material) of a component such as, for example, an alkali metal, and dried and burned, as desired, to thereby prepare a complete catalyst.
    (3 ') A method in which a compound (raw material) of a catalyst component (precious metal) and a mixture of oxide are combined and a fire resistant inorganic oxide (supported component) is mixed into it, as desired,
    45/84 to form an aqueous slurry, the aqueous sludge is coated in a three-dimensional structure and then dried and burned as needed, and the three-dimensional structure is still immersed in an aqueous solution of a compound (raw material) of a component such as , for example, an alkali metal, and then dried and burned, if necessary, to thereby prepare a complete catalyst.
    (4) A method in which a mixture of oxide (carrier) is added to an aqueous solution of a compound (raw material) of a component such as an alkali metal and sufficiently mixed, then drying and burning, as desired , in order to obtain the powder of a carrier with supported alkali metal (oxide mixture). The powder is formed in an aqueous slurry and the aqueous sludge is coated in a three-dimensional structure and then dried and burned, as desired, and the three-dimensional structure is further immersed in an aqueous solution of a compound (raw material) of a catalyst component and then dried and burnt, as desired to thereby prepare a complete catalyst.
    (4 ') A method in which a mixture of oxide (carrier) is added to an aqueous solution of a compound (raw material) of a component, for example, an alkali metal, and sufficiently mixed and an inorganic oxide resistant to fire (supported component) is further mixed in it, as desired, then drying and burning, as desired, to obtain powder from a carrier with supported alkali metal (oxide mixture). The powder is formed in an aqueous slurry and the aqueous sludge is coated in a three-dimensional structure and then dried and
    46/84 is burnt, as desired, and the three-dimensional structure is further immersed in an aqueous solution of a compound (raw material) of a catalyst component and then dried and burned, as desired to thereby prepare a complete catalyst.
    (5) A method in which a compound (raw material) of a catalyst component (precious metal), a mixture of oxide and a compound (raw material) of a component, such as an alkali metal, are joined and a fire-resistant inorganic oxide (supported component) is further mixed therein, as desired, to form an aqueous slurry and the aqueous sludge is coated in a three-dimensional structure and then dried and burned, as desired to thereby prepare a catalyst complete.
    In the support methods described above in the present invention, the catalyst is preferably produced by method (1) in which the powder of a carrier with supported catalyst component (oxide mixture) is first obtained, the powder is then formed in an aqueous slurry, and the aqueous sludge 20 is coated in a three-dimensional structure and then dried and burned in order to prepare a complete catalyst, or the method (1 ') in which the powder of a carrier with supported catalyst component (oxide mixture) is first obtained, the powder is then formed into an aqueous slurry 25, an inorganic oxide resistant to fire (supported component) is still mixed in it, and the aqueous sludge is coated in a three-dimensional structure and then dried and burned to prepare a complete catalyst. Methods (1) and (1 ') will be described below.
    A catalyst component used in the present invention and
    47/84 a compound (raw material) of a catalyst component used in the production methods described above are not particularly limited, and a catalyst component can be added directly or in another form and then converted to a desired form (a precious metal). In the present invention, a catalyst component is preferably added in another form, in particular, a water-soluble precious metal salt (a water-soluble compound of a precious metal), that is, a form of a salt solution containing a precious metal, to in order to add a compound of a catalyst component to an aqueous medium. Here, water-soluble precious metal salt is not particularly limited, and materials used in the exhaust gas purification field can be used. Specifically, examples in the case of palladium include palladium; halides such as, for example, palladium chloride; inorganic salts, such as palladium nitrate and sulfate; carboxylates such as, for example, palladium acetate; and palladium hydroxides, halides; inorganic salts; carboxylates;
    and tetraamine palladium and hexamine palladium hydroxides, alkoxides, dinitrodiamine palladium, nitrate, Nd oxides. Preferable examples include and nitrates; carboxylates; and palladium dinitrodiamine hydroxides, palladium tetraamine and palladium hexamine, and more preferable examples include nitrate (palladium nitrate), and nitrates; carboxylates; and tetraamine palladium and hexamine palladium hydroxides. Examples in the case of platinum include platinum; halides such as, for example, platinum bromide and platinum chloride; inorganic salts, such as a hexahydroxy acid salt and
    48/84 is a tetranitro acid platinum salt; carboxylates such as, for example, platinum acetate; and platinum hydroxides, halides; inorganic salts; carboxylates; and platinum tetraamine and platinum hexamine hydroxides;
    alkoxides, platinum dinitrodiamine, and oxides.
    Preferable examples include nitrates, carboxylates, hydroxides and hexahydroxic acid salts of platinum dinitrodiamine, platinum tetraamine, and platinum hexamine, and more preferable examples include nitrate, carboxylates, hydroxides, and hexahydroxy acid salts of platinum dinitrodiamine, platinum tetraamine, and hexamine platinum. Examples in the case of rhodium include rhodium; halides, such as rhodium chloride; inorganic salts such as, for example, nitrates, sulfates, hexamine salts and hexacid rhodium salts; carboxylates, such as rhodium acetate; and hydroxide, alkoxides and rhodium oxides. Preferable examples include nitrates and hexamine salts, and more preferable examples include nitrate (rhodium nitrate). The precious metal compounds (precious metal sources) described above in the present invention can be used alone or in a mixture of two or more compounds. In the case of mixing, the same types of compounds are preferably used.
    A use amount (supported amount) of a compound of a catalyst component is not particularly limited, and can be appropriately selected according to a concentration of a toxic component to be purified (removed). Specifically, it is a usage amount of the type (supported amount; precious metal conversion) of the catalyst component described above.
    For an aqueous solution that uniformly dissolves the
    49/84 compound of the catalyst component described above (water-soluble precious metal salt), water and a mixture of water and alcohol can be used. For alcohol, ethanol, 1propanol or 2-propanol can be used. A concentration (content) of the water-soluble metal salt in an aqueous solution is not particularly limited and can be suitably selected according to the amount of support of the catalyst component. For example, a content of a water-soluble precious metal salt in an aqueous solution is preferably 0.01 to 80% by weight.
    A method in which a catalyst component is supported in the oxide mixture (carrier) is not particularly limited, as long as the method is carried out under the condition that the catalyst component is sufficiently and uniformly in an aqueous solution in contact with the oxide mixture and , in the next drying and firing step, sufficiently supporting the catalyst component in the oxide mixture. The oxide mixture added to the aqueous solution of the water-soluble precious metal salt described above and sufficiently mixed, and then dried at 50 to 250 ° C, preferably at 200 ° C, more preferably 80 to
    150 ° C, for 10 minutes to 20 hours, preferably 3 to 15 hours, and the product obtained is still burned in the atmosphere at
    100 to
    1,200 ° C, preferably
    200 to 1.10 0 ° C, more minutes to 20 hours, preferably for 1 to 15 hours to obtain powder from a carrier with supported catalyst component (oxide mixture). In addition, burning can be carried out in a flow of inert gas, such as nitrogen gas, before
    50/84 of the burning in the atmosphere.
    In a preferred embodiment of the present invention, a mixture of oxide with supported catalyst component (carrier with supported catalyst component) is supported in a three-dimensional structure.
    In a preferred embodiment in the present invention, a carrier with supported catalyst component (oxide mixture) that supports the catalyst component and a fire resistant inorganic oxide (supported component) are supported in a three-dimensional structure.
    A method of supporting the carrier with supported catalyst component obtained in the above method or the carrier with supported catalyst component and fire resistant inorganic oxide (supported component) in a three-dimensional structure is not particularly limited, and it is preferable that an aqueous sludge containing these components are prepared, and the aqueous sludge is then coated (supported) in a three-dimensional structure.
