Patent Application
20250235822
The present invention relates to an exhaust gas purification catalyst composition, an exhaust gas purification catalyst and an exhaust gas purification system.
Exhaust gas emitted from an internal combustion engine of an automobile, a motorcycle or the like contains harmful components such as hydrocarbon (HC), carbon monoxide (CO) and nitrogen oxide (NOx). A three-way catalyst is used to purify and detoxify those harmful components. A catalyst containing noble metal elements such as platinum element (Pt), palladium element (Pd) and rhodium element (Rh) is used as a three-way catalyst. Pt and Pd are mainly involved in oxidative purification of HC and CO and Rh is mainly involved in reductive purification of NOx.
Various techniques have been developed to improve the exhaust gas purification performance of an exhaust gas purification catalyst. For example, Patent Document 1 discloses a technique for forming a catalyst layer including: a lower layer containing Pd and an alkaline-earth metal element; and an upper layer containing Rh on the upstream side of a substrate, and a catalyst layer including: a lower layer containing Pt and an alkaline-earth metal element; and an upper layer containing Rh on the downstream side of the substrate. In addition, Patent Document 2 discloses a technique for forming a catalyst layer including: a lower layer containing Pd and Ba; and an upper layer containing Rh on the upstream side of a substrate, and a catalyst layer including: a lower layer containing Pt and Ba; and an upper layer containing Rh on the downstream side of the substrate.
Patent Document 1: Japanese Patent Laid-Open No. 2020-157263
Patent Document 2: Japanese Patent Laid-Open No. 2016-185495
It is considered that if NOx adsorption performance is imparted to a catalyst layer, this will compensate for the exhaust gas purification performance and thus improve the exhaust gas purification performance. Conventionally, Ba is known as a NOx adsorbent. On the other hand, from the viewpoint of cost reduction, it is required to utilize Pt instead of Rh and Pd. However, the present inventors have found that if Ba is added to a catalyst layer containing Pt, the added Ba will decrease the dispersibility of Pt, thereby decreasing the exhaust gas purification performance.
Accordingly, an object of the present invention is to provide a new technique to impart NOx adsorption performance to a catalyst layer containing Pt, thereby improving the exhaust gas purification performance, while suppressing decrease in the dispersibility of Pt.
In order to solve the above problem, the present invention provides the following inventions.
[1] An exhaust gas purification catalyst composition containing Pt and Mg, wherein a content of Mg in terms of metal is 2.0% by mass or more and 9.0% by mass or less based on a mass of the exhaust gas purification catalyst composition.
[2] The exhaust gas purification catalyst composition according to [1], wherein a content of an alkaline-earth metal element other than Mg in terms of metal is 4.0% by mass or less based on the mass of the exhaust gas purification catalyst composition.
[3] The exhaust gas purification catalyst composition according to [1] or [2], wherein Mg is present in one or two forms selected from MgO and MgCO3.
[4] The exhaust gas purification catalyst composition according to any one of [1] to [3], wherein Mg is present in a form other than a complex oxide comprising Mg and Al.
[5] The exhaust gas purification catalyst composition according to any one of [1] to [4], wherein when, in an X-ray diffraction pattern of the exhaust gas purification catalyst composition, a diffraction intensity of a peak present at 2θ=64 to 67° among peaks derived from MgAl2O4 is expressed as A, and, in an X-ray diffraction pattern of α-Al2O3 which is Standard Reference Material 674a distributed by the National Institute of Standards and Technology, a diffraction intensity of a peak present at 2θ=55° to 58° among peaks derived from the α-Al2O3 is expressed as B, a ratio of A to B is less than 0.060.
[6] The exhaust gas purification catalyst composition according to any one of [1] to [5], wherein the exhaust gas purification catalyst composition contains a modified alumina containing La, and wherein a content of La derived from the modified alumina in terms of La2O3 is 0.20% by mass or more and 5.0% by mass or less based on the mass of the exhaust gas purification catalyst composition.
[7] An exhaust gas purification catalyst including a substrate and a first catalyst layer provided on the substrate, wherein the first catalyst layer is composed of the exhaust gas purification catalyst composition according to any one of [1] to [6].
[8] The exhaust gas purification catalyst according to [7], wherein the exhaust gas purification catalyst further includes a second catalyst layer provided on the substrate and/or a third catalyst layer provided on the substrate, wherein the second catalyst layer is provided on an upside of the first catalyst layer, and wherein the third catalyst layer is provided on an upstream side of the first catalyst layer.
[9] The exhaust gas purification catalyst according to [8], wherein the second catalyst layer and/or the third catalyst layer contains Rh.
[10] The exhaust gas purification catalyst according to [8] or [9], wherein a content of an alkaline-earth metal element in terms of metal in the second catalyst layer is 5.0% by mass or less based on a mass of the second catalyst layer, and wherein a content of an alkaline-earth metal element in terms of metal in the third catalyst layer is 5.0% by mass or less based on a mass of the third catalyst layer.
[11] An exhaust gas purification system including: an exhaust gas path through which exhaust gas flows; a first exhaust gas purification catalyst provided on a downstream side of the exhaust gas path; and a second exhaust gas purification catalyst provided on an upstream side of the exhaust gas path, wherein the first exhaust gas purification catalyst includes a first substrate and a catalyst layer provided on the first substrate, and wherein the catalyst layer provided on the first substrate is composed of the exhaust gas purification catalyst composition according to any one of [1] to [6].
[12] The exhaust gas purification system according to [11], wherein the second exhaust gas purification catalyst includes a second substrate and a catalyst layer provided on the second substrate.
[13] The exhaust gas purification system according to [12], wherein the catalyst layer provided on the second substrate contains Rh.
[14] The exhaust gas purification system according to [12] or [13], wherein a content of an alkaline-earth metal element in terms of metal in the catalyst layer provided on the second substrate is 5.0% by mass or less based on a mass of the catalyst layer provided on the second substrate.
According to the present invention, there is provided a new technique to impart NOx adsorption performance to a catalyst layer containing Pt, thereby improving the exhaust gas purification performance, while suppressing decrease in the dispersibility of Pt.
In the present specification, the term “alkaline-earth metal element” means an element selected from Be, Mg, Ca, Sr, Ba and Ra.
The exhaust gas purification catalyst composition of the present invention will now be described. In the present specification, an “exhaust gas purification catalyst composition” may be referred to as a “catalyst composition”.
The catalyst composition of the present invention is in the form of, for example, a powder, a molded body, a layered body, or the like.
The catalyst composition of the present invention contains Pt.
Pt contained in the catalyst composition of the present invention is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing Pt, such as metal Pt, an alloy containing Pt, a compound containing Pt (e.g., an oxide of Pt), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing Pt is in the form of a particle.
From the viewpoint of balancing the exhaust gas purification performance and the cost, the content of Pt in terms of metal in the catalyst composition of the present invention is preferably 0.050% by mass or more and 5.0% by mass or less, more preferably 0.10% by mass or more and 3.0% by mass or less, and still more preferably 0.30% by mass or more and 1.0% by mass or less, based on the mass of the catalyst composition of the present invention.
In the present specification, the expression “the mass of a catalyst composition” means the total mass calculated by categorizing all metal elements contained in the catalyst composition into a noble metal element(s) and a metal element(s) other than the noble metal element(s), obtaining the mass(es) of the noble metal element(s) in terms of metal and the mass(es) of the metal element(s) other than the noble metal element(s) in terms of oxide, and totalizing the obtained masses. That is, the expression “the mass of a catalyst composition” means the calculated mass obtained by totalizing the mass(es) of a noble metal element(s) in terms of metal in the catalyst composition and the mass(es) of a metal element(s) other than the noble metal element(s) in terms of oxide in the catalyst composition. The term “metal element” encompasses a metalloid element such as Si, B, or the like.
In the present specification, the term “noble metal element” encompasses Pt, Pd, Rh, Au, Ag, Ru, Ir and Os.
In the present specification, an oxide of Al means Al2O3, an oxide of Si means SiO2, an oxide of B means B2O3, an oxide of Zr means ZrO2, an oxide of Be means BeO, an oxide of Mg means MgO, an oxide of Ca means CaO, an oxide of Sr means SrO, an oxide of Ba means BaO, an oxide of Ra means RaO, an oxide of Ti means TiO2, an oxide of Ni means NiO, and an oxide of P means P2O5. An oxide of a rare earth element except for Ce, Pr and Tb means a sesquioxide (Ln2O3), an oxide of Ce means CeO2, an oxide of Pr means Pr6O11, and an oxide of Tb means Tb4O7.
In the case where the composition of raw materials used for producing the catalyst composition of the present invention is known, the content of Pt in terms of metal in the catalyst composition of the present invention can be determined from the composition of the raw materials used for producing the catalyst composition of the present invention.
In the case where the composition of raw materials used for producing the catalyst composition of the present invention is not known, the content of Pt in terms of metal in the catalyst composition of the present invention can be determined using a conventional method such as scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX). A specific example is as mentioned below.
Elemental analysis using a conventional method such as SEM-EDX is performed on a sample obtained from the catalyst composition of the present invention to identify the types of constituent elements of the entire sample and obtain the content (% by mass) of the target element in terms of metal. From each of 10 fields of view in SEM, the content (% by mass) of the target element in terms of metal is obtained. The average of the contents (% by mass) of the target element in terms of metal obtained from the 10 fields of view is defined as the content (% by mass) of the target element in terms of metal in the catalyst composition of the present invention.
The catalyst composition of the present invention may contain a noble metal element other than Pt. Examples of the noble metal element other than Pt include Au, Ag, Pd, Rh, Ir, Ru, Os, and the like. The noble metal element other than Pt contained in the catalyst composition of the present invention is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing the noble metal element other than Pt, such as metal, an alloy containing the noble metal element, a compound containing the noble metal element (e.g., an oxide of the noble metal element), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing the noble metal element other than Pt is in the form of a particle.
In the case where the catalyst composition of the present invention contains Pt and the noble metal element other than Pt, Pt and the noble metal element other than Pt may form an alloy, thereby decreasing the active sites of Pt participating in exhaust gas purification. Accordingly, it is preferable that the catalyst composition of the present invention is substantially free from the noble metal element other than Pt. The expression “substantially free from the noble metal element other than Pt” means that the content of the noble metal element other than Pt in terms of metal in the catalyst composition of the present invention is preferably 0.050% by mass or less, and more preferably 0.010% by mass or less, based on the mass of the catalyst composition of the present invention. The lower limit is zero. The expression “the content of the noble metal element other than Pt in terms of metal in the catalyst composition of the present invention” means, in the case where the catalyst composition of the present invention contains one noble metal element other than Pt, the content of the one noble metal element other than Pt in terms of metal, and means, in the case where the catalyst composition of the present invention contains two or more noble metal elements other than Pt, the total content of the two or more noble metal elements other than Pt in terms of metal. The content of the noble metal element other than Pt in terms of metal in the catalyst composition of the present invention can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The catalyst composition of the present invention contains Mg.
Mg contained in the catalyst composition of the present invention can impart NOx adsorption performance to the catalyst composition of the present invention, thereby improving the exhaust gas purification performance, while suppressing decrease in the dispersibility of Pt. It is considered that the weak basic strength and/or the high electronegativity of Mg is associated with this effect. However, when the content of Mg in terms of metal is too small, the NOx adsorption performance of Mg is not fully demonstrated. On the other hand, when the content of Mg in terms of metal is too large, Pt is covered by Mg, thereby decreasing the exhaust gas purification performance. Therefore, the content of Mg in terms of metal in the catalyst composition of the present invention is preferably 2.0% by mass or more and 9.0% by mass or less, more preferably 3.0% by mass or more and 8.0% by mass or less, and still more preferably 4.0% by mass or more and 7.0% by mass or less, based on the mass of the catalyst composition of the present invention. The content of Mg in terms of metal in the catalyst composition of the present invention can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The catalyst composition of the present invention contains one or two or more Mg sources. The Mg source is not particularly limited as long as the Mg source is a compound containing Mg.
