Catalyst support, catalyst, and method for manufacturing the catalyst support

Abstract

The present invention provides a catalyst support, a catalyst, and a method for manufacturing the catalyst support, which can be used even in harsh thermal environments and have improved heat resistance. [Solution] A catalyst support comprising at least one metal (M) element selected from the group consisting of aluminum, zirconium, and lanthanide elements, and mesoporous silica, wherein the mesoporous silica has one or more peaks in the pore size distribution curve obtained by analyzing the adsorption side isotherm of the nitrogen adsorption isotherm by the DH method, in the range of pore size between 1 nm and 5 nm and between 10 nm and 50 nm, and the molar ratio (M / SiO2) of the molar amount of the metal (M) element relative to the molar amount of SiO2 in the mesoporous silica is in the range of 0.01 mol% to 15.0 mol%.

Description

[Technical Field]

[0001] The present invention relates to a catalyst support, a catalyst, and a method for producing a catalyst support. [Background technology]

[0002] For example, exhaust gases emitted from internal combustion engines such as gasoline engines and diesel engines in four-wheeled vehicles and motorcycles (also known as Norikura-type vehicles) contain harmful components such as hydrocarbons (HC) from unburned fuel, carbon monoxide (CO) from incomplete combustion, and nitrogen oxides (NOx) from excessive combustion temperatures. Catalysts are used to treat exhaust gases containing hydrocarbons (HC), carbon monoxide (CO), or nitrogen oxides (NOx). For example, hydrocarbons (HC) are oxidized and converted into water and carbon dioxide for purification. Carbon monoxide (CO) is oxidized and converted into carbon dioxide for purification. Nitrogen oxides (NOx) are reduced and converted into nitrogen for purification. Catalysts used to purify exhaust gases are typically made of precious metals such as platinum, palladium, and rhodium, which have catalytic properties, and are supported on a carrier. Since the catalyst reacts on the surface of the carrier, the larger the specific surface area of ​​the carrier on which the catalyst is supported, the higher the catalytic activity.

[0003] For example, when purifying hydrocarbons (HC) contained in exhaust gas, high temperatures of 300°C or higher are generally required due to the influence of the exhaust gas temperature. In the case of exhaust gas emitted from a vehicle, depending on the vehicle's driving conditions, it may be necessary to purify hydrocarbons contained in gas at temperatures of 800°C or higher, so high heat resistance is required for catalysts or catalyst supports.

[0004] Patent Document 1 discloses an exhaust gas purification catalyst comprising mesoporous silica having peaks in two pore diameter ranges, a first pore diameter range and a second pore diameter range, a noble metal, and an alkali metal. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2021-65837 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] There is a need for a catalyst support or catalyst that can be used under even stricter conditions than those described in Patent Document 1, and that also exhibits improved heat resistance.

[0007] Therefore, the present invention aims to provide a catalyst support, a catalyst, and a method for manufacturing the catalyst support, which can be used even in extremely harsh thermal environments of 800°C or higher, and which have improved catalytic activity and heat resistance. [Means for solving the problem]

[0008] A first aspect of the present invention is a metal (M) element selected from the group consisting of aluminum, zirconium, and lanthanide elements, It contains mesoporous silica, The mesoporous silica, in the pore size distribution curve of the mesoporous silica obtained by analyzing the adsorption-side isotherm of the nitrogen adsorption isotherm by the DH method, has one or more peaks in the range of pore size between 1 nm and 5 nm and between 10 nm and 50 nm, respectively. The catalyst support is such that the molar ratio (M / SiO2) of the molar amount of the metal (M) element, based on the molar amount of SiO2 in the mesoporous silica, is within the range of 0.01 mol% to 15.0 mol%.

[0009] A second aspect of the present invention is a catalyst comprising the catalyst carrier and a noble metal.

[0010] A third aspect of the present invention is to prepare mesoporous silica having one or more peaks in the pore size distribution curve of mesoporous silica obtained by analyzing the adsorption side isotherm of nitrogen adsorption isotherm by the DH method, in the range of pore size from 1 nm to 5 nm and from 10 nm to 50 nm, respectively. The mesoporous silica is brought into contact with a liquid containing at least one metal (M) ion selected from the group consisting of aluminum ions, zirconium ions, and lanthanide ions. A method for producing a catalyst support, comprising heat-treating the mesoporous silica, which has been in contact with a liquid containing the metal (M) ions, at a temperature of 400°C to 700°C to obtain a catalyst support containing the metal (M) element consisting of the metal (M) ions and the mesoporous silica. [Effects of the Invention]

[0011] The catalyst support, catalyst using the same, and method for manufacturing the catalyst support proposed in this invention can provide a catalyst support, a catalyst, and a method for manufacturing the catalyst support that maintain their pore structure even under extremely harsh thermal environments of 800°C or higher, thereby providing improved heat resistance. [Brief explanation of the drawing]

[0012] [Figure 1] The pore size distribution curves obtained by analyzing the adsorption-side isotherm of the nitrogen adsorption isotherm of the mesoporous silica used in the examples and comparative examples using the DH method are shown. [Figure 2] The nitrogen adsorption isotherms used in the analysis to obtain the pore size distribution curve shown in Figure 1 are shown. [Modes for carrying out the invention]

[0013] Next, the present invention will be described based on embodiments. However, the present invention is not limited to the embodiments described below.