    A method of preparing aqueous sludge is not particularly limited, and it is prepared, for example, in wet spray. Wet spraying is generally carried out in a known method, not particularly limited, and a ball mill is preferably used. Alternatively, conventionally known techniques such as, for example, an attritor, a homogenizer, an ultrasonic dispenser, a sand mill, a jet mill and a ball mill can be used. Here, wet spray conditions are not particularly limited. For example, the temperature in the wet spray is usually 5 to 40 ° C, preferably around
    51/84 room temperature (25 ° C). In addition, a wet spray time is usually 10 minutes to 20 hours. Note that the wet spray time differs depending on the wet spray equipment to be used and, for example, when equipment that has a high spray efficiency is used, for example, an attritor, the wet spray time is about 10 to 60 minutes, and is used when a ball mill, the wet spray time is about 5 to 20 hours. In addition, as a solvent used in wet spraying, water, alcohols such as ethanol, 1-propanol and 2-propanol, can be used, and water is particularly preferable. The concentrations (contents) of the supported components (for example, a carrier with supported catalyst component (oxide mixture) and a fire resistant inorganic oxide (supported component)) in a wet spray solvent are not particularly limited, and can be particularly limited. properly selected according to quantities that load the carrier with supported catalyst component (oxide mixture) and the inorganic oxide resistant to fire (supported component). For example, a total amount of contents of a carrier with supported catalyst component (oxide mixture) and a fire resistant inorganic oxide (supported component) in a solution is preferably 0.1 to 80% by mass.
    A support method (coating) of an aqueous sludge obtained in the method described above in a three-dimensional structure is not particularly limited, and the aqueous sludge is preferably supported in the three-dimensional structure by washing coating. The coating
    52/84 per wash is generally carried out in a known method and is not particularly limited, and the conditions of the wash coating are also not particularly limited. For example, a three-dimensional structure is immersed in the aqueous sludge, excess sludge is removed and burned, thereby producing an exhaust gas purification oxidation catalyst in which a carrier with supported catalyst component (oxide mixture), or a carrier with supported catalyst component (oxide mixture) and a fire resistant inorganic oxide (supported component) are supported in a three-dimensional structure. A condition in the washing coating of an aqueous slurry in a three-dimensional structure is not particularly limited, as long as it is a condition of placing sufficiently and uniformly supported components in an aqueous sludge, for example, a carrier with supported catalyst component (mixture of oxide) and an inorganic oxide resistant to fire (supported component), in contact with a three-dimensional structure and which sufficiently supports these components in the three-dimensional structure in the following drying and firing steps.
    In such a method, the fire-resistant inorganic oxide (supported component) supported in a three-dimensional structure can be any inorganic oxide, provided that it is generally used as a catalyst for internal combustion, without particular limitation, and as described above, zeolite , which is a hydrocarbon adsorbent, is preferable. For fire-resistant inorganic oxide (supported component), those obtained
    53/84 in known methods are used and those commercially available can be used and, specifically, the fire resistant inorganic oxide described above is added in a direct manner. A use amount (supported amount) of a fire resistant inorganic oxide (supported component) is not particularly limited and can be appropriately selected according to a concentration of a toxic component to be purified (removed). Specifically, the amount of use should be that amount of a fire-resistant inorganic oxide (supported component) described above.
    Next, a three-dimensional structure coated with a carrier with supported catalyst component (oxide mixture), or a carrier with supported catalyst component (oxide mixture) and a fire resistant inorganic oxide (supported component) is dried at 50 to 250 ° C, preferably at 70 to 200 ° C, more preferably at 80 to 180 ° C, for 1 minute to 20 hours, preferably for 5 minutes to 15 hours, and the product obtained is further burned at 100 to 1,200 ° C, preferably at 200 to 1,100 ° C, more preferably at 300 to 1,000 ° C, for 10 minutes to 20 hours, preferably for 30 minutes to 15 hours in the atmosphere to thereby obtain the exhaust gas purification catalyst of the present invention.
    In the present invention, a three-dimensional structure is preferably treated with a reducing gas (for example, under an air flow of 5% hydrogen and 95% nitrogen) according to the need, after the drying step or described step of drying above. Here, hydrogen gas, carbon monoxide gas, or the like can
    54/84 be used as a reducing gas, and hydrogen gas is preferable. For the reducing gas, one of the gases described above can be used alone, two of the gases described above can be used in mixing, or one or two gases described above can be used in mixing with other gases. The use of the gases described above with other gases in mixing is preferable, and the use of hydrogen gas by dilution with nitrogen gas is more preferable. An amount of addition of a reducing gas in this case is not particularly limited, as long as it is an amount capable of treating a dry three-dimensional structure to a desired level, and a treatment atmosphere of a three-dimensional structure preferably contains 1 to 10% by volume of a reducing gas, more preferably it contains 3 to 5% by volume of a reducing gas. In addition, a condition for treating a dry three-dimensional structure with a reducing gas is not particularly limited. For example, a dry three-dimensional structure is preferably treated at 150 to 600 ° C for 1 to 10 hours while the reducing gas described above flows at 10 to 100 ml / minute.
    Here, the three-dimensional structure is not particularly limited, and similar ones generally used for preparing a catalyst for purifying exhaust gas can be used. Examples of these include fire resistant carriers such as, for example, a honeycomb carrier, an integral honeycomb structure (honeycomb carrier) is preferable and, for example, a monolithic honeycomb carrier, a carrier honeycomb in plug, and the like are included.
    55/84
    As a monolithic carrier, materials called honeycomb ceramic carriers can generally be used, in particular honeycomb carriers containing silicon carbide (SiC), cordierite, mullite, petalite, alumina (α-alumina), silica, zirconia, titania, titanium phosphate, aluminum titanate, spodumene, aluminosilicate, magnesium silicate, zeolite, silica, and the like, as materials are preferable, and among them, a honeycomb carrier made of cordierite is particularly preferable. In addition to the above, honeycomb carriers obtained by forming an integral structure using thermo-resistant metals with oxidation resistance, such as stainless steel and Fe-Cr-Al alloy, called honeycomb metallic carriers, are also used . A three-dimensional structure can be used in any type, for example, through-flow type (open flow type), in which a gas can pass directly through a type of filter capable of filtering soot in an exhaust gas or a type of plug . In addition, not being an integral three-dimensional structure, a pellet carrier and the like can be exemplified. Here, the plug-type honeycomb means a honeycomb that has a large number of permeable pores and that has open and closed pores in a checkerboard pattern on the surface of introducing a gas, in which, when a permeable pore is an open pore, the other side of the same permeable pore is a closed pore. The plug honeycomb carrier has fine pores on the walls between respective pores, and an exhaust gas enters the open pores into the honeycomb and passes other pores through the pores
    56/84 fine to get out of the honeycomb.
    These honeycomb carriers are produced using an extrusion molding method, a method of solidly spiraling a blade-shaped element, or the like. The shape of a gas sigh (cell shape) can be any shape in hexagon, square, triangle and a wrinkled shape. The cell density (the number of cells / unit of cross-sectional area) from 100 to 1,200 cells / square inch (6.45 cm 2 ) is sufficiently usable, preferably 200 to 900 cells / square inch (6.45 cm 2) ) and, more preferably, 300 to 600 cells / square inch (6.45 cm 2 ).