From the viewpoint of more effectively suppressing decrease in the dispersibility of Pt while imparting NOx adsorption performance to the catalyst composition, one or two or more selected from MgO, MgCO3 and Mg(NO3)2 are preferably used as the Mg source, and one or two selected from MgO and MgCO3 are more preferably used as the Mg source. That is, in the catalyst composition of the present invention, Mg is present preferably in one or two or more forms selected from MgO, MgCO3 and Mg(NO3)2, and more preferably in one or two forms selected from MgO and MgCO3.
Mg(NO3)2 can be used as a raw material for producing the catalyst composition of the present invention, and is converted to MgO by calcination.
A complex oxide containing Mg and Al (which may be referred to as a “Mg—Al-based complex oxide” in the present specification) may be used as the Mg source. However, one or two or more selected from MgO, MgCO3 and Mg(NO3)2 as described above is preferable than the Mg—Al-based complex oxide, from the viewpoint of more effectively suppressing decrease in the dispersibility of Pt. That is, in the catalyst composition of the present invention, it is preferable that Mg is present in a form other than the Mg—Al-based complex oxide, from the viewpoint of more effectively improving the dispersibility of Pt. When Mg is present in a form other than the Mg—Al-based complex oxide, the ratio of A to B (A/B) as described below is preferably less than 0.060, more preferably less than 0.050, still more preferably less than 0.040.
When, in an X-ray diffraction pattern of the catalyst composition of the present invention, a diffraction intensity of a peak present at 2θ=64 to 67° among peaks derived from MgAl2O4 is expressed as A, and, in an X-ray diffraction pattern of α-Al2O3 which is Standard Reference Material 674a distributed by the National Institute of Standards and Technology, a diffraction intensity of a peak present at 2θ=55° to 58° among peaks derived from the α-Al2O3 is expressed as B, the ratio of A to B (A/B) is preferably less than 0.060, more preferably less than 0.050, still more preferably less than 0.040, from the viewpoint of more effectively improving the dispersibility of Pt. The lower limit is zero. The ratio of A to B is measured in accordance with the method described in the Examples.
The Mg—Al-based complex oxide may contain a crystal phase having a spinel type crystal structure (hereinafter referred to as a “spinel type crystal phase”). The spinel type crystal structure is a crystal structure of the cubic crystal system and belongs to the space group Fd-3m. The stoichiometric composition of the spinel type crystal phase is MgAl2O4.
The Mg—Al-based complex oxide may be constituted by a single phase of the spinel type crystal phase, or by a phase mixture containing the spinel type crystal phase and one or two more other phases. The other phase may be a crystal phase or an amorphous phase. Examples of the other phase include an alkaline-earth metal oxide phase (e.g., a MgO phase or the like), an a alumina phase, an alumina phase other than an a alumina phase (e.g., a γ alumina phase, a θ alumina phase, or the like), a hydrotalcite phase, and the like.
In the case where the Mg—Al-based complex oxide is constituted by a phase mixture, the spinel type crystal phase may be a first phase, or an a alumina phase may be a first phase. In the case where an a alumina phase is a first phase, the spinel type crystal phase is, for example, a second phase. The “first phase” means a crystal phase from which a peak having a maximum intensity (a main peak) is derived in a diffraction pattern given by powder X-ray diffractometry (XRD) using CuKα. The “second phase” means a crystal phase from which a peak having a maximum intensity, chosen from among peaks other than the peak derived from the first phase, is derived.
The fact that the Mg—Al-based complex oxide contains the spinel type crystal phase can be confirmed by XRD using CuKα. XRD can be performed using a commercially available X-ray diffractometer (e.g., a MiniFlex600 manufactured by Rigaku Corporation).
In the Mg—Al-based complex oxide, Mg, Al and O may form a solid solution phase having the spinel type crystal structure, or may form a single phase (e.g., a MgO phase, an Al2O3 phase, or the like) that is a crystal phase or an amorphous phase. The fact that Mg, Al and O form the solid solution phase can be confirmed using a conventional method such as XRD, SEM-EDX, or the like.
The Mg—Al-based complex oxide may contain one or two or more metal elements other than Mg and Al. Examples of the metal element other than Mg and Al include Ba, Sr, and the like. The metal element other than Mg and Al may form a solid solution phase having the spinel type crystal structure together with Mg, Al and O, or may form a single phase (e.g., a BaO phase, a SrO phase, or the like) that is a crystal phase or an amorphous phase. The fact that the metal element other than Mg and Al forms the solid solution phase together with Mg, Al and O can be confirmed using a conventional method such as XRD, SEM-EDX, or the like.
The catalyst composition of the present invention may contain one or two or more alkaline-earth metal elements other than Mg. The alkaline-earth metal element other than Mg is selected from Be, Ca, Sr, Ba and Ra.
From the viewpoint of more effectively suppressing decrease in the dispersibility of Pt, the content of the alkaline-earth metal element other than Mg in terms of metal in the catalyst composition of the present invention is preferably 4.0% by mass or less, more preferably 2.0% by mass or less, and still more preferably 1.0% by mass or less, based on the mass of the catalyst composition of the present invention. The lower limit is zero. The expression “the content of the alkaline-earth metal element other than Mg in terms of metal in the catalyst composition of the present invention” means, in the case where the catalyst composition of the present invention contains one alkaline-earth metal element other than Mg, the content of the one alkaline-earth metal element in terms of metal, and means, in the case where the catalyst composition of the present invention contains two or more alkaline-earth metal elements other than Mg, the total content of the two or more alkaline-earth metal elements in terms of metal. The content of the alkaline-earth metal element other than Mg in the catalyst composition of the present invention can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The form in which the alkaline-earth metal element other than Mg is present is not particularly limited. In the catalyst composition of the present invention, the alkaline-earth metal element other than Mg can be present in one or two or more forms selected from, for example, an oxide, a carbonate, a nitrate and a sulfate. When the catalyst composition of the present invention contains the Mg—Al-based complex oxide, the alkaline-earth metal element other than Mg can be present as a component of the Mg—Al-based complex oxide.
The catalyst composition of the present invention may contain one or two or more carriers. In the case where the catalyst composition of the present invention contains a carrier, it is preferable that at least part of a catalytically active component is supported on the carrier. The expression that “at least part of a catalytically active component is supported on a carrier” means a state in which at least part of the catalytically active component is physically and/or chemically adsorbed and/or retained on the outer surface of the carrier and/or on the inner surface of pores of the carrier. Whether at least part of a catalytically active component is supported on a carrier can be confirmed using, for example, SEM-EDX or the like. Specifically, when an element mapping obtained by analyzing a catalyst composition by SEM-EDX shows that at least part of a catalytically active component and a carrier exist in the same region, at least part of the catalytically active component can be judged as supported on the carrier.
Examples of the carrier include an inorganic oxide and the like. In the present specification, the term “inorganic oxide” means an inorganic oxide other than oxides of alkaline-earth metal elements (i.e., BeO, MgO, CaO, SrO, BaO and RaO), unless otherwise defined.
The inorganic oxide is, for example, in the form of a particle. The inorganic oxide is preferably porous from the viewpoint that a catalytically active component is easily supported thereon. The inorganic oxide may have oxygen storage capacity (OSC: Oxygen Storage Capacity), or may not have oxygen storage capacity. In the present specification, the inorganic oxide having oxygen storage capacity may be referred to as an “OSC material”. The inorganic oxide used as a carrier is distinct from an inorganic oxide used as a binder (e.g., an inorganic oxide binder such as an alumina binder, a zirconia binder, a titania binder, a silica binder, or the like).
Examples of the inorganic oxide include an Al-based oxide, a Ce—Zr-based complex oxide, an oxide of a rare earth element (e.g., Y2O3, CeO2 or the like), ZrO2, SiO2, TiO2, NiO, and the like.
In the present specification, when, in an oxide containing Ce, Zr and Al, the content of Ce in terms of CeO2 is equal to or greater than the content of Al in terms of Al2O3, the oxide containing Ce, Zr and Al falls into the category of the Ce—Zr-based complex oxide, and when, in an oxide containing Ce, Zr and Al, the content of Ce in terms of CeO2 is smaller than the content of Al in terms of Al2O3, the oxide containing Ce, Zr and Al falls into the category of the Al-based oxide.
The Al-based oxide generally has higher heat resistance than other inorganic oxides (e.g., a Ce—Zr-based complex oxide). When the catalyst composition of the present invention contains the Al-based oxide, the heat resistance of the catalyst composition of the present invention is improved, and thus the exhaust gas purification performance of the catalyst composition of the present invention is improved.
The Al-based oxide contains Al and O. Examples of the Al-based oxide include alumina (Al2O3), a modified alumina, and the like. The Al-based oxide is distinct from alumina used as a binder (which may be referred to as an “alumina binder” in the present specification). The alumina binder is derived from an alumina sol used as a raw material of a catalyst composition. The modified alumina contains one or two or more elements other than Al and O. Examples of the modified alumina include an oxide obtained by modifying the surface of alumina with an element other than Al and O, an oxide obtained by dissolving an element other than Al and O in alumina, and the like. In the Al-based oxide, an element other than Al and O may form a solid solution phase together with Al and O, or may form a single phase (e.g., an oxide phase of the element other than Al and O) that is a crystal phase or an amorphous phase, or may form both the solid solution phase and the single phase.
From the viewpoint of improving the heat resistance, the content of Al in terms of oxide in the Al-based oxide is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass or more, based on the mass of the Al-based oxide. The upper limit is 100% by mass.
In the case where the composition of raw materials used for producing the catalyst composition of the present invention is known, the content of Al in terms of Al2O3 in the Al-based oxide can be determined from the composition of raw materials used for producing the catalyst composition of the present invention.
In the case where the composition of raw materials used for producing the catalyst composition of the present invention is not known, the content of Al in terms of Al2O3 in the Al-based oxide can be determined by analyzing a sample obtained from the catalyst composition of the present invention by energy dispersive X-ray spectroscopy (EDX) to obtain an element mapping, and performing EDX elemental analysis on a designated particle in the obtained element mapping. Specifically, the content of the target element in terms of oxide in the designated particle can be determined by qualitatively identifying (color-coding) an Al-based oxide particle and other oxide particle(s) (e.g., a Ce—Zr-based complex oxide particle) by elemental mapping and performing composition analysis (elemental analysis) on the designated particle.
From the viewpoint of improving the heat resistance, the content of the Al-based oxide in the catalyst composition of the present invention is preferably 10% by mass or more and 95% by mass or less, more preferably 20% by mass or more and 90% by mass or less, and still more preferably 30% by mass or more and 80% by mass or less, based on the mass of the catalyst composition of the present invention.
In the case where the composition of raw materials used for producing the catalyst composition of the present invention is known, the content of the Al-based oxide in the catalyst composition of the present invention can be determined from the composition of raw materials used for producing the catalyst composition of the present invention.
In the case where the composition of raw materials used for producing the catalyst composition of the present invention is not known, the content of the Al-based oxide in the catalyst composition of the present invention can be determined using a conventional method such SEM-EDX. A specific example is as mentioned below.
(A) Elemental analysis using a conventional method such SEM-EDX is performed on a sample obtained from the catalyst composition of the present invention to identify the types of constituent elements of the entire sample, and to obtain the content (% by mass) of the target element in terms of oxide.
(B) Elemental mapping by a conventional method such SEM-EDX is performed on a sample obtained from the catalyst composition of the present invention to identify the types of particles contained in the sample (e.g., an Al-based oxide particle, a Ce—Zr-based complex oxide particle, and optionally other particle(s)).