[0014] The first embodiment is a catalyst support comprising at least one metal (M) element (hereinafter sometimes referred to as "M element") selected from the group consisting of aluminum (Al) element (hereinafter sometimes referred to as "Al element"), Zr element, and lanthanide element (hereinafter sometimes referred to as "Ln element"), and mesoporous silica, wherein the mesoporous silica has one or more peaks in the pore size distribution curve of mesoporous silica obtained by analyzing the adsorption side isotherm of a nitrogen adsorption isotherm by the DH method, in the range of pore size from 1 nm to 5 nm and from 10 nm to 50 nm, and the molar ratio (M / SiO2) of the molar amount of M element relative to the molar amount of SiO2 of the mesoporous silica is in the range of 0.01 mol% to 15.0 mol%.

[0015] Mesoporous silica includes bimodal mesoporous silica (hereinafter also referred to as "BMS") that has one peak each in the range of 1 nm or more and 5 nm or less and in the range of 10 nm or more and 50 nm or less in the pore size distribution curve of mesoporous silica obtained by analyzing the adsorption isotherm on the adsorption side of the nitrogen adsorption isotherm (hereinafter also referred to as the "pore size distribution curve"). The mesoporous silica serves as a carrier for a catalyst containing the mesoporous silica. BMS has a peak in the range of 1 nm or more and 5 nm or less in the pore size distribution curve, and has a first pore with a pore diameter in the range of 1 nm or more and 5 nm or less, and a peak in the range of 10 nm or more and 50 nm or less, and has a second pore with a pore diameter in the range of 10 nm or more and 50 nm or less. The first pore with a pore diameter in the range of 1 nm or more and 5 nm or less is presumed to be a pore derived from a structure-directing agent formed in individual particles of the mesoporous silica. Also, different from ordinary mesoporous silica (hereinafter also referred to as "MS"), BMS has a second pore with a pore diameter in the range of 10 nm or more and 50 nm or less. The second pore with a pore diameter in the range of 10 nm or more and 50 nm or less is presumed to be a pore derived from the interparticle gap of the mesoporous silica. BMS can increase the specific surface area and catalytic activity by the first pore derived from the structure-directing agent, and the second pore with a relatively large pore diameter derived from the interparticle gap can improve the diffusibility of gases such as exhaust gas in the interparticle gap and increase the catalytic activity.

[0016] The silicon dioxide constituting BMS exists in the form of crystals or amorphous, but it is known to be a crystal polymorph in which the crystal structure changes (phase transformation) depending on conditions such as pressure and temperature, and different crystal phases may be included. Generally, when silicon dioxide exists in the form of crystals, it exists as α-quartz under normal temperature and pressure, and the crystal phase changes to β-quartz, tridymite, and cristobalite with temperature changes. The BMS of the present invention is in an amorphous form.

[0017] The decrease in the specific surface area of general silica is considered to occur due to the progress of crystallization into β-quartz type, tridymite type, cristobalite type, etc., starting from the crystal nuclei formed on the surface of silica by thermal durability. On the other hand, in the case of the BMS used in the present invention, since no crystallization is observed even after thermal durability, it is推测 that it proceeds by another mechanism. For example, when the temperature changes from room temperature (e.g., 25 °C) to high temperature (e.g., 800 °C or higher or 850 °C or higher), adjacent hydroxyl groups present on the surface of BMS undergo dehydration condensation, resulting in a change in the Si-O-Si network in amorphous SiO2 and the collapse of the pore walls, and thus it is推测 that the specific surface area decreases. In a catalyst, when the specific surface area of the catalyst support decreases, the contact area with exhaust gas, etc. decreases, which becomes a factor for the decrease in catalytic performance. In this specification, "thermal durability" refers to a state in which an object is exposed to a specific temperature for a specific time. "Thermal durability" means, for example, that an object is exposed to a temperature of 800 °C or higher, preferably 850 °C or higher, for 2 hours or more and within 20 hours. Thermal durability may be carried out by the thermal durability test performed in the examples and comparative examples described later.

[0018] The catalyst support contains BMS and at least one M element selected from the group consisting of an Al element, a Zr element, and a Ln element. By containing the M element, BMS stabilizes the surface of BMS, preventing the collapse of the pore walls, and as a result, suppressing the decrease in the specific surface area after thermal durability.

[0019] The catalyst support has a molar ratio (M / SiO2) of the molar amount of M element relative to the molar amount of SiO2 in the mesoporous silica, which is within the range of 0.01 mol% to 15.0 mol%. Including M element within this range stabilizes the surface of the BMS, preventing the collapse of pore walls, and consequently suppressing the decrease in specific surface area after thermal endurance. If the molar ratio (M / SiO2) of the catalyst support is 0.01 mol% or higher, the surface of the BMS is stabilized, preventing the collapse of pore walls, suppressing the decrease in specific surface area, and improving heat resistance. If the molar ratio (M / SiO2) of the catalyst support exceeds 15.0 mol%, the amount of M element is too high, which may clog the first pore of the BMS, potentially reducing the specific surface area of ​​the BMS. Preferably, the molar ratio (M / SiO2) of the catalyst support is within the range of 0.02 mol% to 12.0 mol%, and more preferably within the range of 0.02 mol% to 10.0 mol%. The molar ratio (M / SiO2) of the catalyst support may vary depending on the type of M element.