    The exhaust gas purification catalyst of the present invention may contain other components, in addition to a mixture of oxide and a catalyst component, as described in methods (3) to (5). These components are not particularly limited, and examples of these include alkali metals, alkaline earth metals, rare earth elements and manganese, and oxides of these substances, beta type zeolites, type ZSM-5 and type Y, and ion exchange substances with iron, copper and cerium (hereinafter also called components, for example, alkali metals or simply as components). Examples of alkali metals used herein include sodium, potassium, rubidium and cesium. Likewise, examples of alkaline earth metals used here include strontium and barium. Examples of rare earth elements used here include cerium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium and
    57/84 erbium. Components, for example, the alkali metals described above, can be added in a direct metal form or an oxide form. In addition, the components described above can be added directly, or added to other shapes and then converted to a desired shape (for example, an alkali metal shape). A component, such as an alkali metal, is preferably added in another form, in particular, a form of a water-soluble compound in the present invention. Here, the water-soluble compound is not particularly limited, and materials used in the exhaust gas purification field can be used. Note that components, for example, alkali metals described above, can be used alone or a mixture of two or more of them can be used in the present invention.
    When the exhaust gas purification catalyst of the present invention contains other components, a method of adding or supporting a compound (raw material) of a component such as, for example, an alkali metal in a final stage of a complete catalyst is preferable , considering the viscosity and convenience of handling a preparation liquid during the preparation of the catalyst.
    As described above, the exhaust gas purification catalyst of the present invention has high durability and is excellent in terms of purification performance in nitrogen oxide (NOx), carbon monoxide (CO) and hydrocarbon (HC), which is a unburned fuel component such as gasoline or
    58/84 fuel from a diesel engine, such as light oil and heavy oil, in particular carbon monoxide (CO) and hydrocarbon (HC), in an exhaust gas at a low temperature.
    Therefore, for the exhaust gas purification performance of the exhaust gas purification catalyst of the present invention to carbon monoxide (CO), a temperature showing a conversion rate of 50% CO is not particularly limited, and is preferably 200 ° C or less, more preferably 195 ° C or less, even more preferably 190 ° C and, particularly preferably, 180 ° C or less. Note that a lower conversion rate limit of 50% CO is more preferable, but in order to constantly maintain catalytic performance, it is preferably 140 ° C or more. For the performance of purification of exhaust gas to hydrocarbon (HC), a temperature showing a conversion rate of 50% HC is not particularly limited, and is preferably 200 ° C or less, more preferably 195 ° C or less, even more preferably 190 ° C and, particularly preferably, 180 ° C or less. Note that a lower conversion rate limit of 50% HC is more preferable, but in order to constantly maintain catalytic performance, it is preferably 140 ° C or more. Note that the measurements of the 50% CO conversion rate and the 50% HC conversion rate described above are followed by methods in the examples described later.
    Therefore, an exhaust gas purification catalyst that is produced by the method of the present invention can be used favorably for purification of an exhaust gas.
    59/84 exhaust (in particular, HC and CO) of internal combustion. The catalyst according to the present invention can be used favorably for processing an exhaust gas that contains a reducing gas in the exhaust gas of internal combustion and has an excellent effect on the purification of hydrocarbon (HC) and carbon monoxide (CO ) contained in the exhaust gas with a high internal combustion reducing property such as, for example, gasoline engine and accelerating diesel engine, and the like.
    As described above, the second exhaust gas purification catalyst of the present invention has high durability, and excellent in terms of purification performance in nitrogen oxide (NOx), carbon monoxide (CO) and hydrocarbon (HC), which is an unburned fuel component such as gasoline or diesel engine fuel, such as light oil and heavy oil, in particular carbon monoxide (CO), in an exhaust gas at a low temperature ( for example, 160 ° C or less).
    The second exhaust gas purification catalyst of the present invention increases the thermal resistance of the catalytic performance and can transmit a protective effect of the catalytic performance due to poisoning caused by a sulfur component in a fuel.
    Therefore, the present invention also provides an exhaust gas purification method, which includes placing an exhaust gas in contact with the exhaust gas purification catalyst according to the present
    60/84 invention.
    An exhaust gas composition is not particularly limited, and the catalyst of the present invention is excellent in terms of the decomposition activity of carbon monoxide (CO) discharged from a heater, an incinerator, a diesel engine and various industrial processes and, therefore, used favorably in the processing of an exhaust gas containing this carbon monoxide (CO). In addition, the second catalyst of the present invention suppresses the reduction in catalytic performance, even when given sulfur poisoning and is therefore used favorably in the processing of exhaust gas containing sulfur oxide (SO X ), in particular, SO2.
    catalyst of the present invention is used for purification of an exhaust gas from internal combustion such as, for example, a gasoline engine and a diesel engine, in particular a diesel engine, and an exhaust gas and a catalyst during purification are brought into contact at a spatial speed preferably from 1,000 to 500,000 h _ 1 , more preferably 5,000 to 150,000 h _ 1 , at a linear gas speed of preferably 0.1 to 8.5 m / second, more preferably 0.2 to 4, 2 m / second.
    The catalyst of the present invention is used to purify an exhaust gas from internal combustion such as a gasoline engine and a diesel engine, in particular a diesel engine, and can favorably oxidize CO when CO in a gas exhaust is contained in an amount of, for example, preferably 10 to 50,000 ppm by volume, more preferably 50 to
    61/84
    15,000 ppm by volume, even more preferably 50 to 5,000 ppm by volume in a dry atmosphere. In addition, the catalyst can favorably oxidize HC when HC in an exhaust gas is contained in an amount of, for example, preferably 10 to 50,000 ppm by volume (carbon conversion (Cl)), more preferably 10 to 10,000 ppm by volume , even more preferably 10 to 5,000 ppm by volume in a dry atmosphere.
    In addition, similar or different exhaust gas purification catalysts can be arranged in a front step (inflow side) or a rear step (outflow side) of the catalyst according to the present invention.
    Examples
    In the following, the present invention will be described in more detail with reference to the examples; however, obviously the present invention is not limited to these examples only, and can be performed with the addition of appropriate changes within the range capable of adapting to the purposes described previously or later, and all changes are included in the technical scope of the present invention.
    In addition, unless otherwise noted,% and ppm are based on mass in the following production examples.
    Example 1-1
    1,442.22 g of aluminum nitrate nonahydrate (Al (NO 3 ) 3 * 9H 2 O) were completely dissolved in 0.95 liters of deionized water, and added to it
    20.0 g of an aqueous solution of zirconyl nitrate (concentration of 20% by mass in conversion to ZrO 2 ), and the
    The mixture was stirred well to prepare a mixed aqueous solution. This solution was dripped into liters of an aqueous solution that was obtained by adjusting to pH with ammonia.
    During dripping, the solution was adjusted to a pH within the range of 7 with ammonia water at a temperature of 25 ° C. A precipitate was generated, filtered, washed well with deionized water and then dried at 120 ° C for 8 hours, and calcined at 400 ° C for 5 hours and at 700 ° C for 5 hours to obtain zirconia-alumina A (2% by mass of zirconia, 98% by mass of alumina).
    Next, 60 g of zirconia-alumina A were impregnated with 42.22 g of a mixed aqueous solution obtained by diluting an aqueous solution of platinum dinitrodiamine containing platinum in an amount corresponding to 0.887 g and a palladium nitrate solution containing palladium in an amount corresponding to 0.443 g with deionized water, the zirconia-alumina A was then dried at 120 ° C for 8 hours to obtain a powder, and the powder was further calcined at 500 ° C for 1 hour to obtain metal precious metal supported by zirconia-alumina A. 61.33 g of this precious metal supported by zirconia-alumina A and 90 ml of deionized water were mixed and ground with moisture to form a sludge. 0.0303 liter of a cordierite substrate (trade name Celcor manufactured by Corning Incorporated, the number of cells: 400 cells / square inch of cross-sectional area), which was cut into a column shape with a diameter of 24 mm and a length of 67 mm, was immersed in this mud, coated by washing and dried at 150 ° C for 5 minutes, and then calcined in air at 500 ° C for 1 hour, and treated under a stream with 5% hydrogen and 95% nitrogen at 500 ° C
    63/84 for 3 hours to obtain a catalyst 1-a coated with a catalyst component in an amount of 61.33 g (0.887 g platinum, 0.443 g palladium, 60.0 g zirconia-alumina A) by volume 1 liter of substrate.