(C) For each type of particle, elemental analysis by SEM-EDX is performed on a plurality of randomly selected particles (e.g., 50 particles) to identify the types of constituent elements of the particles and to obtain the content (% by mass) of the target element in terms of oxide. For each type of particle, the average value of the content (% by mass) of the target element in terms of oxide is obtained, and the average value is defined as the content (% by mass) of the target element in terms of oxide in each type of particle.
(D) The content (% by mass) of each type of particle in the sample is calculated by drawing up and solving equations representing the relationship among the content (% by mass) of the target element in terms of oxide in the sample, the content (% by mass) of the target element in terms of oxide in each type of particle, and the content (% by mass) of each type of particle in the sample, and is defined as the content (% by mass) of each type of particle in the catalyst composition of the present invention.
The element other than Al and O in the modified alumina can be selected from La, Zr, Ce, Pr, Ba, Sr, P, Ni and the like, and is preferably La from the viewpoint of improving the heat resistance.
From the viewpoint of improving the heat resistance, the content of La in terms of La2O3 in the modified alumina is preferably 0.10% by mass or more and 20% by mass or less, more preferably 0.50% by mass or more and 15% by mass or less, and still more preferably 1.0% by mass or more and 10% by mass or less, based on the mass of the modified alumina. The content of La in terms of La2O3 in the modified alumina can be determined in the same manner as the content of Al in terms of Al2O3 in the Al-based oxide.
From the viewpoint of improving the heat resistance, the catalyst composition of the present invention preferably contains a modified alumina containing La. From the viewpoint of improving the heat resistance, the content of La derived from the modified alumina in terms of La2O3 is preferably 0.20% by mass or more and 5.0% by mass or less, more preferably 0.30% by mass or more and 3.0% by mass or less, based on the mass of the catalyst composition of the present invention. The content of La derived from the modified alumina in terms of La2O3 can be determined from the content of the modified alumina in the catalyst composition of the present invention and the content of La in terms of La2O3 in the modified alumina.
The Ce—Zr-based complex oxide has an oxygen storage capacity (i.e., an ability to absorb oxygen when the oxygen concentration in exhaust gas is high and release oxygen when the oxygen concentration in exhaust gas is low), and mitigate fluctuations in the oxygen concentration in exhaust gas and expand the operating window of a catalytically active component. Therefore, when the catalyst composition of the present invention contains the Ce—Zr-based complex oxide, the exhaust gas purification performance of the catalyst composition of the present invention is improved. In particular, when the catalyst composition of the present invention contains the Ce—Zr-based complex oxide and is used as a three-way catalyst for purifying exhaust gas emitted from a gasoline engine, both control of oxygen concentration by the Ce—Zr-based complex oxide and control of NOx concentration by Mg in the catalyst composition of the present invention are achieved. As a result, the exhaust gas atmosphere becomes favorable for Pt in the catalyst composition of the present invention to exhibit catalytic activity, and thus the purification performance of Pt is further improved. Usually, a catalyst for purifying exhaust gas emitted from a diesel engine does not contain a material with oxygen storage capacity, such as the Ce—Zr-based complex oxide. This is because in a diesel engine, combustion in fuel-lean atmosphere with excessive intake air significantly increases the oxygen concentration in exhaust gas, and thus the amount of oxygen in exhaust gas greatly exceeds the amount that can be stored by the Ce—Zr-based complex oxide or the like.
The Ce—Zr-based complex oxide contains Ce, Zr and O. In the Ce—Zr-based complex oxide, Ce, Zr and O preferably form a solid solution phase. Ce, Zr and O may form a single phase (e.g., a CeO2 phase, a ZrO2 phase or the like) that is a crystal phase or an amorphous phase in addition to the solid solution phase. The fact that Ce, Zr and O form the solid solution can be confirmed using SEM-EDX or the like.
From the viewpoint of improving the oxygen storage capacity, the content of Ce in terms of CeO2 in the Ce—Zr-based complex oxide is preferably 5.0% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and still more preferably 20% by mass or more and 50% by mass or less, based on the mass of the Ce—Zr-based complex oxide. The content of Ce in terms of CeO2 in the Ce—Zr-based complex oxide can be determined in the same manner as the content of Al in terms of Al2O3 in the Al-based oxide.
From the viewpoint of improving the heat resistance, the content of Zr in terms of ZrO2 in the Ce—Zr-based complex oxide is preferably 10% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and still more preferably 40% by mass or more and 70% by mass or less, based on the mass of the Ce—Zr-based complex oxide. The content of Zr in terms of ZrO2 in the Ce—Zr-based complex oxide can be determined in the same manner as the content of Al in terms of Al2O3 in the Al-based oxide.
From the viewpoint of improving the oxygen storage capacity and the heat resistance, the total content of Ce in terms of CeO2 and Zr in terms of ZrO2 in the Ce—Zr-based complex oxide is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more, based on the mass of the Ce—Zr-based complex oxide. The upper limit is 100% by mass.
The Ce—Zr-based complex oxide may contain one or two or more metal elements other than Ce and Zr. Examples of the metal element other than Ce and Zr include a rare earth element other than Ce, and the like. Examples of the rare earth element other than Ce include Y, Pr, Sc, La, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the like. The metal element other than Ce and Zr may form a solid solution phase together with Ce, Zr and O, or may form a single phase that is a crystal phase or an amorphous phase, or may form both the solid solution phase and the single phase.
From the viewpoint of improving the oxygen storage capacity and the heat resistance, the content of the Ce—Zr-based complex oxide in the catalyst composition of the present invention is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and still more preferably 30% by mass or more and 50% by mass or less, based on the mass of the catalyst composition of the present invention. The content of the Ce—Zr-based complex oxide in the catalyst composition can be determined in the same manner as the content of the Al-based oxide in the catalyst composition of the present invention.
From the viewpoint of improving the noble metal dispersibility, the oxygen storage capacity and the heat resistance, the content of the inorganic oxide other than the Al-based oxide and the Ce—Zr-based complex oxide in the catalyst composition of the present invention is preferably 1.0% by mass or more and 50% by mass or less, more preferably 2.0% by mass or more and 30% by mass or less, and still more preferably 5.0% by mass or more and 20% by mass or less, based on the mass of the catalyst composition of the present invention. The expression “the content of the inorganic oxide other than the Al-based oxide and the Ce—Zr-based complex oxide in the catalyst composition of the present invention” means, in the case where the catalyst composition of the present invention contains one inorganic oxide other than the Al-based oxide and the Ce—Zr-based complex oxide, the content of the one inorganic oxide, and means, in the case where the catalyst composition of the present invention contains two or more inorganic oxides other than the Al-based oxide and the Ce—Zr-based complex oxide, the total content of the two or more inorganic oxides. The content of the inorganic oxide other than the Al-based oxide and the Ce—Zr-based complex oxide in the catalyst composition of the present invention can be determined in the same manner as the content of the Al-based oxide in the catalyst composition of the present invention.
From the viewpoint of effectively suppressing A/F fluctuation, the content of Ce in terms of CeO2 in the catalyst composition of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, and still more preferably 13% by mass or more, based on the mass of the catalyst composition of the present invention. From the viewpoint of suppressing oxidation of Pt, the content of Ce in terms of CeO2 in the catalyst composition of the present invention is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less, based on the mass of the catalyst composition of the present invention. Each of these upper limits may be combined with any of the above-described lower limits. The expression “the content of Ce in terms of CeO2 in the catalyst composition of the present invention” means, in the case where the catalyst composition of the present invention contains one Ce source, the content of Ce derived from the one Ce source in terms of CeO2, and means, in the case where the catalyst composition of the present invention contains two or more Ce sources, the total content of Ce derived from the two or more Ce sources in terms of CeO2. The Ce source is not particularly limited as long as the Ce source is an oxide containing Ce. Examples of the Ce source include a Ce—Zr-based complex oxide, ceria (CeO2), an oxide containing Ce and a rare earth element other than Ce, an Al-based oxide containing Ce, and the like. In the case where the composition of raw materials used for producing the catalyst composition of the present invention is known, the content of Ce in terms of CeO2 in the catalyst composition of the present invention can be determined from the composition of raw materials used for producing the catalyst composition of the present invention. In the case where the composition of raw materials used for producing the catalyst composition of the present invention is not known, the content of Ce in terms of CeO2 in the catalyst composition of the present invention can be determined using a conventional method such inductively coupled plasma atomic emission spectroscopy (ICP), X-ray fluorescence spectroscopy (XRF), SEM-EDX, or the like.
The catalyst composition of the present invention can be produced, for example, by mixing a Pt supply source, a Mg supply source and other component(s) (e.g., an inorganic oxide, a binder, a solvent, and the like), followed by drying and calcination. The calcined product may be pulverized as necessary. The pulverization can be carried out by a dry process or a wet process, using, for example, a mortar, a hammer mill, a ball mill, a bead mill, a jet mill, a roller mill, or the like. Examples of the Pt supply source include a Pt salt. Examples of the Pt salt include a nitrate, an ammine complex salt, a chloride, and the like. Examples of the Mg supply source include a Mg salt. Examples of the Mg salt include a nitrate, an acetate, a carbonate, a chloride, and the like. Examples of the binder include an alumina sol, a zirconia sol, a titania sol, a silica sol, a ceria sol, and the like. Examples of the solvent include water, an organic solvent, and the like. The drying temperature is, for example, 70° C. or more and 150° C. or less, and the drying time is, for example, 5 minutes or more and 1 hour or less. The calcination temperature is, for example, 200° C. or more and 700° C. or less, and the calcination time is, for example, 0.5 hours or more and 5 hours or less. The calcination can be carried out, for example, in an air atmosphere.
The exhaust gas purification catalyst of the present invention will now be described.
Hereinafter, an exhaust gas purification catalyst 1A (which may be referred to as a “catalyst 1A” in the present specification) according to a first embodiment of the present invention will be described with reference to
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In the exhaust gas path of the exhaust pipe P, another exhaust gas purification catalyst may be disposed on the upstream or downstream side of the catalyst 1A. Examples of the other exhaust gas purification catalyst include an exhaust gas purification catalyst 1B and an exhaust gas purification catalyst 1C, which are described below.
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The second catalyst layer 30 is a layer optionally provided. Thus, the present invention also encompasses an embodiment wherein the second catalyst layer 30 is omitted from the catalyst 1A. However, from the viewpoint of improving the exhaust gas purification performance, it is preferable that the second catalyst layer 30 is provided.
The material constituting the substrate 10 can be appropriately selected from known materials. Examples of the material constituting the substrate 10 include a ceramic material, a metal material, and the like. The ceramic material is preferable. Examples of the ceramic material include carbide ceramics such as silicon carbide, titanium carbide, tantalum carbide and tungsten carbide, nitride ceramics such as aluminum nitride, silicon nitride, boron nitride and titanium nitride, oxide ceramics such as alumina, zirconia, cordierite, mullite, zircon, aluminum titanate and magnesium titanate, and the like. Examples of the metal material include alloys such as stainless steel.
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The cell density per square inch of the substrate 10 is, for example, 100 cells or more and 1200 cells or less. The cell density per square inch of the substrate 10 means the total number of cells 13 per square inch in a cross-section obtained by cutting the substrate 10 by a plane perpendicular to the exhaust gas flow direction X.
The volume of the substrate 10 is, for example, 0.1 L or more and 20 L or less. The volume of the substrate 10 means the apparent volume of the substrate 10. In the case where the substrate 10 is in the form of a cylinder, the outer diameter of the substrate 10 is 2r, and the length of the substrate 10 is L10, the volume of the substrate 10 is represented by the formula: Volume of substrate 10=π×r2×L10.