[0020] The catalyst support preferably contains at least one M element selected from the group consisting of Al, Zr, and Ln elements, which includes Al, and the molar ratio of the amount of Al (Al / SiO2) relative to the molar amount of SiO2 in the mesoporous silica is preferably in the range of 0.02 mol% to 5.0 mol%. When the M element includes Al, the ionic radius of Al is close to that of the Si element constituting the BMS, resulting in high affinity and enabling more effective surface stabilization on or near the surface of the BMS. Changes in temperature from room temperature (e.g., 25°C) to high temperatures (e.g., 800°C or higher or 850°C or higher) suppress the dehydration condensation of adjacent hydroxyl groups present on the surface of the BMS, preventing the collapse of pore walls and suppressing a decrease in specific surface area. When element M is Al or Al, the catalyst support preferably has a molar ratio (Al / SiO2) of 0.02 mol% to 5.0 mol%, more preferably 0.03 mol% to 4.0 mol%, and even more preferably 0.05 mol% to 3.0 mol%. When element M is Al or Al, a molar ratio (Al / SiO2) of 0.02 mol% to 5.0 mol% can suppress the decrease in specific surface area due to the collapse of pore walls due to the effects described above. When metal element M is Al or Al, the ionic radius of Al is smaller than that of at least one element selected from the group consisting of Zr and Ln elements other than Al, and is close to that of Si. Therefore, even when the molar ratio (Al / SiO2) is as small as 5.0 mol%, it can stabilize the surface or near the surface of the BMS, prevent the collapse of pore walls, and suppress the decrease in specific surface area.

[0021] The catalyst support preferably contains at least one M element selected from the group consisting of Al, Zr, and Ln elements, which includes Zr, and the molar ratio of the amount of Zr (Zr / SiO2) relative to the molar amount of SiO2 in the mesoporous silica is in the range of 0.02 mol% to 6.0 mol%. When the M element contains Zr, the ionic radius of Zr is larger than that of the Si elements constituting the BMS, and its coordination number is larger. Therefore, it is presumed that this prevents silanol group sites from being positioned adjacent to each other on or near the surface of the BMS, thereby suppressing dehydration condensation and preventing the collapse of the pore walls. Furthermore, when the catalyst support contains or is composed of Zr, if the molar ratio (Zr / SiO2) is in the range of 0.02 mol% to 6.0 mol%, the Zr bond to the hydroxyl groups present on the BMS surface, stabilizing the surface state of the BMS. This prevents the hydroxyl groups on the surface from dehydrating and condensing due to temperature changes, which can cause the pore walls to collapse, thus suppressing a decrease in specific surface area. From this viewpoint, when the catalyst support contains or is composed of Zr, the molar ratio (Zr / SiO2) is preferably in the range of 0.02 mol% to 6.0 mol%, more preferably in the range of 0.03 mol% to 5.0 mol%, and even more preferably in the range of 0.03 mol% to 4.0 mol%. When the catalyst support contains or is composed of Zr, the ionic radius of Zr is larger than that of Al and smaller than that of Ln. For example, Zr ions are known to hydrolyze in aqueous solution to form a tetranuclear complex structure, and it is presumed that they are difficult to disperse because they tend to bond unevenly to hydroxyl groups present on the surface of the BMS. Therefore, it is preferable that the Zr element be included in the catalyst support in a molar ratio (Zr / SiO2) that is similar to or greater than that of the Al element.

[0022] The catalyst support preferably contains at least one M element selected from the group consisting of Al, Zr, and Ln elements, which includes Ln, and the molar ratio (Ln / SiO2) of the amount of Ln element relative to the molar amount of SiO2 in the mesoporous silica is in the range of 0.02 mol% to 3.0 mol%. When the M element contains Ln, it is presumed that the ionic radius of Ln is larger than that of the Si element constituting the structure of the BMS, and that it binds to the surface of the BMS in a way that covers a wide area of ​​the hydroxyl groups present on the surface. When the catalyst support contains Ln, or when the M element is Ln, and the molar ratio (Ln / SiO2) is in the range of 0.02 mol% to 3.0 mol%, the Ln element binds to the hydroxyl groups present on the BMS surface in a way that covers a wide area, stabilizing the surface state of the BMS. This prevents the hydroxyl groups on the surface from dehydrating and condensing due to temperature changes, which can cause the pore walls to collapse, and suppresses a decrease in specific surface area. When the catalyst support contains an Ln element or when the M element is an Ln element, the molar ratio (Ln / SiO2) is preferably in the range of 0.02 mol% to 3.0 mol%, and more preferably in the range of 0.02 mol% to 2.5 mol%. The Ln element is preferably at least one element selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). The Ln element is preferably at least one element selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, and Gd, and more preferably at least one element selected from the group consisting of La and Ce. When the metal element M contains or is an Ln element, the ionic radius of the Ln element is larger than that of the Al element or the Zr element.When the catalyst support contains an Ln element or when the M element is an Ln element, it is preferable that the Ln element is included in the catalyst support such that its molar ratio (Ln / SiO2) is smaller than that of the Al element or Zr element, in order to bond to a wider area of ​​the hydroxyl groups present on the surface of the BMS.

[0023] The catalyst support preferably contains an alkali metal element. By containing an alkali metal element (hereinafter sometimes referred to as "alk element"), the catalyst support increases the electron density of oxygen atoms near the surface of the BMS by cleaving the oxygen bonds near the surface of the BMS or by cleaving the hydroxyl group bonds attached to the surface of the BMS, thereby facilitating bonding with the M element. The M element then acts to stabilize the surface of the BMS, further preventing the collapse of the pore walls and further suppressing the decrease in specific surface area. Furthermore, with temperature changes from room temperature (e.g., 25°C) to high temperatures (e.g., 800°C or higher or 850°C or higher), the catalyst support, by containing the alk element, undergoes hydrolysis simultaneously with the change in the Si-O-Si network due to dehydration condensation of the BMS, thereby suppressing the decrease in specific surface area due to the collapse of the pore walls. The alk element contained in the catalyst support is preferably at least one element selected from the group consisting of Li, Na, K, Rb, and Cs, more preferably at least one element selected from the group consisting of Li, Na, and K, and more preferably contains K. Among the alk elements, K has a relatively large ionic radius, which can limit the effect of the alk element to near the surface of the BMS and increase the amount of hydroxyl groups present on the surface of the BMS.