    Example 1-2
    1,397.7 g of aluminum nitrate nonahydrate (Al (NO3) 3 · 9H 2 O) were completely dissolved in 0.91 liters of deionized water, and 50.0 g of an aqueous solution of nitrate zirconyl (concentration of 20% by mass in conversion to ZrO 2 ), and the mixture was stirred well to prepare a mixed aqueous solution. This solution was dripped into 2 liters of an aqueous solution that was obtained by adjusting to pH 9 with ammonia. During the dripping, the solution was adjusted to a pH within the range of 7 to 10 with ammonia water at a temperature of 25 ° C. A precipitate was generated, filtered, washed well with deionized water and then dried at 120 ° C for 8 hours, and burned at 400 ° C for 5 hours and at 700 ° C for 5 hours to obtain zirconia-alumina B (5% by mass of zirconia, 95% by mass of alumina).
    Next, 60 g of zirconia-alumina B were impregnated with 42.22 g of a mixed aqueous solution obtained by diluting 7.86 g of an aqueous solution of platinum dinitrodiamine containing platinum in an amount corresponding to 0.887 g and 3.16 g of a palladium nitrate solution containing palladium in an amount that corresponds to 0.443 g with deionized water, the zirconia-alumina B was then dried at 120 ° C for 8 hours to obtain a powder, and the powder was further calcined at 500 ° C for 1 hour to obtain precious metal supported by zirconia-alumina B. 61.33 g of this supported precious metal
    64/84 by zirconia-alumina B and 90 ml of deionized water were mixed and ground with moisture to form a sludge.
    0.0303 liter of a cordierite substrate (trade name Celcor manufactured by Corning Incorporated, the number of cells: 400 cells / square inch of cross-sectional area), which was cut into a column shape with a diameter of 24 mm and a length of 67 mm, was immersed in this mud, coated by washing and dried at 150 ° C for 5 minutes, then calcined in air at 500 ° C for 1 hour, and still treated at 500 ° C for 3 hours under a stream with 5% hydrogen and 95% nitrogen to obtain a catalyst 1-b coated with a catalyst component in an amount of 61.33 g (0.87 g of platinum, 0.443 g of palladium,
    60.0 g of zirconia-alumina B) per volume of 1 liter of the substrate.
    Example 1-3
    1,324.3 g of aluminum nitrate nonahydrate (Al (NO3) 3 · 9H 2 O) were completely dissolved in 0.82 liters of deionized water, and added to it
    100.0 g of an aqueous solution of zirconyl nitrate (concentration of% by mass in conversion to ZrO 2 ), and the mixture was stirred well to prepare a mixed aqueous solution. This solution was dripped into liters of an aqueous solution that was obtained by adjusting to pH with ammonia.
    During dripping, the solution was adjusted to a pH within the range of 7 with ammonia water at a temperature of 25 ° C. A precipitate was generated, filtered, washed well with deionized water and then dried at 120 ° C for 8 hours, and calcined at 400 ° C for 5 hours and at 700 ° C for 5 hours to obtain zirconia-alumina C (10% by mass
    65/84 zirconia, 90% by mass of alumina).
    Next, 60 g of zirconia-alumina C were impregnated with 42.22 g of a mixed aqueous solution obtained by diluting 7.86 g of an aqueous solution of platinum dinitrodiamine containing platinum in an amount corresponding to 0.887 g and 3.16 g of a palladium nitrate solution containing palladium in an amount that corresponds to 0.443 g with deionized water, the zirconia-alumina C was then dried at 120 ° C for 8 hours to obtain a powder, and the powder was further calcined at 500 ° C for 1 hour to obtain precious metal supported by zirconia-alumina C. 61.33 g of this precious metal supported by zirconia-alumina C and 90 ml of deionized water were mixed and ground with moisture to form a sludge.
    0.0303 liter of a cordierite carrier (trade name Celcor manufactured by Corning Incorporated, the number of cells: 400 cells / square inch of cross-sectional area), which was cut into a column shape with a diameter of 24 mm and a length of 67 mm, was immersed in this mud, coated by washing and dried at 150 'C for 5 minutes, then calcined in air
    500 ° C for 1 hour, and treated at
    500 ° C for 3 hours under a current with 95% hydrogen and nitrogen to obtain a catalyst
    1-c coated with a catalyst component in a quantity of 61.33 g (0.887 g of platinum, 0.443 g of
    palladium, 60.0 g of zirconia-alumina C) by volume of 1 liter of substrate.Example 1-4 1,250.7 g of nonahydrate nitrate aluminum (Al (NO 3 ) 3 · 9H 2 O) were completely dissolved in 0.82
    liter of deionized water, and added to it
    66/84
    150.0 g of an aqueous solution of zirconyl nitrate (concentration of 20% by mass in conversion to ZrO 2 ), and the mixture was stirred well to prepare a mixed aqueous solution. This solution was dripped into 2 liters of an aqueous solution that was obtained by adjusting to pH 9 with ammonia. During dripping, the solution was adjusted to a pH within the range of 7 to 10 with ammonia at a temperature of 25 ° C. A precipitate was generated, filtered, washed well with deionized water and then dried at 120 ° C for 8 hours, and calcined at 400 ° C for 5 hours and at 700 ° C for 5 hours to obtain zirconia-alumina D (15% by mass of zirconia, 85% by mass of alumina).
    Next, 60 g of zirconia-alumina D were impregnated with 42.22 g of a mixed aqueous solution obtained by diluting 7.86 g of an aqueous solution of platinum dinitrodiamine containing platinum in an amount corresponding to 0.887 g and 3.16 g of a palladium nitrate solution containing palladium in an amount that corresponds to 0.443 g with deionized water, the zirconia-alumina D was then dried at 120 ° C for 8 hours to obtain a powder, and the powder was further calcined at 500 ° C for 1 hour to obtain precious metal supported by zirconia-alumina D. 61.33 g of this precious metal supported by zirconia-alumina C and 90 ml of deionized water were mixed and sprayed with moisture to form a sludge. 0.0303 liter of a cordierite substrate (trade name Celcor manufactured by Corning Incorporated, the number of cells: 400 cells / square inch of cross-sectional area), which was cut into a column shape with a diameter of 24 mm and a length of 67 mm, was immersed in this mud, coated by washing and dried at 150 ° C for 5
    67/84
    minutes later calcined to air treated to 500 ° C for 3 hours hydrogen 5% and nitrogen 95 catalyst 1-d coated with one -
    % to obtain at 500 ° C for 1 hour, and under a current with a catalyst component in an amount of 61.33 g (0.887 g of platinum, 0.443 g of palladium, 60.0 g of zirconia-alumina
    D) per liter volume of the substrate.
    Example 1-5
    1,030.1 g of aluminum nitrate nonahydrate (Al (NO3) 3 · 9H 2 O) were completely dissolved in 0.67 liters of deionized water, and added to it
    300.0 g of an aqueous solution of zirconyl nitrate (mixture concentration was stirred well to prepare a mixed aqueous solution. This solution was dripped into liters of an aqueous solution that was obtained by adjusting to pH with ammonia.