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The first catalyst layer 20 is composed of the catalyst composition of the present invention. Thus, the above descriptions with respect to the catalyst composition of the present invention are also applied to the first catalyst layer 20. Upon application, “the catalyst composition of the present invention” is replaced with “the first catalyst layer 20”.
From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the first catalyst layer 20 per unit volume of the portion of the substrate 10 provided with the first catalyst layer 20 is preferably 50 g/L or more and 230 g/L or less, more preferably 100 g/L or more and 180 g/L or less, and still more preferably 130 g/L or more and 160 g/L or less.
The mass of the first catalyst layer 20 per unit volume of the portion of the substrate 10 provided with the first catalyst layer 20 is calculated from the formula: (Mass of first catalyst layer 20)/((Volume of substrate 10)×(Average length L20 of first catalyst layer 20/Length L10 of substrate 10)). In the present specification, the term “length” means the dimension in the axial direction of the substrate 10, unless otherwise defined.
The above descriptions with respect to “the mass of the catalyst composition” are also applied to “the mass of the first catalyst layer 20”. Upon application, “the catalyst composition” is replaced with “the first catalyst layer 20”. In the case where the information (e.g., composition and amounts) of raw materials used for producing the first catalyst layer 20 is known, the mass of the first catalyst layer 20 can be determined from the information of raw materials used for producing the first catalyst layer 20.
One example of the method of measuring the average length L20 of the first catalyst layer 20 is as follows:
A sample extending in the axial direction of the substrate 10 and having the same length as the length L10 of the substrate 10 is cut out from the catalyst 1A. The sample is, for example, in the form of a cylinder having a diameter of 25.4 mm. The value of the diameter of the sample can be changed as necessary. The sample is cut at 5 mm intervals in planes perpendicular to the axial direction of the substrate 10 to obtain cut pieces, which are referred to as the first cut piece, the second cut piece and so on up to the n-th cut piece, sequentially from the side of the end on the exhaust gas inflow side of the sample. The length of each cut piece is 5 mm. The composition of each cut piece is analyzed using an X-ray fluorescence analyzer (XRF) (e.g., an energy dispersive X-ray analyzer (EDX), a wavelength dispersive X-ray analyzer (WDX) or the like), an inductively coupled plasma emission spectrophotometer (ICP-AES), SEM-EDX or the like, and it is confirmed whether or not each cut piece includes part of the first catalyst layer 20, based on the composition of each cut piece.
The compositional analysis is not necessarily performed for a cut piece that apparently includes part of the first catalyst layer 20. For example, it is possible to confirm whether or not each cut piece includes part of the first catalyst layer 20, by observing the cross section thereof using a scanning electron microscope (SEM), an electron probe microanalyzer (EPMA) or the like. At the time of observing the cross section, element mapping of the cross section may be performed.
After confirming whether or not each cut piece includes part of the first catalyst layer 20, the length of the first catalyst layer 20 included in the sample is calculated based on the following formula:
Length of catalyst layer 20 included in sample=5 mm×(Number of cut pieces each including part of catalyst layer 20)
For example, in a case where each of the first cut piece to the k-th cut piece includes part of the first catalyst layer 20, whereas each of the (k+1)-th to the n-th cut pieces does not include part of the first catalyst layer 20, the length of the first catalyst layer 20 included in the sample is (5×k) mm.
One example of more specifically measuring the length of the first catalyst layer 20 included in the sample is as follows:
The k-th cut piece (namely, the cut piece closest to the exhaust gas outflow side, among the cut pieces each including part of the first catalyst layer 20) is cut in the axial direction of the substrate 10, and part of the first catalyst layer 20 existing in the resulting cross section is observed using SEM, EPMA or the like, to measure the length of part of the first catalyst layer 20 included in the k-th cut piece. Thereafter, the length of the first catalyst layer 20 included in the sample is calculated based on the following formula:
Length of catalyst layer 20 included in sample=(5 mm×(k−1))+(Length of part of catalyst layer 20 included in k-th cut piece)
The length of the first catalyst layer 20 included in the sample is calculated for 8 to 16 samples arbitrarily cut out from the catalyst 1A, and the average value of the measured lengths is defined as the average length L20 of the first catalyst layer 20.
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From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the second catalyst layer 30 per unit volume of the portion of the substrate 10 provided with the second catalyst layer 30 is preferably 20 g/L or more and 150 g/L or less, more preferably 50 g/L or more and 120 g/L or less, and still more preferably 70 g/L or more and 100 g/L or less.
The mass of the second catalyst layer 30 per unit volume of the portion of the substrate 10 provided with the second catalyst layer 30 is calculated from the formula: (Mass of second catalyst layer 30)/((Volume of substrate 10)×(Average length L30 of second catalyst layer 30/Length L10 of substrate 10)).
The above descriptions with respect to “the mass of the catalyst composition” are also applied to “the mass of the second catalyst layer 30”. Upon application, “the catalyst composition” is replaced with “the second catalyst layer 30”. In the case where the information (e.g., composition and amounts) of raw materials used for producing the second catalyst layer 30 is known, the mass of the second catalyst layer 30 can be determined from the information of raw materials used for producing the second catalyst layer 30.
The above descriptions with respect to the method for measuring the average length L20 of the first catalyst layer 20 are also applied to the method for measuring the average length L30 of the second catalyst layer 30. Upon application, “the first catalyst layer 20” and “the average length L20” are replaced with “the second catalyst layer 30” and “the average length L30”, respectively.
From the viewpoint of improving the NOx purification performance, it is preferable that the second catalyst layer 30 contains Rh. Rh contained in the second catalyst layer 30 is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing Rh, such as metal Rh, an alloy containing Rh, a compound containing Rh (e.g., an oxide of Rh), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing Rh is in the form of a particle.
From the viewpoint of balancing the exhaust gas purification performance and the cost, the content of Rh in terms of metal in the second catalyst layer 30 is preferably 0.010% by mass or more and 1.0% by mass or less, more preferably 0.050% by mass or more and 0.50% by mass or less, and still more preferably 0.10% by mass or more and 0.30% by mass or less, based on the mass of the second catalyst layer 30. The content of Rh in terms of metal in the second catalyst layer 30 can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The second catalyst layer 30 may contain a noble metal element other than Rh. Examples of the noble metal element other than Rh include Au, Ag, Pt, Pd, Ir, Ru, Os, and the like. The noble metal element other than Rh contained in the second catalyst layer 30 is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing the noble metal element other than Rh, such as metal, an alloy containing the noble metal element, a compound containing the noble metal element (e.g., an oxide of the noble metal element), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing the noble metal element other than Rh is in the form of a particle.
In the case where the second catalyst layer 30 contains Rh and the noble metal element other than Rh, Rh and the noble metal element other than Rh may form an alloy, thereby decreasing the active sites of Rh participating in exhaust gas purification. Accordingly, it is preferable that the second catalyst layer 30 is substantially free from the noble metal element other than Rh.
In the present specification, the expression that “a catalyst layer is substantially free from a noble metal element other than Rh” means that the content of the noble metal element other than Rh in terms of metal in the catalyst layer is preferably 0.050% by mass or less, and more preferably 0.010% by mass or less, based on the mass of the catalyst layer. The lower limit is zero. In the present specification, the expression “the content of a noble metal element other than Rh in terms of metal in a catalyst layer” means, in the case where the catalyst layer contains one noble metal element other than Rh, the content of the one noble metal element other than Rh in terms of metal, and means, in the case where the catalyst layer contains two or more noble metal elements other than Rh, the total content of the two or more noble metal elements other than Rh in terms of metal. The content of a noble metal element other than Rh in terms of metal in a catalyst layer can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The second catalyst layer 30 may contain one or two or more alkaline-earth metal elements. The alkaline-earth metal element is selected from Be, Mg, Ca, Sr, Ba and Ra.
From the viewpoint of suppressing oxidation of Rh, the content of the alkaline-earth metal element in terms of metal in the second catalyst layer 30 is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and still more preferably 1.0% by mass or less, based on the mass of the second catalyst layer 30. The lower limit is zero.
In the present specification, the expression “the content of an alkaline-earth metal element in terms of metal in a catalyst layer” means, in the case where the catalyst layer contains one alkaline-earth metal element, the content of the one alkaline-earth metal element in terms of metal, and means, in the case where the catalyst layer contains two or more alkaline-earth metal elements, the total content of the two or more alkaline-earth metal elements in terms of metal. The content of an alkaline-earth metal element in terms of metal in a catalyst layer can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
In the second catalyst layer 30, the form in which the alkaline-earth metal element is present is not particularly limited. In the second catalyst layer 30, the alkaline-earth metal element can be present in one or two or more forms selected from, for example, an oxide, a carbonate, a nitrate and a sulfate.
The second catalyst layer 30 may contain one or two or more carriers. In the case where the second catalyst layer 30 contains a carrier, it is preferable that at least part of a catalytically active component is supported on the carrier. The descriptions with respect to the carrier (including the descriptions with respect to an inorganic oxide), and the meaning of “supported” and the confirmation method of “supported” are the same as described above.
In the catalyst 1A, the second catalyst layer 30 is provided on the upside of the first catalyst layer 20. Thus, exhaust gas that has flowed in from the end (opening) on the exhaust gas inflow side of the cell 13 contacts with the second catalyst layer 30, and then contacts with the first catalyst layer 20. The exhaust gas is purified by Rh in the second catalyst layer 30. NOx that is not purified and passes through the second catalyst layer 30 is adsorbed onto Mg in the first catalyst layer 20. In this manner, the first catalyst layer 20 compensates for the exhaust gas purification performance of the catalyst 1A by adsorbing NOx in the exhaust gas. Thereafter, NOx adsorbed on Mg in the first catalyst layer 20 is released, and the released NOx is purified by, for example, Rh in the second catalyst layer 30. In this manner, the catalyst 1A can exert an improved exhaust gas purification performance.
The catalyst 1A can be produced by forming the first catalyst layer 20 on the substrate 10 and then forming the second catalyst layer 30 on the upside of the first catalyst layer 20.
The first catalyst layer 20 can be formed by mixing a Pt supply source (e.g., a Pt salt), a Mg supply source (e.g., a Mg salt) and other component(s) (e.g., an inorganic oxide, a binder, a solvent, and the like) to prepare a first slurry, coating the substrate 10 with the first slurry, drying the resulting material, and calcining the resulting material.
The second catalyst layer 30 can be formed by mixing a Rh supply source (e.g., a Rh salt) and other component(s) (e.g., an inorganic oxide, a binder, a solvent, and the like) to prepare a second slurry, coating the first catalyst layer 20 with the second slurry, drying the resulting material, and calcining the resulting material.
The descriptions with respect to the Pt salt, the Mg salt, the inorganic oxide, the binder and the solvent are the same as described above. Examples of the Rh salt include a nitrate, an ammine complex salt, an acetate, a chloride, and the like. The drying temperature is, for example, 70° C. or more and 150° C. or less, and the drying time is, for example, 5 minutes or more and 1 hour or less. The calcination temperature is, for example, 200° C. or more and 700° C. or less, and the calcination time is, for example, 0.5 hours or more and 5 hours or less. The calcination can be carried out, for example, in an air atmosphere.
Hereinafter, an exhaust gas purification catalyst 1B (which may be referred to as a “catalyst 1B” in the present specification) according to a second embodiment of the present invention will be described with reference to
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Each of the second catalyst layer 30, the third catalyst layer 40 and the fourth catalyst layer 50 is a layer optionally provided. Thus, the present invention also encompasses embodiments wherein one or two or more of the second catalyst layer 30, the third catalyst layer 40 and the fourth catalyst layer 50 are omitted from the catalyst 1B (e.g., an embodiment wherein the second catalyst layer 30 is omitted, an embodiment wherein the third catalyst layer 40 is omitted, an embodiment wherein the fourth catalyst layer 50 is omitted, an embodiment wherein the second catalyst layer 30 and the third catalyst layer 40 are omitted, an embodiment wherein the second catalyst layer 30 and the fourth catalyst layer 50 are omitted, and the like). However, from the viewpoint of improving the exhaust gas purification performance in the embodiments wherein one or two or more of the second catalyst layer 30, the third catalyst layer 40 and the fourth catalyst layer 50 are omitted from the catalyst 1B, at least one of the second catalyst layer 30 and the third catalyst layer 40 is preferably provided, and both of the second catalyst layer 30 and the third catalyst layer 40 are more preferably provided.