[0024] When the catalyst support contains the element alk, it is preferable that the molar ratio (alk / SiO2) of the amount of alk to the amount of SiO2 in the mesoporous silica is in the range of 0.01 mol% to 0.5 mol%. When the catalyst support contains the element alk, if the molar ratio (alk / SiO2) is in the range of 0.01 mol% to 0.5 mol%, it is easier to break the oxygen bonds near the surface of the BMS and the hydroxyl group bonds present on the surface of the BMS with temperature changes from room temperature (e.g., 25°C) to high temperatures (e.g., 800°C or higher or 850°C or higher), and easier to recombine the broken parts with the metal element M. When the catalyst support contains the element alk, it is more preferable that the molar ratio (alk / SiO2) is in the range of 0.02 mol% to 0.4 mol%, even more preferable that it is in the range of 0.03 mol% to 0.3 mol%, and particularly preferable that it is in the range of 0.04 mol% to 0.2 mol%. When a catalyst support contains the element alk, if the molar ratio (alk / SiO2) exceeds 0.5 mol%, at high temperatures of 800°C or above, or 850°C or above, the pores of the mesoporous silica may condense and recombine, making the pores fragile and reducing the specific surface area.

[0025] BMS, a mesoporous silica having binary pores, has a pore volume ratio V1 / Va, where the total integrated pore volume V1 (mL / g) in the range of 1 nm to 5 nm is to the total integrated pore volume Va (mL / g) in the range of 1 nm to 100 nm, preferably in the range of 0.300 to 0.600, more preferably in the range of 0.400 to 0.580, and even more preferably in the range of 0.420 to 0.550, in its pore size distribution curve. In this specification, the pore volume ratio V1 / Va is determined from the pore size distribution curve of the BMS. The pore size distribution curve of the BMS is measured before the heat resistance test. If the pore volume ratio V1 / Va of the BMS is in the range of 0.300 to 0.600, there are sufficient first pores derived from the structure-determining agent in the range of 1 nm to 5 nm formed in the particles, which increases the specific surface area and improves catalytic activity. Here, the total integrated pore volume Va (mL / g) refers to the value obtained by integrating the pore size distribution curve in the range of 1 nm to 100 nm, which was obtained by analyzing the adsorption-side isotherm of the nitrogen adsorption isotherm using the DH method. The integrated pore volume V1 (mL / g) refers to the value obtained by integrating the pore size distribution curve in the range of 1 nm to 5 nm.

[0026] In the BMS, the pore volume ratio V2 / Va, where the total integrated pore volume V2 (mL / g) in the range of 10 nm to 50 nm is to the total integrated pore volume Va (mL / g) in the range of 1 nm to 100 nm, is preferably in the range of 0.300 to 0.600, more preferably in the range of 0.400 to 0.550, and even more preferably in the range of 0.450 to 0.520, is determined in the BMS pore volume distribution curve. In the pore size distribution curve of the BMS before the heat resistance test, if the pore volume ratio V2 / Va is within the range of 0.300 to 0.600, then there is a sufficient presence of second pores originating from interparticle gaps in the range of 10 nm to 50 nm. The presence of the aforementioned metal element M stabilizes the surface of the BMS, prevents the collapse of pore walls, suppresses the decrease in specific surface area, and improves heat resistance. Furthermore, it improves the diffusivity of gas within the interparticle gaps in the BMS. Here, the cumulative pore volume V2 (mL / g) refers to the value obtained by integrating the range of 10 nm to 50 nm of the pore size distribution curve obtained by analyzing the adsorption-side isotherm of the nitrogen adsorption isotherm using the DH method.

[0027] In the BMS, the integrated pore volume V1 (mL / g) in the range of 1 nm to 5 nm in the pore size distribution curve of the BMS is preferably in the range of 0.300 to 0.670, more preferably in the range of 0.320 to 0.660, even more preferably in the range of 0.350 to 0.650, and particularly preferably in the range of 0.380 to 0.640. If the integrated pore volume V1 (mL / g) in the range of 1 nm to 5 nm in the pore size distribution curve of the BMS is within the above range, the specific surface area of ​​the catalyst support increases, and when a catalyst support containing BMS is used as a catalyst together with a noble metal, the catalytic activity can be improved.

[0028] In the BMS, the cumulative pore volume V2 (mL / g) in the range of 10 nm to 50 nm in the pore size distribution curve of the BMS is preferably in the range of 0.400 to 0.660, more preferably in the range of 0.420 to 0.650, and even more preferably in the range of 0.450 to 0.640. If the cumulative pore volume V2 (mL / g) in the range of 10 nm to 50 nm in the pore size distribution curve of the BMS is within the above range, then there are sufficient second pores originating from the gaps between particles. When a catalyst support containing BMS is used as a catalyst together with a noble metal, the presence of the aforementioned metal element M stabilizes the surface of the BMS, prevents the collapse of the pore walls, suppresses a decrease in specific surface area and aggregation of the noble metal, improves heat resistance, and improves the diffusivity of gases such as exhaust gases within the particle gaps.

[0029] The second embodiment is a catalyst comprising the catalyst carrier described above and a noble metal. The precious metal is at least one selected from the group consisting of gold (Au), silver (Ag), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru), and osmium (Os). Alternatively, at least one of the precious metals may be selected from the platinum group, consisting of Rh, Pd, Pt, Ir, Ru, and Os. It is preferable that the precious metal is at least one selected from the group consisting of Pt, Pd, and Rh, in order to further promote catalytic purification of hydrocarbons (HC) in exhaust gases even at high temperatures.