    During dripping, the solution was adjusted to a pH within the range of 7 with ammonia water at a temperature of 25 ° C. A precipitate was generated, filtered, washed well with deionized water and then dried at 120 ° C for 8 hours, and calcined at 400 ° C for 5 hours and at 700 ° C for 5 hours to obtain zirconia-alumina E (30% by mass of zirconia, 70% by mass of alumina).
    Next, 60 g of zirconia-alumina E were impregnated with 42.22 g of a mixed aqueous solution obtained by diluting 7.86 g of an aqueous solution of platinum dinitrodiamine containing platinum in an amount corresponding to 0.887 g and 3.16 g of a palladium nitrate solution containing palladium in an amount that corresponds to 0.443 g with deionized water, the zirconia-alumina E was then dried at 120
    68/84 ° C for 8 hours to obtain a powder, and the powder was further calcined at 500 ° C for 1 hour to obtain precious metal supported by zirconia-alumina E. 61.33 g of this precious metal supported by zirconia-alumina E and 90 ml of deionized water were mixed and ground with moisture to form a sludge.
    0.0303 liter of a cordierite substrate (trade name Celcor manufactured by Corning Incorporated, the number of cells: 400 cells / square inch of cross-sectional area), which was cut into a column shape with a diameter of 24 mm and a length of 67 mm, was immersed in this mud, coated by washing and dried at 150 ° C for 5 minutes, then calcined in air
    500 ° C for 1 hour, and treated at
    500 ° C for 3 hours under a current with 95% hydrogen and nitrogen to obtain a catalyst
    1-e coated with a catalyst component in an amount of 61.33 g (0.887 g platinum, 0.443 g palladium, 60.0 g zirconia-alumina E) per 1 liter volume of the subtract.
    Comparative example 1-1
    735.8 g of aluminum nitrate nonahydrate (Al (N0 3 ) 3 · 9H 2 O) were completely dissolved in 0.48 liters of deionized water, and 500.0 g of an aqueous nitrate solution were added to it zirconyl (concentration of 20% by mass in ZrO 2 conversion) r and the mixture was stirred well to prepare a mixed aqueous solution. This solution was dripped into liters of an aqueous solution that was obtained by adjusting to pH with ammonia.
    During dripping, the solution was adjusted to a pH within the range of 7 with ammonia water at a temperature of 25 ° C. A precipitate was generated, filtered,
    69/84 well washed with deionized water and then dried at 120 ° C for 8 hours, and calcined at 400 ° C for 5 hours and at 700 ° C for 5 hours to obtain zirconia-alumina F (50% by mass of zirconia) , 50% by mass of alumina).
    Next, 60 g of zirconia-alumina F were impregnated with 42.22 g of a mixed aqueous solution obtained by diluting 7.86 g of an aqueous solution of platinum dinitrodiamine containing platinum in an amount corresponding to 0.887 g and 3.16 g of a palladium nitrate solution containing palladium in an amount that corresponds to 0.443 g with deionized water, zirconia-alumina
    F was then dried at 120 ° C for 8 hours to obtain a powder, and the powder was further calcined at 500 ° C for 1 hour to obtain precious metal supported by zirconia-alumina F.
    61.33 g of this precious metal supported by zirconia-alumina F and ml of deionized water were mixed and ground with moisture to form a sludge.
    0.0303 liter of a cordierite substrate (trade name
    Celcor manufactured by Corning Incorporated, the number of cells: 400 cells / transverse square inch), which was cut into a diameter of 24 mm and a length of that mud, coated by washing minutes, then calcined in air at
    500
    in area in an 67 ΠΎΓΠ f the a 150 ° C per
    column was immersed at 5 ° C for 5 hours, and treated at
    500 ° C for 3 hours under a current with 95% hydrogen and nitrogen to obtain a catalyst
    1-f coated with a catalyst component in an amount of 61.33 g (0.887 g platinum, 0.443 g palladium, 60.0 g zirconia-alumina F) per liter volume of the substrate.
    Comparative example 1-2
    70/84
    1,471.7 g of aluminum nitrate nonahydrate (Al (NO3) 3 · 9Η 2 Ο) were weighed and completely dissolved in 0.96 liters of deionized water. This solution was dripped into 2 liters of an aqueous solution that was obtained by adjusting to pH 9 with ammonia. During dripping, the solution was adjusted to a pH within the range of 7 to 10 with ammonia at a temperature of 25 ° C. A precipitate was generated, filtered, washed well with deionized water and then dried at 120 ° C for 8 hours, and calcined at 400 ° C for 5 hours and at 700 ° C for 5 hours to obtain zirconia-alumina G (0% by mass of zirconia, 100% by mass of alumina).
    Next, alumina G was impregnated with 42.22 g of a mixed aqueous solution obtained by diluting 7.86 g of an aqueous solution of platinum dinitrodiamine containing platinum in an amount corresponding to 0.887 g and 3.16 g of a solution of palladium nitrate containing palladium in an amount corresponding to 0.443 g with deionized water, the alumina was then dried at 120 ° C for 8 hours to obtain a powder, and the powder was further calcined at 500 ° C for 1 hour to obtain precious metal supported by alumina. 61.33 g of this precious metal supported by alumina and 90 ml of deionized water were mixed and ground with moisture to form a sludge. 0.0303 liter of a cordierite substrate (trade name Celcor manufactured by Corning Incorporated, the number of cells: 400 cells / square inch of cross-sectional area), which was cut into a column shape with a diameter of 24 mm and a length of 67 mm, was immersed in this mud, coated by washing and dried at 150 ° C for 5 minutes, then calcined in air at 500 ° C for 1 hour, and treated at 500 ° C for 3 hours under
    71/84 a stream with 5% hydrogen and 95% nitrogen to obtain a 1-g catalyst coated with a component
    catalyst in an amount 61.33 g (0.887 g in platinum, 0.443 g of palladium, 60.0 g of alumina G) per volume of 1 liter of substrate. Analysis by XRD Reviews per XRD (diffractometer lightning X
    fully automatic multi-purpose, XX 'Pert PRO MPD ray tube (PW3040 / 60): Cu, manufactured by Spectris Co., Ltd.) were carried out on the respective zirconia-alumina carriers A to F obtained in Examples 1-1 to 1- 5 and in Comparative Example 1-1 (Fig. 1).
    It was found, as shown in Fig. 1, that the carriers of zirconia-alumina A (zirconia content is 2% by mass), zirconia-alumina B (zirconia content is% by mass) and zirconia -alumina C (zirconia content is 10% by mass) do not have peaks between 29 29 ° and 32 °, they do not have tetragonal crystal. It was also found that zirconia-alumina D (zirconia content is 15% by mass), zirconia-alumina E (zirconia content is 30% by mass) and zirconia-alumina F (zirconia content is 50 % by mass) have peaks between 29 29 ° and
    32 ° and have tetragonal crystals. In addition, peaks that appear slightly between about 29 ° and 29 ° are peaks derived from a monoclinic zirconia crystal.
    Next, zirconia-alumina D (zirconia content is 15% by mass), zirconia-alumina E (zirconia content is 30) and zirconia-alumina F (zirconia content is 50% by mass) were mixed with alumina (G) shown in Comparative Example 1-2 and zirconia in the measurement samples
    72/84 were diluted to 10% by weight. These were called zirconia-alumina (15% by mass of the zirconia content was diluted to 10% by mass), the zirconia-alumina E '(30% by mass of the zirconia content was diluted to 10% by mass) and the zirconia-alumina F '(50% by mass of the zirconia content were diluted to 10% by mass). Analyzes by XRD (fully automatic multi-purpose X-ray diffractometer, XX 'Pert PRO MPD ray tube (PW3040 / 60): Cu, manufactured by Spectris Co., Ltd.) were carried out on the respective D', E zirconia-alumina dealers. 'e F' and zirconia-alumina C (Fig. 2).