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From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the first catalyst layer 20 per unit volume of the portion of the substrate 10 provided with the first catalyst layer 20 is preferably 5 g/L or more and 60 g/L or less, more preferably 10 g/L or more and 40 g/L or less, and still more preferably 10 g/L or more and 30 g/L or less.
The mass of the first catalyst layer 20 per unit volume of the portion of the substrate 10 provided with the first catalyst layer 20 can be determined in the same manner as in the first embodiment.
The method of measuring the average length L20 of the first catalyst layer 20 in the second embodiment is the same as in the first embodiment, except that in the method of measuring the average length L20 of the first catalyst layer 20 in the second embodiment, a sample is cut at 5 mm intervals in planes perpendicular to the axial direction of the substrate 10 to obtain cut pieces, which are referred to as the first cut piece, the second cut piece and so on up to the n-th cut piece, sequentially from the side of the end on the exhaust gas outflow side of the sample.
The average length L20 of the first catalyst layer 20 can be appropriately adjusted in consideration of, for example, the exhaust gas purification performance and the PM collection performance. From the viewpoint of improving the exhaust gas purification performance and the PM collection performance, the percentage of the average length L20 of the first catalyst layer 20 to the length L10 of the substrate 10 (L20/L10×100) is preferably 15% or more and 90% or less, more preferably 20% or more and 80% or less, and still more preferably 30% or more and 80% or less.
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From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the second catalyst layer 30 per unit volume of the portion of the substrate 10 provided with the second catalyst layer 30 is preferably 5 g/L or more and 60 g/L or less, more preferably 10 g/L or more and 40 g/L or less, and still more preferably 10 g/L or more and 30 g/L or less.
The mass of the second catalyst layer 30 per unit volume of the portion of the substrate 10 provided with the second catalyst layer 30 can be determined in the same manner as in the first embodiment.
The method of measuring the average length L30 of the second catalyst layer 30 in the second embodiment is the same as in the first embodiment, except that in the method of measuring the average length L30 of the second catalyst layer 30 in the second embodiment, a sample is cut at 5 mm intervals in planes perpendicular to the axial direction of the substrate 10 to obtain cut pieces, which are referred to as the first cut piece, the second cut piece and so on up to the n-th cut piece, sequentially from the side of the end on the exhaust gas outflow side of the sample.
The average length L30 of the second catalyst layer 30 can be appropriately adjusted in consideration of, for example, the exhaust gas purification performance and the PM collection performance. From the viewpoint of improving the exhaust gas purification performance and the PM collection performance, the percentage of the average length L30 of the second catalyst layer 30 to the length L10 of the substrate 10 (L30/L10×100) is preferably 15% or more and 90% or less, more preferably 20% or more and 80% or less, and still more preferably 30% or more and 80% or less.
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From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the third catalyst layer 40 per unit volume of the portion of the substrate 10 provided with the third catalyst layer 40 is preferably 5 g/L or more and 100 g/L or less, more preferably 10 g/L or more and 70 g/L or less, and still more preferably 15 g/L or more and 50 g/L or less.
The mass of the third catalyst layer 40 per unit volume of the portion of the substrate 10 provided with the third catalyst layer 40 is calculated from the formula: (Mass of third catalyst layer 40)/((Volume of substrate 10)×(Average length L40 of third catalyst layer 40/Length L10 of substrate 10)).
The above descriptions with respect to “the mass of the catalyst composition” are also applied to “the mass of the third catalyst layer 40”. Upon application, “the catalyst composition” is replaced with “the third catalyst layer 40”. In the case where the information (e.g., composition and amounts) of raw materials used for producing the third catalyst layer 40 is known, the mass of the third catalyst layer 40 can be determined from the information of raw materials used for producing the third catalyst layer 40.
The above descriptions with respect to the method for measuring the average length L20 of the first catalyst layer 20 in the first embodiment are also applied to the method for measuring the average length L40 of the third catalyst layer 40. Upon application, “the first catalyst layer 20” and “the average length L20” are replaced with “the third catalyst layer 40” and “the average length L40”, respectively.
The average length L40 of the third catalyst layer 40 can be appropriately adjusted in consideration of, for example, the exhaust gas purification performance and the PM collection performance. From the viewpoint of improving the exhaust gas purification performance and the PM collection performance, the percentage of the average length L40 of the third catalyst layer 40 to the length L10 of the substrate 10 (L40/L10×100) is preferably 15% or more and 90% or less, more preferably 20% or more and 80% or less, and still more preferably 30% or more and 80% or less.
From the viewpoint of improving the exhaust gas purification performance and the PM collection performance, the percentage of the total of the average length L20 of the first catalyst layer 20 or the average length L30 of the second catalyst layer 30 and the average length L40 of the third catalyst layer 40 to the length L10 of the substrate 10 (((L20 or L30)+L40)/L10×100) is preferably 100% or more and 180% or less, more preferably 105% or more and 150% or less, and still more preferably 110% or more and 130% or less.
From the viewpoint of improving the NOx purification performance, it is preferable that the third catalyst layer 40 contains Rh. Rh contained in the third catalyst layer 40 is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing Rh, such as metal Rh, an alloy containing Rh, a compound containing Rh (e.g., an oxide of Rh), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing Rh is in the form of a particle.
From the viewpoint of balancing the exhaust gas purification performance and the cost, the content of Rh in terms of metal in the third catalyst layer 40 is preferably 0.050% by mass or more and 2.0% by mass or less, more preferably 0.10% by mass or more and 1.5% by mass or less, and still more preferably 0.20% by mass or more and 1.0% by mass or less, based on the mass of the third catalyst layer 40. The content of Rh in terms of metal in the third catalyst layer 40 can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The third catalyst layer 40 may contain a noble metal element other than Rh. Examples of the noble metal element other than Rh include Au, Ag, Pt, Pd, Ir, Ru, Os, and the like. The noble metal element other than Rh contained in the third catalyst layer 40 is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing the noble metal element other than Rh, such as metal, an alloy containing the noble metal element, a compound containing the noble metal element (e.g., an oxide of the noble metal element), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing the noble metal element other than Rh is in the form of a particle.
In the case where the third catalyst layer 40 contains Rh and the noble metal element other than Rh, Rh and the noble metal element other than Rh may form an alloy, thereby decreasing the active sites of Rh participating in exhaust gas purification. Accordingly, it is preferable that the third catalyst layer 40 is substantially free from the noble metal element other than Rh. The meanings of the expression “substantially free from the noble metal element other than Rh” and the expression “the content of the noble metal element other than Rh in terms of metal”, and the method for determining the content of the noble metal element other than Rh are the same as described above.
The third catalyst layer 40 may contain one or two or more alkaline-earth metal elements. The alkaline-earth metal element is selected from Be, Mg, Ca, Sr, Ba and Ra.
From the viewpoint of suppressing oxidation of Rh, the content of the alkaline-earth metal element in terms of metal in the third catalyst layer 40 is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and still more preferably 1.0% by mass or less, based on the mass of the third catalyst layer 40. The lower limit is zero. The meaning of the expression “the content of the alkaline-earth metal element in terms of metal”, and the method for determining the content of the alkaline-earth metal element are the same as described above.
In the third catalyst layer 40, the form in which the alkaline-earth metal element is present is not particularly limited. In the third catalyst layer 40, the alkaline-earth metal element can be present in one or two or more forms selected from, for example, an oxide, a carbonate, a nitrate and a sulfate.
The third catalyst layer 40 may contain one or two or more carriers. In the case where the third catalyst layer 40 contains a carrier, it is preferable that at least part of a catalytically active component is supported on the carrier. The descriptions with respect to the carrier (including the descriptions with respect to an inorganic oxide), the meaning of “supported” and the confirmation method of “supported” are the same as described above.
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From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the fourth catalyst layer 50 per unit volume of the portion of the substrate 10 provided with the fourth catalyst layer 50 is preferably 5 g/L or more and 100 g/L or less, more preferably 10 g/L or more and 70 g/L or less, and still more preferably 15 g/L or more and 50 g/L or less.
The mass of the fourth catalyst layer 50 per unit volume of the portion of the substrate 10 provided with the fourth catalyst layer 50 is calculated from the formula: (Mass of fourth catalyst layer 50)/((Volume of substrate 10)×(Average length L50 of fourth catalyst layer 50/Length L10 of substrate 10)).
The above descriptions with respect to “the mass of the catalyst composition” are also applied to “the mass of the fourth catalyst layer 50”. Upon application, “the catalyst composition” is replaced with “the fourth catalyst layer 50”. In the case where the information (e.g., composition and amounts) of raw materials used for producing the fourth catalyst layer 50 is known, the mass of the fourth catalyst layer 50 can be determined from the information of raw materials used for producing the fourth catalyst layer 50.
The above descriptions with respect to the method for measuring the average length L20 of the first catalyst layer 20 in the first embodiment are also applied to the method for measuring the average length L50 of the fourth catalyst layer 50. Upon application, “the first catalyst layer 20” and “the average length L20” are replaced with “the fourth catalyst layer 50” and “the average length L50”, respectively.
The average length L50 of the fourth catalyst layer 50 can be appropriately adjusted in consideration of, for example, the exhaust gas purification performance and the PM collection performance. From the viewpoint of improving the exhaust gas purification performance and the PM collection performance, the percentage of the average length L50 of the fourth catalyst layer 50 to the length L10 of the substrate 10 (L50/L10×100) is preferably 15% or more and 90% or less, more preferably 20% or more and 80% or less, and still more preferably 30% or more and 80% or less.
From the viewpoint of improving the exhaust gas purification performance and the PM collection performance, the percentage of the total of the average length L20 of the first catalyst layer 20 or the average length L30 of the second catalyst layer 30 and the average length L50 of the fourth catalyst layer 50 to the length L10 of the substrate 10 (((L20 or L30)+L50)/L10×100) is preferably 100% or more and 180% or less, more preferably 105% or more and 150% or less, and still more preferably 110% or more and 130% or less.
From the viewpoint of improving the exhaust gas purification performance, it is preferable that the fourth catalyst layer 50 contains Pd. Pd contained in the fourth catalyst layer 50 is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing Pd, such as metal Pd, an alloy containing Pd, a compound containing Pd (e.g., an oxide of Pd), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing Pd is in the form of a particle.
From the viewpoint of balancing the exhaust gas purification performance and the cost, the content of Pd in terms of metal in the fourth catalyst layer 50 is preferably 0.50% by mass or more and 10% by mass or less, more preferably 1.0% by mass or more and 7.0% by mass or less, and still more preferably 2.0% by mass or more and 5.0% by mass or less, based on the mass of the fourth catalyst layer 50. The content of Pd in terms of metal in the fourth catalyst layer 50 can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The fourth catalyst layer 50 may contain a noble metal element other than Pd. Examples of the noble metal element other than Pd include Au, Ag, Rh, Pt, Ir, Ru, Os, and the like. The noble metal element other than Pd contained in the fourth catalyst layer 50 is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing the noble metal element other than Pd, such as metal, an alloy containing the noble metal element, a compound containing the noble metal element (e.g., an oxide of the noble metal element), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing the noble metal element other than Pd is in the form of a particle.