[0030] In the catalyst, the content of noble metals is preferably in the range of 0.1% to 20.0% by mass, more preferably in the range of 0.2% to 15.0% by mass, and even more preferably in the range of 0.5% to 10.0% by mass, based on the total mass of the catalyst support containing noble metals, metal (M) elements, alkali metal (alk) elements, and mesoporous silica as 100% by mass. In a catalyst, if the content of noble metals is within the range of 0.1% to 20.0% by mass, based on 100% by mass of the total weight of the catalyst support containing noble metals, metal (M) elements, alkali metal (alk) elements, and mesoporous silica, then even when a gas containing water (H2O), oxygen (O2), propylene (C3H6), and nitrogen (N2) is passed through it for 1 to 20 hours at a temperature range of, for example, 800°C to 1000°C, preferably 850°C to 1000°C, the catalyst performance will not be reduced and sufficient catalytic function can be exhibited.

[0031] The third embodiment involves preparing mesoporous silica having one or more peaks in the pore size distribution curve obtained by analyzing the adsorption-side isotherm of nitrogen adsorption isotherms using the DH method, in the range of pore size between 1 nm and 5 nm and between 10 nm and 50 nm. The mesoporous silica is brought into contact with a liquid containing at least one metal (M) ion selected from the group consisting of aluminum ions, zirconium ions, and lanthanide ions. A method for producing a catalyst support, comprising heat-treating the mesoporous silica, which has been in contact with a liquid containing the metal (M) ions, at a temperature of 400°C to 700°C to obtain a catalyst support containing the metal (M) element composed of the metal (M) ions and the mesoporous silica.

[0032] In a method for producing a catalyst support, BMS, which is mesoporous silica having binary pores, is brought into contact with a liquid containing at least one metal ion selected from the group consisting of aluminum ions (hereinafter sometimes referred to as "Al ions," etc.), Zr ions, and lanthanide ions (hereinafter sometimes referred to as "Ln ions") (hereinafter sometimes referred to as "M ions"). The BMS that has been brought into contact with the liquid containing M ions is then heat-treated at a temperature of 400°C to 700°C. This stabilizes the surface of the BMS, preventing the collapse of the pore walls and suppressing a decrease in specific surface area, thereby obtaining a catalyst support with excellent heat resistance.

[0033] In a method for manufacturing a catalyst support, it is preferable that the liquid contacted with BMS, a mesoporous silica having binary pores, contains M ions such that the molar ratio of M ions in terms of metal (M / SiO2) is in the range of 0.01 mol% to 15.0 mol%, based on the molar amount of SiO2 in the BMS before contact with the liquid. If the liquid contacted with the BMS contains M ions in the range of 0.01 mol% to 15.0 mol%, based on the molar amount of SiO2 in the BMS, then in the resulting catalyst support, the surface of the BMS is stabilized, preventing the collapse of the pore walls, suppressing a decrease in specific surface area, and allowing a sufficient amount of M element to act on the BMS to improve its heat resistance. The liquid is preferably water.

[0034] In the method for producing a catalyst support, the M ions contained in the liquid contacted with BMS may be Zr ions. The Zr ions have a larger ionic radius than the Si elements that constitute BMS, and have a larger coordination number. Therefore, it is presumed that they prevent silanol group sites from being positioned adjacent to each other on or near the surface of BMS, thereby suppressing dehydration condensation and preventing the collapse of the pore walls. It is also presumed that the Zr elements, when present on the BMS surface, bond to cover the oxygen and hydroxyl groups. When the M ions contained in the liquid contacted with BMS are Zr ions, the molar ratio (Zr / SiO2) of Zr ions in terms of metal, based on the molar amount of SiO2 in the BMS before contact with the liquid, is preferably in the range of 0.02 mol% to 6.0 mol%, more preferably in the range of 0.03 mol% to 6.0 mol%, and even more preferably in the range of 0.05 mol% to 6.0 mol%.

[0035] In the method for producing a catalyst support, the M ions contained in the liquid contacted with BMS may be Al ions. Since Al ions have an ionic radius close to that of the Si elements that make up BMS, they have high affinity and are presumed to be able to more effectively stabilize the surface of BMS or near its surface. When the M ions contained in the liquid contacted with BMS are Al ions, the molar ratio (Al / SiO2) of Al ions in metallic terms is preferably in the range of 0.02 mol% to 5.0 mol%, more preferably in the range of 0.03 mol% to 4.0 mol%, and even more preferably in the range of 0.05 mol% to 3.0 mol%, based on the molar amount of SiO2 in the BMS before contact with the liquid.

[0036] In the method for producing a catalyst support, the M ions contained in the liquid contacted with the BMS may be Ln ions. The Ln ions have an ionic radius larger than that of the Si elements that make up the BMS, and it is presumed that they bond to the surface or near the surface of the BMS in a way that broadly covers oxygen and hydroxyl groups. When the M ions contained in the liquid contacted with the BMS are Ln ions, the molar ratio (Ln / SiO2) of the Ln ions in terms of metal, based on the molar amount of SiO2 in the BMS before contact with the liquid, is preferably in the range of 0.02 mol% to 3.0 mol%, and more preferably in the range of 0.02 mol% to 2.5 mol%.

[0037] The Ln ion is preferably at least one metal ion selected from the group consisting of La ions, Ce ions, Pr ions, Nd ions, Pm ions, Eu ions, Gd ions, Tb ions, Dy ions, Ho ions, Er ions, Tm ions, Yb ions, and Lu ions. The Ln ion is preferably at least one metal ion selected from the group consisting of La ions, Ce ions, Pr, Nd, Sm, Eu, and Gd, and more preferably at least one metal ion selected from the group consisting of La ions and Ce ions.