    It is verified by Fig. 2 that, when zirconiaalumina D 'and F' are compared with zirconia-alumina C, although the zirconia content is 10% by mass, the peak intensities between 29 29 ° and 32 ° are different .
    Therefore, this result suggests that tetragonal crystals were present in zirconia-alumina D ', E' and F 'and, on the other hand, there are no tetragonal crystals in zirconia-alumina A, B and C.
    Consequently, it can be suggested that tetragonal crystals are present in zirconia-alumina D, E and F, and that zirconia-alumina D, E and F have a metal oxide (zirconia) with a primary particle diameter of 5 nm or more. Furthermore, it can be considered that peaks are not observed in zirconia-alumina A, B and C between 29 27 ° and 29 ° and between 29 29 ° and 32 ° and, thus, zirconia in zirconia-alumina has a very crystal structure fine with a particle diameter less than 5 nm or an amorphous structure.
    The particle diameters of zirconia-alumina D, E and
    73/84
    F, in which tetragonal crystals were observed were calculated from the peaks between 29 29 ° and 32 ° (peaks of tetragonal crystals), using the Scherrer equation. Note that a crystallite diameter was found to be a particle diameter.
    Formula 1
    Scherrer equation D = Κλ / βαοδθ
    D: crystallite diameter (a crystallite diameter is used as a particle diameter)
    K: form factor (0.9 is used) λ: X-ray wavelength (1.5406 Â) β: peak width after correction of the diffraction line length depending on the device
    Θ: diffraction angle
    As a result, mean valleys of particle diameters were zirconia-alumina D: 5 nm, zirconia-alumina E: 7 to 8 nm and zirconia-alumina F: 7 to 8 nm.
    Observation by electron microscope
    Observation by electron microscope (H-7650, manufactured by Hitachi High-Technologies Corporation) was performed on the respective zirconia-alumina carriers A to G obtained in Examples 1-1 to 1-5 and in Comparative Examples 1-1 and 1- 2, and she was able to confirm that an alumina particle diameter is 10 to 30 nm.
    Thermal aging
    Thermal aging was carried out on the respective catalysts 1-a, 1-b, 1-c, 1-d, 1-e, 1-f and 1g, which were shown in Examples 1-1 to 1-5 and in Comparative Examples 1- 1 and 1-2, by treatment of
    74/84 catalysts at 700 ° C for 30 hours in an electric furnace in an atmosphere with 6% by volume of steam, 10% by volume of oxygen and 84% by volume of nitrogen. This is thermal aging assuming that catalysts are used in a diesel engine.
    Performance evaluation of catalysts for exhaust gas purification
    While a gas (space velocity of 40,000 h 1 , linear gas velocity of 0.75 m / second) under the condition in Table 1 is fluid through each catalyst after the thermal treatment described above, when the gas temperature is increased by a temperature at a rate of temperature increase of 20 ° C / min, Fig. 3 and Fig. 4 showed graphs of the tabulation of ZrO 2 contents in zirconia-alumina and alumina that are carriers of precious metal support in the respective catalysts, assuming that the catalyst inlet temperature at the time when 50% carbon monoxide is purified at a catalyst outlet are COT50 and, likewise, a catalyst inlet temperature at the time when 50% of propylene is purified on a catalyst outlet are HCT50.
    Table 1 - Reaction gas conditions.
    Components Concentrations c 3 h 6 280 ppm Cl * CO 1,000 ppm AT THE 80 ppm The 2 12% co 2 6%
    75/84
    h 2 o 7% n 2 BALANCE
    Cl *: conversion of Cl
    Table 2 - ZrO 2 contents in catalysts (% by mass).
    Catalyst names ZrO 2 concentrations in carriers of precious metal support (zirconiaalumina or alumina) [% by mass] 1-a 2 1-b 5 1-c 10 1-d 15 1 and 30 1-f 50 1-g 0
    It has been possible to confirm, as shown in Fig. 3 and Fig. 4, that catalysts 1-a, 1-b, 1-c, 1-de 1-and 5 in Examples 1-1 to 1-5 can oxidize CO and propylene at lower temperatures, when compared to catalysts 1-f and 1-g in Comparative Examples 1-1 and 12, On the other hand, it was also possible to confirm that catalyst 1-f with excessive ZrO 2 , in contrast , 10 hardly causes oxidation of CO and propylene.
    Example 2-1
    6,917 g of aluminum nitrate nonahydrate (Al (NO3) 3 · 9H 2 O) were completely dissolved in 4.5 liters of deionized water, and 15 250.0 g of an aqueous solution of zirconyl nitrate were added to it (concentration of 20% by mass in conversion of ZrO 2 ) and 100.0 g of a solution in sulfuric acid of titanium sulfate (concentration of 30% by mass in conversion of
    76/84
    TiO 2 ), and the mixture was stirred well to prepare a mixed aqueous solution. This solution was dripped into 10 liters of an aqueous solution at 25 ° C, which was obtained by adjusting to pH 10 with ammonia. During the dripping, the solution was adjusted to a pH within the range of 7 to 10 with ammonia water. A precipitate was generated, filtered, washed well with deionized water and then dried at 120 ° C for 8 hours, and calcined at 400 ° C for 5 hours and at 700 ° C for 5 hours to obtain titania-zirconia-alumina A ( 0.1% by mass of titania, 5.0% by mass of zirconia, 94.9% by mass of alumina).
    700.8 g of titania-zirconia-alumina A (0.1% by mass of titania, 5.0% by mass of zirconia, 94.9% by mass of alumina) were impregnated with 480 ml of a mixed aqueous solution obtained by diluting an aqueous solution of platinum dinitrodiamine containing platinum in an amount corresponding to 12.6 g and a palladium nitrate solution containing palladium in an amount corresponding to 6.3 g with deionized water, titania-zirconia-alumina A it was then dried at 120 ° C for 8 hours to obtain a powder, and the powder was further calcined at 500 ° C for 1 hour 10 to obtain 719.7 g of precious metal supported by titania-zirconiaalumina A. This precious metal supported by titaniazirconia-alumina A, 280.3 g beta-zeolite (silica / alumina ratio (molar ratio) = 35, surface area 543 m 2 / g, average particle diameter of 0.6 pm) and 1,200 ml of Deionized water was mixed and ground with moisture to form a sludge. A cordierite substrate with a diameter of 103 mm and a length of 130 mm (manufactured by NGK Insulators, Ltd., the number of cells: 600
    77/84 cells / square inch cross-sectional area) was immersed in this mud and coated by washing, an excess mud was removed, and the carrier was then dried at 150 ° C for 5 minutes, calcined in air at 500 ° C for 1 hour and treated at 500 ° C for 3 hours under a stream of air with 5% hydrogen and 95% nitrogen to obtain a 2-a catalyst coated with a catalyst component in an amount of 148.2 g (1.8 g platinum, 0.9 g of palladium, 100 g of titania-zirconia-alumina A, 40 g of betazeolite) per volume of 1 liter of the subtract.