In the case where the fourth catalyst layer 50 contains Pd and the noble metal element other than Pd, Pd and the noble metal element other than Pd may form an alloy, thereby decreasing the active sites of Pd participating in exhaust gas purification. Accordingly, it is preferable that the fourth catalyst layer 50 is substantially free from the noble metal element other than Pd.
In the present specification, the expression that “a catalyst layer is substantially free from a noble metal element other than Pd” means that the content of the noble metal element other than Pd in terms of metal in the catalyst layer is preferably 0.050% by mass or less, and more preferably 0.010% by mass or less, based on the mass of the catalyst layer. The lower limit is zero. In the present specification, the expression “the content of a noble metal element other than Pd in terms of metal in a catalyst layer” means, in the case where the catalyst layer contains one noble metal element other than Pd, the content of the one noble metal element other than Pd in terms of metal, and means, in the case where the catalyst layer contains two or more noble metal elements other than Pd, the total content of the two or more noble metal elements other than Pd in terms of metal. The content of a noble metal element other than Pd in terms of metal in a catalyst layer can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The fourth catalyst layer 50 may contain one or two or more alkaline-earth metal elements. The alkaline-earth metal element is selected from Be, Mg, Ca, Sr, Ba and Ra.
From the viewpoint of maintaining oxidized state of Pd, the content of the alkaline-earth metal element in terms of metal in the fourth catalyst layer 50 is preferably 1.0% by mass or more and 10.0% by mass or less, more preferably 2.0% by mass or more and 6.0% by mass or less, and still more preferably 3.0% by mass or more and 4.0% by mass or less, based on the mass of the fourth catalyst layer 50. The meaning of the expression “the content of the alkaline-earth metal element in terms of metal”, and the method for determining the content of the alkaline-earth metal element are the same as described above.
In the fourth catalyst layer 50, the form in which the alkaline-earth metal element is present is not particularly limited. In the fourth catalyst layer 50, the alkaline-earth metal element can be present in one or two or more forms selected from, for example, an oxide, a carbonate, a nitrate and a sulfate.
The fourth catalyst layer 50 may contain one or two or more carriers. In the case where the fourth catalyst layer 50 contains a carrier, it is preferable that at least part of a catalytically active component is supported on the carrier. The descriptions with respect to the carrier (including the descriptions with respect to an inorganic oxide), the meaning of “supported” and the confirmation method of “supported” are the same as described above.
In the exhaust gas purification catalyst 1B, exhaust gas that has flowed in through the exhaust gas in-flow side end (opening) of the in-flow cell 13a passes through the porous partition wall 12, and flows out through the exhaust gas out-flow side end (opening) of the out-flow cell 13b. Such a manner is called a wall-flow type.
In the catalyst 1B, when exhaust gas that has flowed in through the exhaust gas in-flow side end (opening) of the in-flow cell 13a passes through the porous partition wall 12, particulate matter (PM) in the exhaust gas is collected in pores of the partition wall 12. Accordingly, the catalyst 1B is useful as a gasoline particulate filter for a gasoline engine or a diesel particulate filter for a diesel engine.
In the catalyst 1B, the third catalyst layer 40 and the fourth catalyst layer 50 are provided on the upstream of the first catalyst layer 20 and the second catalyst layer 30. Thus, exhaust gas that has flowed in from the end (opening) on the exhaust gas inflow side of the in-flow cell 13a contacts with the third catalyst layer 40 and the fourth catalyst layer 50, then passes through the porous partition wall 12, and then contacts with the first catalyst layer 20 and the second catalyst layer 30. NOx in the exhaust gas is purified by Rh in the third catalyst layer 40 and Pd in the fourth catalyst layer 50. NOx that is not purified and passes through the third catalyst layer 40 and the fourth catalyst layer 50 is adsorbed onto Mg in the first catalyst layer 20. In this manner, the first catalyst layer 20 compensates for the exhaust gas purification performance of the catalyst 1B by adsorbing NOx in the exhaust gas. Thereafter, NOx adsorbed on Mg in the first catalyst layer 20 is released, and the released NOx is purified by, for example, Rh in the second catalyst layer 30. In this manner, the catalyst 1B can exert an improved exhaust gas purification performance.
The catalyst 1B can be produced by the following method. The production conditions and the like of the catalyst 1B are the same as those of the catalyst 1A.
The first catalyst layer 20 can be formed by coating a portion on the exhaust gas outflow side of the substrate 10 with a slurry for forming the first catalyst layer 20, drying the slurry, and calcining the slurry as necessary. After the formation of the first catalyst layer 20, the second catalyst layer 30 can be formed by coating a portion on the exhaust gas outflow side of the substrate 10 with a slurry for forming the second catalyst layer 30, drying the slurry, and calcining the slurry as necessary.
The fourth catalyst layer 50 can be formed by coating a portion on the exhaust gas inflow side of the substrate 10 with a slurry for forming the fourth catalyst layer 50, drying the slurry, and calcining the slurry as necessary. After the formation of the fourth catalyst layer 50, the third catalyst layer 40 can be formed by coating a portion on the exhaust gas inflow side of the substrate 10 with a slurry for forming the third catalyst layer 40, drying the slurry, and calcining the slurry as necessary.
The third catalyst layer 40 can be prepared by mixing a Rh supply source (e.g., a Rh salt) and other component(s) (e.g., an inorganic oxide, a binder, a solvent, and the like). The descriptions with respect to the Rh salt, the inorganic oxide, the binder and the solvent are the same as described above.
The fourth catalyst layer 50 can be prepared by mixing a Pd supply source (e.g., a Pd salt) and other component(s) (e.g., an inorganic oxide, a binder, a solvent, and the like). Examples of the Pd salt include a nitrate, an ammine complex salt, an acetate, a chloride, and the like. The descriptions with respect to the inorganic oxide, the binder and the solvent are the same as described above.
Hereinafter, an exhaust gas purification catalyst 1C (which may be referred to as a “catalyst 1C” in the present specification) according to a third embodiment of the present invention will be described with reference to
As shown in
The second catalyst layer 30 is a layer optionally provided. The present invention also encompasses an embodiment wherein the second catalyst layer 30 is omitted from the catalyst 1C. However, from the viewpoint of improving the exhaust gas purification performance, it is preferable that the second catalyst layer 30 is provided.
As shown in
In the present embodiment, as shown in
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The end on the exhaust gas inflow side of the first catalyst layer 20 may have a portion that overlaps with the end on the exhaust gas outflow side of the fifth catalyst layer 60 (i.e., a portion that is located on the upside of the end on the exhaust gas outflow side of the fifth catalyst layer 60 and covers the end on the exhaust gas outflow side of the fifth catalyst layer 60). Alternatively, the end on the exhaust gas outflow side of the fifth catalyst layer 60 may have a portion that overlaps with the end on the exhaust gas inflow side of the first catalyst layer 20 (i.e., a portion that is located on the upside of the end on the exhaust gas inflow side of the first catalyst layer 20 and covers the end on the exhaust gas inflow side of the first catalyst layer 20). These cases are also included in the expression that “the fifth catalyst layer 60 is provided on the upstream side of the first catalyst layer 20”.
From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the first catalyst layer 20 per unit volume of the portion of the substrate 10 provided with the first catalyst layer 20 is preferably 50 g/L or more and 230 g/L or less, more preferably 100 g/L or more and 180 g/L or less, and still more preferably 130 g/L or more and 160 g/L or less.
The mass of the first catalyst layer 20 per unit volume of the portion of the substrate 10 provided with the first catalyst layer 20 can be determined in the same manner as in the first embodiment.
The method of measuring the average length L20 of the first catalyst layer 20 in the third embodiment is the same as in the first embodiment, except that in the method of measuring the average length L20 of the first catalyst layer 20 in the third embodiment, a sample is cut at 5 mm intervals in planes perpendicular to the axial direction of the substrate 10 to obtain cut pieces, which are referred to as the first cut piece, the second cut piece and so on up to the n-th cut piece, sequentially from the side of the end on the exhaust gas outflow side of the sample.
From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the fifth catalyst layer 60 per unit volume of the portion of the substrate 10 provided with the fifth catalyst layer 60 is preferably 20 g/L or more and 150 g/L or less, more preferably 50 g/L or more and 120 g/L or less, and still more preferably 70 g/L or more and 100 g/L or less.
The mass of the fifth catalyst layer 60 per unit volume of the portion of the substrate 10 provided with the fifth catalyst layer 60 is calculated from the formula: (Mass of fifth catalyst layer 60)/((Volume of substrate 10)×(Average length L60 of fifth catalyst layer 60/Length L10 of substrate 10)).
The above descriptions with respect to “the mass of the catalyst composition” are also applied to “the mass of the fifth catalyst layer 60”. Upon application, “the catalyst composition” is replaced with “the fifth catalyst layer 60”. In the case where the information (e.g., composition and amounts) of raw materials used for producing the fifth catalyst layer 60 is known, the mass of the fifth catalyst layer 60 can be determined from the information of raw materials used for producing the fifth catalyst layer 60.
The above descriptions with respect to the method for measuring the average length L20 of the first catalyst layer 20 in the first embodiment are also applied to the method for measuring the average length L60 of the fifth catalyst layer 60. Upon application, “the first catalyst layer 20” and “the average length L20” are replaced with “the fifth catalyst layer 60” and “the average length L60”, respectively.
From the viewpoint of improving the exhaust gas purification performance, it is preferable that the fifth catalyst layer 60 contains Pd. Pd contained in the fifth catalyst layer 60 is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing Pd, such as metal Pd, an alloy containing Pd, a compound containing Pd (e.g., an oxide of Pd), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing Pd is in the form of a particle.
From the viewpoint of balancing the exhaust gas purification performance and the cost, the content of Pd in terms of metal in the fifth catalyst layer 60 is preferably 0.50% by mass or more and 10% by mass or less, more preferably 1.0% by mass or more and 7.0% by mass or less, and still more preferably 2.0% by mass or more and 5.0% by mass or less, based on the mass of the fifth catalyst layer 60. The content of Pd in terms of metal in the fifth catalyst layer 60 can be determined in the same manner as the content of Pt in terms of metal in the catalyst composition of the present invention.
The fifth catalyst layer 60 may contain a noble metal element other than Pd. Examples of the noble metal element other than Pd include Au, Ag, Rh, Pt, Ir, Ru, Os, and the like. The noble metal element other than Pd contained in the fifth catalyst layer 60 is in the form capable of functioning as a catalytically active component, for example, in the form of a catalytically active component containing the noble metal element other than Pd, such as metal, an alloy containing the noble metal element, a compound containing the noble metal element (e.g., an oxide of the noble metal element), or the like. From the viewpoint of improving the exhaust gas purification performance, it is preferable that the catalytically active component containing the noble metal element other than Pd is in the form of a particle.
In the case where the fifth catalyst layer 60 contains Pd and the noble metal element other than Pd, Pd and the noble metal element other than Pd may form an alloy, thereby decreasing the active sites of Pd participating in exhaust gas purification. Accordingly, it is preferable that the fifth catalyst layer 60 is substantially free from the noble metal element other than Pd. The meanings of the expressions “substantially free from the noble metal element other than Pd” and “the content of the noble metal element other than Pd in terms of metal”, and the method for determining the content of the noble metal element other than Pd are the same as described above.
The fifth catalyst layer 60 may contain one or two or more alkaline-earth metal elements. The alkaline-earth metal element is selected from Be, Mg, Ca, Sr, Ba and Ra.
From the viewpoint of maintaining oxidized state of Pd, the content of the alkaline-earth metal element in terms of metal in the fifth catalyst layer 60 is preferably 1.0% by mass or more and 10.0% by mass or less, more preferably 2.0% by mass or more and 6.0% by mass or less, and still more preferably 3.0% by mass or more and 4.0% by mass or less, based on the mass of the fifth catalyst layer 60. The meaning of the expression “the content of the alkaline-earth metal element in terms of metal”, and the method for determining the content of the alkaline-earth metal element are the same as described above.