[0038] A method for producing a catalyst support preferably involves contacting BMS, which is mesoporous silica having binary pores, with a liquid containing alkali metal ions (hereinafter sometimes referred to as "alk ions"). By contacting BMS with a liquid containing alk ions, the alk ions break the oxygen bonds near the surface of BMS, increasing the amount of hydroxyl groups present on the surface of BMS, or increasing the electron density of oxygen atoms near the surface of BMS, making it easier for them to bond with M ions. When M ions bond with oxygen on the surface of BMS or hydroxyl groups present on the surface of BMS, the surface structure is further stabilized, preventing the collapse of pore walls, further suppressing the decrease in specific surface area, and a catalyst support with high heat resistance can be obtained. Furthermore, by contacting BMS with a liquid containing alk ions, alk can be incorporated into BMS, and with temperature changes from room temperature (e.g., 25°C) to high temperatures (e.g., 800°C or higher or 850°C or higher), hydrolysis occurs simultaneously with the change in the Si-O-Si network due to dehydration condensation of BMS, thereby suppressing the decrease in specific surface area due to the collapse of pore walls. The alk ion is preferably at least one ion selected from the group consisting of Li ions, Na ions, K ions, Rb ions, and Cs ions, more preferably at least one ion selected from the group consisting of Li ions, Na ions, and K ions, and more preferably contains a K ion. Among the alk ions, the ionic radius of the K ion is relatively large, which allows the effect of the alk ion to be kept near the surface of the BMS, and can increase the amount of hydroxyl groups present on the surface of the BMS.

[0039] In the method for producing a catalyst support, the alk ions contained in the liquid contacted with the BMS preferably have a molar ratio (alk / SiO2) of 0.01 mol% to 0.5 mol%, more preferably 0.02 mol% to 0.4 mol%, even more preferably 0.03 mol% to 0.3 mol%, and particularly preferably 0.04 mol% to 0.2 mol%. When the molar ratio (alk / SiO2) of the alk ions in the liquid is within the range of 0.01 mol% to 0.5 mol%, they increase the amount of hydroxyl groups present on the surface of the BMS by breaking the oxygen bonds on the surface of the BMS, and facilitate the recombination of the hydroxyl groups present on the surface of the BMS with M ions.

[0040] In a method for manufacturing catalyst supports, it is preferable to contact BMS, which is mesoporous silica having binary pores, with a liquid containing alk ions before heat treatment. By contacting BMS with a liquid containing alk ions before heat treatment and then performing heat treatment, the alk element can be incorporated into the BMS.

[0041] In a method for manufacturing a catalyst support, the order in which BMS is brought into contact with a liquid containing at least one M ion selected from the group consisting of Al ions, Zr ions, and Ln ions, and a liquid containing alk ions, may be as follows: Before heat treatment, BMS may be brought into contact with the liquid containing M ions, then the liquid containing alk ions may be added, BMS may be brought into contact with the liquid containing alk ions, and then the BMS may undergo its first heat treatment. Alternatively, before heat treatment, BMS may be brought into contact with a liquid containing both M ions and alk ions, followed by a single heat treatment.

[0042] In a method for manufacturing a catalyst support, when BMS is brought into contact with a liquid containing M ions and a liquid containing alk ions, after contacting the BMS with the liquid containing alk ions, the BMS that has been in contact with the liquid containing alk ions may be subjected to a first heat treatment. After the heat treatment, the BMS may be brought into contact with the liquid containing M ions, and the BMS that has been in contact with the liquid containing M ions may be subjected to a second heat treatment.

[0043] In a method for manufacturing a catalyst support, when BMS is brought into contact with a liquid containing M ions and a liquid containing alk ions, after contacting the BMS with the liquid containing M ions, the BMS that has been in contact with the liquid containing M ions may be subjected to a first heat treatment. After the heat treatment, the BMS may be brought into contact with the liquid containing alk ions, and the BMS that has been in contact with the liquid containing alk ions may be subjected to a second heat treatment.

[0044] In a method for manufacturing catalyst supports, if the liquid contains both M ions and alk ions, the BMS may be brought into contact with the liquid containing both M ions and alk ions, and the BMS in contact with the liquid may be subjected to a single heat treatment.

[0045] This document describes an example of a method for preparing mesoporous silica as a catalyst support. The method for producing mesoporous silica is not limited to the example described below. Mesoporous silica can generally be formed by the sol-gel method. First, a surfactant at a concentration equal to or greater than the critical micelle concentration is dissolved in water as a structure-controlling agent to form rod-shaped micelle particles. After standing for a while, these particles become colloidal. Then, a silica source is added to the solution, and a predetermined acid or base is added as a catalyst to achieve a predetermined pH. A sol-gel reaction proceeds in the gaps between the colloidal particles, forming a gel with a silica gel skeleton. Subsequently, the gel can be heat-treated at a temperature of 500°C or higher to produce mesoporous silica. Examples of surfactants include cetyltrimethylammonium chloride (CH3(CH2)). 15Examples include N(CH3)3Cl:CTAC). As a silica source, for example, tetraethoxysilane (Si(OC2H5)4:TEOS) can be used. The obtained mesoporous silica has pores where the rod-shaped micelle particles were located, leaving voids. By adjusting the pH value when forming the mesoporous silica, the degree of aggregation of the mesoporous silica changes, and BMS, which is mesoporous silica having a binary pore structure consisting of a first pore derived from the structure-determining agent and a second pore derived from the interparticle gaps, can be produced. For BMS, it is preferable to adjust the pH of a solution containing a surfactant and tetraethoxysilane by adding a basic compound to make the pH between 9 and 10.5. In the method for producing BMS, after obtaining a gel, it may be dried at a temperature of 50°C or higher, for example, to obtain a mesoporous silica precursor, and this mesoporous silica precursor may be heat-treated to obtain BMS. In this specification, the heat treatment performed on the gel or mesoporous silica precursor may be referred to as precursor heat treatment. The temperature at which the obtained gel or mesoporous silica precursor is heat-treated for the precursor is preferably 500°C or higher, but may also be in the range of 550°C to 800°C, or 700°C or lower. The atmosphere for the precursor heat treatment may be an atmospheric atmosphere, or an inert gas atmosphere such as nitrogen. The atmospheric pressure for the precursor heat treatment may be atmospheric pressure.