    Example 2-2
    Titania-zirconia-alumina B (1.0 per mass of titania,
    5.0% by mass of zirconia,
    94.0 per mass of alumina) was obtained by the same method as
    Example 2-1, changing the amounts of aluminum nitrate nonahydrate, an aqueous solution of zirconyl nitrate and a solution in sulfate sulfuric acid to follow, catalyst 2-b was obtained by the same method as Example 2-1, except for the exchange of titania-zirconia-alumina A for titania-zirconia-alumina B (1.0% by mass of titania, 5.0% by mass of zirconia, 94.0% by mass of alumina).
    Example 2-3
    Titania-zirconia-alumina C (5.0% by mass of titania, 5.0% by mass of zirconia, 90.0% by mass of alumina) was obtained by the same method as Example 2-1, changing the amounts of aluminum nitrate nonahydrate, an aqueous solution of zirconyl nitrate and a solution in titanium sulfate sulfuric acid.
    Next, catalyst 2-c was obtained by the same
    78/84 method as Example 2-1, except for the exchange of titania-zirconia-alumina A for titania-zirconia-alumina C (5.0% by mass of titania, 5.0% by mass of zirconia, 90.0% by mass of alumina).
    Example 2-4
    6,917 g (Al (ΝΟ 3 ) 3 · 9Η 2 Ο) of aluminum nitrate nonahydrate were completely dissolved in 4.5 liters of deionized water, and added to it
    250.0 g of an aqueous solution of zirconyl nitrate (mass concentration in conversion of ZrO 2 ) and the mixture was stirred well to prepare a mixed aqueous solution. This solution was dripped into 10 liters of an aqueous solution at 25 ° C, which was obtained by adjusting to pH with
    7.3 g of sodium metasilicate and ammonia.
    During dripping, the solution was adjusted to a pH within the range of 7 with ammonia water.
    After dripping, pH was adjusted to be around neutral pH (pH 8) with nitric acid.
    A generated precipitate was filtered, washed well with deionized water, and then dried at 120 ° C for 8 hours and burned at 400 ° C for 5 hours
    700 ° C for hours to obtain silica zirconia-alumina D (0.1 by mass of silica, 5.0% by mass of zirconia,
    94.9% by mass of alumina).
    Next, catalyst 2-d was obtained by the same method as Example 2-1, except for the exchange of titaniazirconia-alumina A for silica-zirconia-alumina D (0.1% by mass of silica, 5.0% by mass of zirconia, 94.9% by mass of alumina).
    Example 2-5
    Silica-zirconia-alumina E (1.0% by mass of silica,
    79/84
    5.0% by mass of zirconia, 94.0% by mass of alumina) was obtained by the same method as Example 2-4, changing the amounts of aluminum nitrate nonahydrate, an aqueous solution of zirconyl nitrate and metasilicate sodium.
    Then, catalyst 2-e was obtained by the same method as Example 2-1, except for the exchange of titaniazirconia-alumina A for silica-zirconia-alumina E (1.0% by mass of silica, 5.0% by mass of zirconia, 94.0% by mass of alumina).
    Example 2-6
    Silica-zirconia-alumina F (5.0% by mass of silica, 5.0% by mass of zirconia, 90.0% by mass of alumina) was obtained by the same method as Example 2-4, changing the amounts of aluminum nitrate nonahydrate, an aqueous solution of zirconyl nitrate and sodium metasilicate.
    Next, catalyst 2-f was obtained by the same method as Example 2-1, except for the exchange of titaniazirconia-alumina A for silica-zirconia-alumina F (5.0% by mass of silica, 5.0% by silica mass of zirconia, 90.0% by mass of alumina).
    Comparative example 2-1
    Zirconia-alumina G (zirconia 5.0% by mass, alumina 95.0% by mass) was obtained by the same method as the
    Example 2-1, changing the amounts of aluminum nitrate nonahydrate, an aqueous solution of zirconyl nitrate and a solution in titanium sulfate sulfuric acid.
    Then, the 2-g catalyst was obtained by the same
    80/84 method as Example 2-1, except for the exchange of titaniazirconia-alumina Ά for zirconia-alumina G (5.0% by mass of zirconia, 95.0% by mass of alumina).
    XRD Analysis
    Analyzes by XRD (fully automatic multi-purpose X-ray diffractometer, XX 'Pert PRO MPD ray tube (PW3040 / 60): Cu, manufactured by Spectris Co., Ltd.) were carried out on the respective titania-zirconia-alumina carriers a C, silica-zirconia-alumina D to F and zirconia-alumina G obtained in Examples 2-1 to 2- and in Comparative Example 2-1 (Fig. 5 and Fig. 6).
    titania-zirconia-alumina (1) XRD analysis
    At the graph in Fig. 5, (A) expresses a carrier titania -zirconia-alumina A (0.1 % by mass of titania, 5.0 % per zirconia mass, 94.9 % by mass alumina) obtained in Example 2-1, (B) expresses a carrier titania -zirconia-alumina B (1.0 % by mass of titania, 5.0 % per zirconia mass, 94.0 % by mass alumina) obtained in Example 2-2, (Ç) expresses a carrier titania -zirconia-alumina C (5.0 % by mass of titania, 5.0 % per zirconia mass, 90.0 % by mass alumina) obtained in Example 2-3, and (G) expresses a carrier zirconia-alumina G (5.0% by mass of zirconia a, 95.0% per
    obtained in
    Comparative example 2-1.
    mass of alumina)
    At the graph shown at Fig. 5, observed between 2Θ30 ° and 70 ° were the pi alumina. Zirconia has one peak in between (crystal tetragonal) and in between 2Θ 27th
    monoclinic derivatives), but that peak was not all the peaks
    2Θ 29 ° and 32 °
    Consequently, it is assumed that zirconia in carriers of the
    81/84 titania-zirconia-alumina (A) to (C) has a very fine crystal structure with a particle diameter of less than 5 nm or an amorphous structure. In addition, titania has a peak around 2Θ25 ° (anatase type crystal) and around 2Θ28 ° (rutile type crystal), but this peak was not observed in (A) to (C). Consequently, it is assumed that titania in titania-zirconia-alumina carriers (A) to (C) has a very fine crystal structure with a particle diameter of less than 5 nm or an amorphous structure.
    (2) XRD analysis on silica-zirconia-alumina
    In the graph in Fig. 6, (D) expresses a carrier of silica-zirconia-alumina D (0.1% by mass of silica, 5.0% by mass of zirconia, 94.9% by mass of alumina) obtained in Example 2-4, (E) expresses a silica zirconia-alumina carrier (1.0% 5 by mass of silica, 5.0% by mass of zirconia, 94.0% by mass of alumina) obtained in Example 2- 5, (F) expresses a silica-zirconiaalumina carrier F (5.0% by mass of silica, 5.0% by mass of zirconia, 90.0% by mass of alumina) obtained in Example 26, and (G) expresses a zirconia-alumina carrier G (5.0% by mass of zirconia, 95.0% by mass of alumina) obtained in Comparative Example 2-1.
    In the graph shown in Fig. 6, all peaks observed between 2Θ30 ° and 70 ° were the peaks derived from alumina. No peak of a crystal zirconia (between 2Θ29 ° and 32 ° (tetragonal crystal) and between 2Θ 27 ° and 29 ° (monoclinic crystal)) was observed in (D) to (F) and, consequently, zirconia is assumed in silica-zirconia-alumina carriers (D) to (F) has a structure
    82/84 very fine crystal with a particle diameter less than 5 nm or an amorphous structure. In addition, silica has a peak around 2Θ20 ° to 28 °, but this peak was not observed in (D) to (F). Consequently, it is assumed that silica in silica-zirconia-alumina carriers (D) to (F) has a very fine crystal structure with a particle diameter of less than 5 nm or an amorphous structure.