In the fifth catalyst layer 60, the form in which the alkaline-earth metal element is present is not particularly limited. In the fifth catalyst layer 60, the alkaline-earth metal element can be present in one or two or more forms selected from, for example, an oxide, a carbonate, a nitrate and a sulfate.
The fifth catalyst layer 60 may contain one or two or more carriers. In the case where the fifth catalyst layer 60 contains a carrier, it is preferable that at least part of a catalytically active component is supported on the carrier. The descriptions with respect to the carrier (including the descriptions with respect to an inorganic oxide), the meaning of “supported” and the confirmation method of “supported” are the same as described above.
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From the viewpoint of balancing the exhaust gas purification performance and the cost, the mass (mass after calcination) of the second catalyst layer 30 per unit volume of the portion of the substrate 10 provided with the second catalyst layer 30 is preferably 20 g/L or more and 150 g/L or less, more preferably 50 g/L or more and 120 g/L or less, and still more preferably 70 g/L or more and 100 g/L or less.
The mass of the second catalyst layer 30 per unit volume of the portion of the substrate 10 provided with the second catalyst layer 30 can be determined in the same manner as in the first embodiment.
In the catalyst 1C, the second catalyst layer 30 is provided on the upside of the first catalyst layer 20 and the fifth catalyst layer 60. Thus, exhaust gas that has flowed in from the end (opening) on the exhaust gas inflow side of the cell 13 contacts with the second catalyst layer 30, and then contacts with the first catalyst layer 20 and the fifth catalyst layer 60. The exhaust gas is purified by Rh in the second catalyst layer 30 and Pd in the fifth catalyst layer 60. NOx that is not purified and passed through the second catalyst layer 30 and/or the fifth catalyst layer 60 is adsorbed onto Mg in the first catalyst layer 20. In this manner, the first catalyst layer 20 compensates for the exhaust gas purification performance of the catalyst 1C by adsorbing NOx in the exhaust gas. Thereafter, NOx adsorbed on Mg in the first catalyst layer 20 is released, and the released NOx is purified by, for example, Rh in the second catalyst layer 30 and Pd in the fifth catalyst layer 60. In this manner, the catalyst 1C can exert an improved exhaust gas purification performance.
The catalyst 1C can be produced by the following method. The production conditions and the like of the catalyst 1C are the same as those of the catalyst 1A.
The first catalyst layer 20 can be formed by coating a portion on the exhaust gas outflow side of the substrate 10 with a slurry for forming the first catalyst layer 20, drying the slurry, and calcining the slurry as necessary. The fifth catalyst layer 60 can be formed by coating a portion on the exhaust gas inflow side of the substrate 10 with a slurry for forming the fifth catalyst layer 60, drying the slurry, and calcining the slurry as necessary.
The catalyst 1C can be produced by forming the first catalyst layer 20 and the fifth catalyst layer 60 on the substrate 10 and then forming the second catalyst layer 30 on the upside of the first catalyst layer 20 and the fifth catalyst layer 60.
The fifth catalyst layer 60 can be prepared by mixing a Pd supply source (e.g., a Pd salt) and other component(s) (e.g., an inorganic oxide, a binder, a solvent, and the like). The descriptions with respect to the Pd salt, the inorganic oxide, the binder and the solvent are the same as described above.
The exhaust gas purification system of the present invention will now be described.
Hereinafter, an exhaust gas purification system 100 according to one embodiment of the present invention will be described with reference to
As shown in
One end P1 of the exhaust pipe P is connected to an internal combustion engine (e.g., a gasoline engine), and exhaust gas emitted from the internal combustion engine flows through the exhaust pipe P from the one end P1 to the other end P2. That is, the exhaust pipe P forms an exhaust gas path through which exhaust gas flows. In the drawings, the exhaust gas flow direction is denoted by the reference sign X. The exhaust gas flowing through the exhaust pipe P is treated by the second catalyst 102 provided on the upstream side of the exhaust gas path in the exhaust pipe P, and the exhaust gas that passed through the second catalyst 102 is treated by the first catalyst 101 provided on the downstream side of the exhaust gas path in the exhaust pipe P.
The first catalyst 101 includes a first substrate and a catalyst layer provided on the first substrate. The catalyst layer provided on the first substrate is composed of the catalyst composition of the present invention. Thus, the above descriptions with respect to the catalyst composition of the present invention are also applied to the catalyst layer provided on the first substrate. Upon application, “the catalyst composition of the present invention” is replaced with “the catalyst layer provided on the first substrate”.
Examples of an exhaust gas purification catalyst that can be used as the first catalyst 101 include the catalyst 1A, an exhaust gas purification catalyst differing from the catalyst 1A in that the second catalyst layer 30 is omitted, the catalyst 1B, an exhaust gas purification catalyst differing from the catalyst 1B in that one or two or more of the second catalyst layer 30, the third catalyst layer 40 and the fourth catalyst layer 50 are omitted (e.g., an exhaust gas purification catalyst differing from the catalyst 1B in that the second catalyst layer 30 is omitted, in that the third catalyst layer 40 is omitted, in that the fourth catalyst layer 50 is omitted, in that the second catalyst layer 30 and the third catalyst layer 40 are omitted, or in that the second catalyst layer 30 and the fourth catalyst layer 50 are omitted), the catalyst 1C, an exhaust gas purification catalyst differing from the catalyst 1C in that the second catalyst layer 30 is omitted, and the like. In the case where these exhaust gas purification catalysts are used as the first catalyst 101, the substrate 10 corresponds to “the first substrate”, and the first catalyst layer 20 corresponds to “the catalyst layer provided on the first substrate”. From the viewpoint of improving the exhaust gas purification performance of an exhaust gas purification catalyst differing from the catalyst 1B in that one or two or more of the second catalyst layer 30, the third catalyst layer 40 and the fourth catalyst layer 50 are omitted, at least one of the second catalyst layer 30 and the third catalyst layer 40 is preferably provided, and both of the second catalyst layer 30 and the third catalyst layer 40 are more preferably provided.
The second catalyst 102 includes a second substrate and a catalyst layer provided on the second substrate.
Examples of an exhaust gas purification catalyst that can be used as the second catalyst 102 include an exhaust gas purification catalyst 1D (which may be referred to as a “catalyst 1D” in the present specification) shown in
Hereinafter, the catalyst 1D will be described with reference to
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In the exhaust gas purification system 100, the second catalyst 102 is provided on the upstream side of the first catalyst 101. Thus, exhaust gas flowing through the exhaust pipe P passes through the second catalyst 102, and then passes through the first catalyst 101. When the exhaust gas passes through the second catalyst 102, the exhaust gas is purified by the catalyst layer provided on the second substrate. When passing through the first catalyst 101, NOx that is not purified and passes through the second catalyst 102 is adsorbed onto Mg in the catalyst layer provided on the first substrate. In this manner, the catalyst layer provided on the first substrate compensates for the exhaust gas purification performance of the exhaust gas purification system 100 by adsorbing NOx in the exhaust gas. Thereafter, NOx adsorbed on Mg in the catalyst layer provided on the first substrate is released, and the released NOx is purified by, for example, Rh in the second catalyst layer 30. In this manner, the exhaust gas purification system 100 can exert an improved exhaust gas purification performance.
The present invention will be more specifically described with reference to Examples and Comparative Examples.
An OSC material having the following composition was prepared.
Content of Ce in terms of CeO2: 40.0% by mass, Content of Zr in terms of ZrO2: 50.0% by mass, Content of a rare earth element other than Ce in terms of oxide: 10.0% by mass
To a mixing vessel, platinum nitrate solution, the OSC material, La2O3-modified alumina (La2O3 modification content: 1% by mass), magnesium nitrate, alumina sol and water were added, mixed and stirred to prepare a slurry for forming a lower layer. The contents of components in the slurry for forming a lower layer were adjusted so that the content of Pt in terms of metal was 0.6% by mass, the content of the OSC material was 44.7% by mass, the content of the La2O3-modified alumina was 39.8% by mass, the content of Mg in terms of metal was 3.2% by mass, and the solid content of the alumina sol was 9.5% by mass, based on the mass (100% by mass) of a lower layer after calcination. Note that magnesium nitrate (Mg(NO3)2) is converted to magnesium oxide (MgO) by calcination.
A flow-through type substrate was prepared, which included cells each extending in the axial direction and separated by a partition wall having a thickness of 50 to 70 μm, at a density of 600 cells/inch2 in a plane perpendicular to the axial direction, and had a volume of 1.0 L.
The flow-through type substrate was dipped in the slurry for forming a lower layer. The flow-through type substrate coated with the slurry for forming a lower layer was dried at 150° C. for 0.5 hours, and then calcined at 500° C. for 1 hour to form a lower layer. The mass of the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer was 140.9 g/L. The mass of Pt in terms of metal in the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer was 0.9 g/L. The content of Ce in terms of CeO2 in the lower layer was 17.9% by mass based on the mass of the lower layer. Note that the mass of the lower layer means the mass after calcination.
An OSC material having the following composition was prepared.
Content of Ce in terms of CeO2: 15.0% by mass, Content of Zr in terms of ZrO2: 75.0% by mass, Content of a rare earth element other than Ce in terms of oxide: 10.0% by mass
To a mixing vessel, rhodium nitrate solution, the OSC material, La2O3-modified alumina (La2O3 modification content: 1% by mass), alumina sol, zirconia sol and water were added, mixed and stirred to prepare a slurry for forming an upper layer. The contents of components in the slurry for forming an upper layer were adjusted so that the content of Rh in terms of metal was 0.2% by mass, the content of the OSC material was 69.9% by mass, the content of the La2O3-modified alumina was 22.0% by mass, the solid content of the alumina sol was 3.5% by mass, and the solid content of the zirconia sol was 4.4% by mass, based on the mass (100% by mass) of an upper layer after calcination.
The flow-through type substrate on which the lower layer was formed was dipped in the slurry for forming an upper layer. The flow-through type substrate coated with the slurry for forming an upper layer was dried at 150° C. for 0.5 hours, and then calcined at 500° C. for 1 hour to form an upper layer on the lower layer. The mass of the upper layer per unit volume of the portion of the flow-through type substrate provided with the upper layer was 80.2 g/L. The mass of Rh in terms of metal in the upper layer per unit volume of the portion of the flow-through type substrate provided with the upper layer was 0.2 g/L. Note that the mass of the upper layer means the mass after calcination.
As described above, an exhaust gas purification catalyst (which is referred to as a “catalyst”) including the lower layer formed on the flow-through type substrate and the upper layer formed on the lower layer was produced.
Using a quartz tubular furnace, the catalyst cored to 30 mL was subjected to a heat treatment under the conditions of 1000° C.×20 hours in an atmosphere containing a 10% by volume H2O in the following FC mode.
FC mode: Model gas having the following composition (3 L/min) and air (3 L/min) were made to flow alternately.
Model gas flow rate: C3H6 6 mL/min, O2 71 mL/min, and N2 2923 mL/min (3 L/min in total).
10% by volume H2O: Water was vaporized from a tank containing water and incorporated as water vapor into the model gas or the air. The saturated water vapor pressure was adjusted to a water vapor amount of the above-mentioned % by volume by regulating the temperature.