[0046] In the method for producing a catalyst support, the temperature at which the BMS and the liquid containing M ions are brought into contact is preferably within the range of 0°C to 45°C, but may also be room temperature of 5°C to 35°C. The contact time between BMS and the liquid containing M ions is preferably 0.1 hours to 6 hours, and more preferably 0.5 hours to 3 hours. After adding BMS to the liquid containing BMS and M ions, the mixture may be stirred to allow contact.

[0047] In the method for producing a catalyst support, the temperature at which BMS and the liquid containing alk ions are brought into contact is preferably within the range of 0°C to 45°C, and may also be room temperature between 5°C and 35°C. The contact time between BMS and the liquid containing alk ions is preferably between 0.1 hours and 6 hours, and more preferably between 0.5 hours and 3 hours. After adding BMS to the liquid containing BMS and alk ions, the mixture may be stirred and then brought into contact.

[0048] In a method for producing a catalyst support, it is preferable to include drying the BMS, which is mesoporous silica having binary pores that has been in contact with a liquid, at a temperature of 20°C to 200°C before heat treatment. By drying the BMS that has been in contact with a liquid before heat treatment, M ions or alk ions can be attached to the surface of the BMS at a temperature that does not cause the components in the liquid to decompose, so that M elements or alk elements are included in the BMS within a desired range after subsequent heat treatment. The temperature for drying the BMS that has been in contact with a liquid may be 25°C to 180°C or 30°C to 150°C. The drying time for the BMS that has been in contact with a liquid is preferably 0.1 hours to 6 hours, and more preferably 0.5 hours to 3 hours. The method for drying the BMS is not particularly limited, and known methods can be used, but examples include evaporation to dryness.

[0049] In the method for manufacturing catalyst supports, the temperature at which BMS contacted with a liquid containing M ions, and BMS contacted with a liquid containing M ions and a liquid containing alk are heat-treated is preferably 400°C to 700°C, and more preferably 450°C to 650°C. The atmosphere for heat treatment may be an atmospheric atmosphere containing 20% ​​or more by volume of oxygen, or an inert gas atmosphere such as nitrogen. The atmospheric pressure for heat treatment may be standard atmospheric pressure (0.101 MPa), 0.101 MPa or higher, or a pressurized atmosphere of 0.11 MPa to 1 MPa. A holding time may be provided during the heat treatment to maintain the temperature at a predetermined level. The heat treatment time is preferably 0.5 hours to 7 hours, and more preferably 1 hour to 5 hours.

[0050] A method for producing a catalyst using a catalyst support involves contacting the catalyst support obtained by the aforementioned production method with a precious metal or a compound containing a precious metal to adhere the precious metal to the catalyst support. Methods for adhering the precious metal to the catalyst support include impregnation, precipitation, and ion exchange. Impregnation methods include the incipient wetness method, evaporation to dryness method, pore-filling method, spray method, and equilibrium adsorption method. Precipitation methods include the kneading method and deposition method.

[0051] When attaching a precious metal to a catalyst support by impregnation, one method is to immerse the catalyst support in a liquid containing the precious metal. The catalyst support is immersed in a liquid containing the precious metal or a liquid containing a compound containing the precious metal to obtain a catalyst support with the precious metal attached. The immersion time of the catalyst support in the liquid containing the precious metal can be 0.5 hours or more and within 5 hours, preferably 1 hour or more and within 4 hours. After immersion, the catalyst support with the attached precious metal may be dried. The drying temperature can be 50°C or more and within 100°C, or 50°C or more and within 80°C. The drying time can be 0.5 hours or more and within 5 hours, or 1 hour or more and within 4 hours. The pressure during drying is not particularly limited and may be atmospheric pressure (0.1 MPa) or reduced pressure of 0.1 MPa or less.

[0052] A method for producing a catalyst using a catalyst support includes, for example, attaching a noble metal to the catalyst support by impregnation, followed by heat treatment to obtain a catalyst containing the noble metal and the catalyst support. The temperature of the heat treatment to obtain the catalyst is preferably in the range of 200°C to 800°C, more preferably in the range of 400°C to 700°C, in order to maintain the BMS skeleton contained in the catalyst support and to support the noble metal. The atmosphere for the heat treatment to obtain the catalyst may be an atmospheric atmosphere or an inert gas atmosphere such as nitrogen. The atmospheric pressure for the heat treatment to obtain the catalyst may be standard atmospheric pressure (0.101 MPa), 0.101 MPa or higher, or a pressurized atmosphere of 0.11 MPa to 1 MPa. A holding time of holding at a predetermined temperature may be provided during the heat treatment to obtain the catalyst. The heat treatment time is preferably 0.5 hours to 7 hours, and more preferably 1 hour to 6 hours.