    Observation by electron microscope
    The observation under an electron microscope (H-7650, manufactured by Hitachi High-Technologies Corporation) was carried out in the respective carriers of titania-zirconiaalumina A to C, silica-zirconia-alumina D to F and zirconia-alumina G obtained in Examples 2 -1 to 2-6 and in Comparative Example 2-1, and it was able to be confirmed that the alumina particle diameter is 10 to 30 nm.
    Aging Treatment
    The following treatments 1, 2 and 3 were carried out by aging catalysts one by one.
    1. Thermal aging
    A heat treatment was carried out on the respective catalysts 2-a to 2-g shown in Examples 2-1 to 2-6 and in Comparative Example 2-1 by aging the carriers at 700 ° C for 50 hours in an electric furnace in the atmosphere.
    2. Sulfur poisoning
    The catalysts after the thermal tolerance treatment were exposed to an exhaust gas flow for 100 minutes using light oil containing 400 ppm of a sulfur component as a fuel in a 3.1 liter displacement diesel engine, under the condition on one
    83/84 torque of 15 Nm and a rotational number of 2,000 rpm. In addition, the total amount of the sulfur component in the exhaust gas was 10.8 g (± 10%) in conversion of sulfur dioxide.
    3. Regeneration treatment
    N ° JIS2 light oil was added to an exhaust gas flow on the upper flow side of the exhaust gas flow catalyst using N ° JIS2 light oil as a fuel in the same engine as in the sulfur poisoning described in 2, under the condition of a torque of 13 Nm and a rotational number of 2,000 rpm and maintained for 15 minutes. In addition, the added amount of light oil No. JIS2 is an amount at a level such that a temperature at the catalyst outlet is 670 ° C with combustion heat in an oxidation catalyst. As described above, the sulfur component deposited in the sulfur poisoning described in 2 was partially desorbed by combustion heat.
    This is aging that simulates the deterioration in catalytic performance caused by thermal aging and poisoning caused by a sulfur component in use of a general diesel engine.
    Performance evaluation of catalyst for exhaust gas purification
    The evaluation of the purification performance over CO was carried out on each catalyst after the aging treatment described above, partially diverging an exhaust gas from an exhaust gas flow path of a 9.84 liter diesel engine and allowing the exhaust gas is passed through the catalyst. The evaluation was carried out going from idle to a torque of 250 Nm
    84/84 and a rotational number of 1,110 rpm over 13 seconds. During the performance evaluation, the temperature of the exhaust gas at a catalyst inlet increased from 110 ° C to 160 ° C. The results were shown in Fig.
    7 and Fig. 8.
    As is obvious from Fig. 7 and Fig. 8, when compared to a catalyst obtained by supporting a precious metal in zirconia-alumina, zirconia-alumina including titania and silica showed even high CO oxidation performance after poisoning with a sulfur component in an exhaust gas.
    In addition, this application is based on Japanese Patent Application No. 2011-047643 filed on March 4, 2011 and Japanese Patent Application No. 2011-101608 filed on March 28, 2011, the disclosures of which are incorporated herein by reference.
    权利要求:
    Claims (9)
    [1]
    1. Catalyst for purification of exhaust gas, characterized by being obtained by having a carrier comprising aluminum oxide (Al 2 O3) and one or more metal oxides selected from the group consisting of zirconium oxide (ZrO2), cerium oxide (CeO2), yttrium oxide (Y2O3), neodymium oxide (Nd2O3), silicon oxide (SiO2) and titanium oxide (TiO2) which support one or more catalyst components selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru) and osmium (Os), in which the metal oxides have particle diameters less than 10 nm, where the mass ratio of aluminum oxide and metal oxide is 99: 1 to 80:20, respectively.
    [2]
    2. Catalyst for purification of exhaust gas, according to claim 1, characterized by the fact that a mass ratio of aluminum oxide to metal oxide is 98.2: 85.15.
    [3]
    3. Exhaust gas purification catalyst according to claim 1 or 2, characterized by the fact that the metal oxide is zirconium oxide (ZrO2) or a mixture obtained by mixing zirconium oxide (ZrO2) with one or most selected from the group consisting of cerium oxide (CeO2), yttrium oxide (Y2O3), neodymium oxide (Nd2O3), silicon oxide (SiO2) and titanium oxide (TiO2).
    [4]
    4. Catalyst for purification of exhaust gas, according to claim 1, characterized by the fact that the carrier consists of 60 to 99.49 parts per mass of aluminum oxide (Al2O3), 0.5 to 20 parts per mass of zirconium oxide (ZrO2) and a second oxide
    Petition 870190049342, of 05/27/2019, p. 13/15
    2/3 metallic selected from the group consisting of 0.01 to 10 parts by mass of silicon oxide (S1O2) and 0.01 to 10 parts by mass of titanium oxide (TiO2) (the total mass of aluminum oxide, zirconium oxide and metal oxides is 100 parts per mass) and where the zirconium oxide particle diameter is less than 10 nm.
    [5]
    Exhaust gas purification catalyst according to any one of claims 1, 2, 3 or 4, characterized in that the particle diameter of the aluminum oxide is 10 to 100 nm.
    [6]
    Exhaust gas purification catalyst according to any one of claims 1, 2, 3, 4 or 5, characterized by the fact that the catalyst component is (i) Pt, or (ii) Pt and Pd, and in the case of (ii) the mass ratio of Pt and Pd is from 1: 0 to 1: 1.
    [7]
    7. Method for producing the exhaust gas purification catalyst as defined in any one of claims 1, 2, 3, 4, 5 or 6, characterized in that it comprises a step of adding a solution containing:
    - a water-soluble Al compound and
    - a water-soluble compound of one or more metals selected from the group consisting of Zr, Ce, Y, Nd, Si and Ti to an alkaline solution to be mixed and coprecipitated to obtain a coprecipitated product, and then the calcination of the coprecipitated product to obtain , thus, a
    carrier which comprises O oxide in aluminum and the oxide metallic in a reason in pasta in 99: 1 for 80:20, respectively. 8. Method for production of catalyst for
    Petition 870190049342, of 05/27/2019, p. 14/15
    3/3 exhaust gas purification according to claim 7, further comprising a step of impregnating the carrier containing aluminum oxide and metal oxide with an aqueous solution of a compound of a catalyst component and then burning the carrier obtained by impregnation to obtain a carrier with supported catalyst component.
    [8]
    9. Method for producing the exhaust gas purification catalyst according to claim 7 or 8, further comprising a step of preparing a sludge comprising the carrier with supported catalyst component, or the carrier with supported catalyst component and a refractory inorganic oxide (supported component), and coating the mud to a three-dimensional structure.
    [9]
    10. Exhaust gas purification method, characterized by the fact that an exhaust gas is processed with the catalyst as defined in any one of claims 1, 2, 3, 4, 5 or 6 or a catalyst obtained by the method as defined in any of claims 7, 8 or 9.
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    同族专利:
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    US9561494B2|2017-02-07|
    EP2682185A4|2014-12-03|
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    EP2682185A1|2014-01-08|
    JP5746318B2|2015-07-08|
    CN103402627A|2013-11-20|
    JPWO2012121085A1|2014-07-17|
    WO2012121085A1|2012-09-13|
    CN107413336A|2017-12-01|
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    法律状态:
    2019-02-26| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-07-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-08-13| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/02/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/02/2012, 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
    JP2011047643|2011-03-04|
    JP2011101608|2011-04-28|
    PCT/JP2012/055132|WO2012121085A1|2011-03-04|2012-02-29|Catalyst for exhaust gas purification, method for producing same, and exhaust gas purification method using same|
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