The above catalyst was placed in an exhaust gas path. While exhaust model gas (CO: 0.50%, H2: 0.17%, O2: 0.50%, NO: 400 ppm, C3H6: 1180 ppm, CO2: 14%, H2O: 10%, and N2: balance) was allowed to flow through at a space velocity of 100000/h, the purification rates of hydrocarbon (HC), nitrogen oxide (NOx) and carbon monoxide (CO) were continuously measured with the temperature increase at an increasing temperature of 20° C./minute to 500° C. The temperature at which each of the purification rates of hydrocarbon (HC), nitrogen oxide (NOx) and carbon monoxide (CO) reached 50% (light-off temperature T50) (° C.) was determined. The light-off temperature T50 was determined while the temperature was rising. The results are shown in Table 1.
A catalyst was produced in the same manner as in Example 1, except that in the production of the catalyst, the contents of components in the slurry for forming a lower layer were adjusted so that the content of Pt in terms of metal was 0.6% by mass, the content of the OSC material was 44.7% by mass, the content of the La2O3-modified alumina was 36.8% by mass, the content of Mg in terms of metal was 5.1% by mass, and the solid content of the alumina sol was 9.5% by mass, based on the mass (100% by mass) of the lower layer after calcination. In the catalyst of Example 2, the mass of the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (140.9 g/L), the mass of Pt in terms of metal in the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (0.9 g/L), and the content of Ce in terms of CeO2 in the lower layer (17.9% by mass based on the mass of the lower layer) were the same as those of the catalyst of Example 1.
A part of the slurry for forming a lower layer obtained in Example 2 was calcined at 500° C. for 1 hour to obtain a sintered powder.
An X-ray diffraction spectrum of the sintered powder thus obtained and an X-ray diffraction spectrum of α-Al2O3 which is Standard Reference Material 674a distributed by the National Institute of Standards and Technology were measured under the following conditions. In the X-ray diffraction spectrum of the sintered powder, the diffraction intensity A of a peak present at 2θ=64 to 67° among peaks derived from MgAl2O4 was measured. In the X-ray diffraction spectrum of Standard Reference Material 674a, the diffraction intensity B of a peak present at 2θ=55° to 58° among peaks derived from the α-Al2O3 was measured. Note that each of the diffraction intensities A and B refers to the height of the peak in the X-ray diffraction pattern.
Using a commercially available powder X-ray diffractometer (“MiniFlex 600”, manufactured by Rigaku Corporation), X-ray diffraction (XRD) of the sintered powder was performed under the conditions of: X-ray source: CuKα, operating axis: 2θ/θ, measuring method: continuous, counting unit: cps, start angle: 5°, end angle: 90°, sampling width: 0.02°, scan speed: 10° /min, voltage: 40 kV, and current: 150 mA. In the XRD spectrum of the sintered powder, the diffraction intensity A of a peak present at 2θ=64 to 67° among peaks derived from MgAl2O4 was automatically calculated using analysis software (“PDXL version 2”, manufactured by Rigaku Corporation). X-ray diffraction (XRD) of Standard Reference Material 674a was performed in the same as that of the sintered powder. In the XRD spectrum of Standard Reference Material 674a, the diffraction intensity B of a peak present at 2θ=55° to 58° among peaks derived from the α-Al2O3 was automatically calculated using analysis software (“PDXL version 2”, manufactured by Rigaku Corporation).
As a result, A was 1051, B was 27892, and A/B was 0.038.
The catalyst of Example 2 was used to evaluate the exhaust gas purification performance (T50) in the same manner as in Example 1. The results were shown in Table 1.
The slurry for forming a lower layer to be used for producing the catalyst of Example 2 was dried at 150° C. for 0.5 hours, and then calcined at 500° C. for 1 hour to prepare a powdered catalyst composition.
Using the heat-treated catalyst composition and a metal dispersion measurement device (BELMETAL3 manufactured by MicrotracBel Corp.), the amount of CO adsorbed onto Pt was measured by a CO pulse method, and the degree of Pt dispersion was calculated. The results were shown in Table 1. Note that the degree of Pt dispersion is the ratio of the number Y of Pt atoms exposed to the surfaces of Pt particles in the catalyst composition to the total number X of Pt atoms in the catalyst composition, and is calculated based on the formula: the degree of Pt dispersion (%)=(Y/X)×100. The number Y of Pt atoms exposed to the surfaces of Pt particles in the catalyst composition is calculated from the amount of the adsorbed CO measured by the CO pulse method, based on the premise that a Pt atom exposed to the surfaces of Pt particle in the catalyst composition adsorbs CO at a ratio of 1:1.
A catalyst was produced in the same manner as in Example 1, except that in the production of the catalyst, the contents of components in the slurry for forming a lower layer were adjusted so that the content of Pt in terms of metal was 0.6% by mass, the content of the OSC material was 44.7% by mass, the content of the La2O3-modified alumina was 32.7% by mass, the content of Mg in terms of metal was 7.5% by mass, and the solid content of the alumina sol was 9.5% by mass, based on the mass (100% by mass) of the lower layer after calcination. In the catalyst of Example 3, the mass of the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (140.9 g/L), the mass of Pt in terms of metal in the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (0.9 g/L), and the content of Ce in terms of CeO2 in the lower layer (17.9% by mass based on the mass of the lower layer) were the same as those of the catalyst of Example 1.
The catalyst of Example 3 was used to evaluate the exhaust gas purification performance (T50) in the same manner as in Example 1. The results were shown in Table 1.
A catalyst was produced in the same manner as in Example 1, except that in the production of the catalyst, MgAl2O4 was used instead of magnesium nitrate, and the contents of components in the slurry for forming a lower layer were adjusted so that the content of Pt in terms of metal was 0.6% by mass, the content of the OSC material was 44.7% by mass, the content of the La2O3-modified alumina was 15.3% by mass, the content of Mg in terms of metal was 5.1% by mass, and the solid content of the alumina sol was 9.5% by mass, based on the mass (100% by mass) of the lower layer after calcination. In the catalyst of Example 4, the mass of the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (140.9 g/L), the mass of Pt in terms of metal in the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (0.9 g/L), and the content of Ce in terms of CeO2 in the lower layer (17.9% by mass based on the mass of the lower layer) were the same as those of the catalyst of Example 1. Note that MgAl2O4 remains without change after calcination. That is, in the lower layer after calcination, Mg is present in the form of MgAl2O4.
Except that a part of the slurry for forming a lower layer obtained in Example 4 was calcined at 500° C. for 1 hour and the sintered powder thus obtained was used, an X-ray diffraction spectrum of the sintered powder, an X-ray diffraction spectrum of Standard Reference Material 674a, the diffraction intensity A of a peak present at 2θ=64 to 67° among peaks derived from MgAl2O4 in the X-ray diffraction spectrum of the sintered powder, and the diffraction intensity B of a peak present at 2θ=55° to 58° among peaks derived from the α-Al2O3 in the X-ray diffraction spectrum of Standard Reference Material 674a were measured in the same manner as in Example 2.
As a result, A was 1744, B was 27892, and A/B was 0.063.
The catalyst of Example 4 was used to evaluate the exhaust gas purification performance (T50) in the same manner as in Example 1. The results were shown in Table 1.
The slurry for forming a lower layer to be used for producing the catalyst of Example 4 was dried at 150° C. for 0.5 hours, and then calcined at 500° C. for 1 hour to prepare a powdered catalyst composition. Using the prepared catalyst composition, the degree of Pt dispersion was measured in the same manner as in Example 2. The results were shown in Table 1.
A catalyst was produced in the same manner as in Example 1, except that in the production of the catalyst, magnesium oxide was used instead of magnesium nitrate, and the contents of components in the slurry for forming a lower layer were adjusted so that the content of Pt in terms of metal was 0.6% by mass, the content of the OSC material was 44.7% by mass, the content of the La2O3-modified alumina was 36.8% by mass, the content of Mg in terms of metal was 5.1% by mass, and the solid content of the alumina sol was 9.5% by mass, based on the mass (100% by mass) of the lower layer after calcination. In the catalyst of Example 5, the mass of the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (140.9 g/L), the mass of Pt in terms of metal in the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (0.9 g/L), and the content of Ce in terms of CeO2 in the lower layer (17.9% by mass based on the mass of the lower layer) were the same as those of the catalyst of Example 1.
The catalyst of Example 5 was used to evaluate the exhaust gas purification performance (T50) in the same manner as in Example 1. The results were shown in Table 1.
A catalyst was produced in the same manner as in Example 1, except that in the production of the catalyst, the contents of components in the slurry for forming a lower layer were adjusted so that the content of Pt in terms of metal was 0.6% by mass, the content of the OSC material was 44.7% by mass, the content of the La2O3-modified alumina was 28.6% by mass, the content of Mg in terms of metal was 9.9% by mass, and the solid content of the alumina sol was 9.5% by mass, based on the mass (100% by mass) of the lower layer after calcination. In the catalyst of Comparative Example 1, the mass of the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (140.9 g/L), the mass of Pt in terms of metal in the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (0.9 g/L), and the content of Ce in terms of CeO2 in the lower layer (17.9% by mass based on the mass of the lower layer) were the same as those of the catalyst of Example 1.
The catalyst of Comparative Example 1 was used to evaluate the exhaust gas purification performance (T50) in the same manner as in Example 1. The results were shown in Table 1.
A catalyst was produced in the same manner as in Example 1, except that in the production of the catalyst, the contents of components in the slurry for forming a lower layer were adjusted so that the content of Pt in terms of metal was 0.6% by mass, the content of the OSC material was 44.7% by mass, the content of the La2O3-modified alumina was 42.6% by mass, the content of Mg in terms of metal was 1.5% by mass, and the solid content of the alumina sol was 9.5% by mass, based on the mass (100% by mass) of the lower layer after calcination. In the catalyst of Comparative Example 2, the mass of the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (140.9 g/L), the mass of Pt in terms of metal in the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (0.9 g/L), and the content of Ce in terms of CeO2 in the lower layer (17.9% by mass based on the mass of the lower layer) were the same as those of the catalyst of Example 1.
The catalyst of Comparative Example 2 was used to evaluate the exhaust gas purification performance (T50) in the same manner as in Example 1. The results were shown in Table 1.
A catalyst was produced in the same manner as in Example 1, except that in the production of the catalyst, barium nitrate was used instead of magnesium nitrate, and the contents of components in the slurry for forming a lower layer were adjusted so that the content of Pt in terms of metal was 0.6% by mass, the content of the OSC material was 44.7% by mass, the content of the La2O3-modified alumina was 39.5% by mass, the content of Ba in terms of metal was 5.0% by mass, and the solid content of the alumina sol was 9.5% by mass, based on the mass (100% by mass) of the lower layer after calcination. In the catalyst of Comparative Example 3, the mass of the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (140.9 g/L), the mass of Pt in terms of metal in the lower layer per unit volume of the portion of the flow-through type substrate provided with the lower layer (0.9 g/L), and the content of Ce in terms of CeO2 in the lower layer (17.9% by mass based on the mass of the lower layer) were the same as those of the catalyst of Example 1. Note that barium nitrate (Ba(NO3)2) is converted to barium oxide (BaO) by calcination.
The catalyst of Comparative Example 3 was used to evaluate the exhaust gas purification performance (T50) in the same manner as in Example 1. The results were shown in Table 1.
The slurry for forming a lower layer to be used for producing the catalyst of Comparative Example 3 was dried at 150° C. for 0.5 hours, and then calcined at 500° C. for 1 hour to prepare a powdered catalyst composition. Using the prepared catalyst composition, the degree of Pt dispersion was measured in the same manner as in Example 2. The results were shown in Table 1.
As shown in Table 1, Examples 1 to 5, which satisfy the conditions that the lower layer in the catalyst contains Pt and Mg, and that the content of Mg in terms of metal is 2.0% by mass or more and 9.0% by mass or less based on the mass of the lower layer, had a higher exhaust gas purification performance, compared to Comparative Examples 1 to 3, which do not satisfy the above conditions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-112637 | Jul 2022 | JP | national |
| 2022-182083 | Nov 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/025271 | 7/7/2023 | WO |