[0053] The catalyst support or catalyst obtained by the above-described manufacturing method exhibits suppressed reduction in specific surface area and maintains high catalytic activity even when exposed to harsh thermal environments of 800°C or higher, or 850°C or higher, and demonstrates stable and high purification performance of hydrocarbons (HC). The catalyst support or catalyst can purify exhaust gases from gasoline engines, diesel engines, etc., with stable and high purification performance, and is suitable for use in purifying exhaust gases emitted from internal combustion engines such as automobiles and motorcycles. Furthermore, since the catalyst support or catalyst has the characteristic of high heat resistance, it can be suitable for use as a support for catalysts that react at high temperatures for long periods of time. Examples of suitable catalytic reactions include hydrogenation and dehydrogenation of hydrocarbons, oxidation treatment of organic solvents, high-temperature steam reforming, flameless combustion, and high-temperature denitrification of flue gas.

[0054] Embodiments of the present invention encompass the following technical concepts. [1] At least one metallic (M) element selected from the group consisting of aluminum, zirconium, and lanthanide elements, It contains mesoporous silica, The mesoporous silica, in the pore size distribution curve of the mesoporous silica obtained by analyzing the adsorption-side isotherm of the nitrogen adsorption isotherm by the DH method, has one or more peaks in the range of pore size between 1 nm and 5 nm and between 10 nm and 50 nm, respectively. A catalyst support wherein the molar ratio (M / SiO2) of the molar amount of the metal (M) element, based on the molar amount of SiO2 in the mesoporous silica, is in the range of 0.01 mol% to 15.0 mol%. [2] The catalyst support according to [1], wherein the metal (M) element contains aluminum (Al), and the molar ratio (Al / SiO2) of the amount of aluminum (Al) based on the molar amount of SiO2 in the mesoporous silica is in the range of 0.02 mol% to 5.0 mol%. [3] The catalyst carrier according to [1], wherein the metal (M) element contains zirconium (Zr) element, and the molar ratio (Zr / SiO2) of the molar amount of zirconium (Zr) element, based on the molar amount of SiO2 in the mesoporous silica, is in the range of 0.02 mol% to 6.0 mol%. [4] The catalyst support according to [1], wherein the metal (M) element comprises at least one selected from the group consisting of lanthanide (Ln) elements, and the molar ratio (Ln / SiO2) of the molar amount of the lanthanide (Ln) element, based on the molar amount of SiO2 in the mesoporous silica, is in the range of 0.02 mol% to 3.0 mol%. [5] A catalyst carrier according to any one of [1] to [4], comprising an alkali metal element. [6] The catalyst support according to [5], wherein the molar ratio (alk / SiO2) of the amount of alkali metal (alk) element relative to the molar amount of SiO2 in the mesoporous silica is in the range of 0.01 mol% or more and 0.5 mol% or less. [7] A catalyst comprising a catalyst carrier as described in any of [1] to [6] and a noble metal. [8] Prepare mesoporous silica having one or more peaks in the pore size distribution curve obtained by analyzing the adsorption side isotherm of nitrogen adsorption isotherms using the DH method, in the range of pore size from 1 nm to 5 nm and from 10 nm to 50 nm. The mesoporous silica is brought into contact with a liquid containing at least one metal (M) ion selected from the group consisting of aluminum ions, zirconium ions, and lanthanide ions. A method for producing a catalyst support, comprising: heat-treating the mesoporous silica, which has been in contact with a liquid containing the metal (M) ions, at a temperature of 400°C to 700°C to obtain a catalyst support containing the metal (M) element consisting of the metal (M) ions and the mesoporous silica. [9] A method for producing a catalyst carrier according to [8], comprising contacting the mesoporous silica with a liquid containing alkali metal (alk) ions.

[10] A method for producing a catalyst carrier according to [9], comprising contacting the mesoporous silica with a liquid containing alkali metal (alk) ions before performing the heat treatment.

[11] A method for producing a catalyst carrier according to any one of [8] to

[10] , wherein the metal (M) ions are contained in the liquid in a metal-equivalent molar ratio (M / SiO2) of the metal (M) ions within the range of 0.01 mol% to 15.0 mol%, based on the molar amount of SiO2 of the mesoporous silica that is brought into contact with the liquid.

[12] A method for producing a catalyst carrier according to [9] or

[10] , wherein the alkali metal (alk) ions are contained in the liquid in a metal-based molar ratio (alk / SiO2) of 0.01 mol% or more and 0.5 mol% or less, based on the molar amount of SiO2 of the mesoporous silica that is brought into contact with the liquid.

[13] A method for producing a catalyst carrier according to [8] or

[11] , wherein the metal ion comprises a zirconium (Zr) ion.

[14] A method for producing a catalyst carrier according to [9],

[10] , or

[12] , wherein the alkali metal ion contains potassium (K) ions.

[15] A method for producing a catalyst carrier according to any one of [8] to

[14] , comprising drying the mesoporous silica that has been in contact with the liquid at a temperature of 20°C or higher and 200°C or lower, after contact with the liquid and before the heat treatment. [Examples]

[0055] The present invention will be described in further detail below based on examples and comparative examples. The present invention is not limited to these examples.

[0056] Manufacturing of Mesoporous Silica (BMS) Mesoporous silica (BMS) with a binary pore structure was produced by the sol-gel method. Cetyltrimethylammonium chloride (CH3(CH2)) was used as the surfactant raw material. 15 N(CH3)3Cl (CTAC) was used as the silica source, and tetraethoxysilane (Si(OC2H5)4 (TEOS)) was used as the silica source. The molar ratio of CTAC:TEOS:water (H2O) was weighed to 0.19:1.0:75. Specifically, 3.88 g of CTAC was added to 80 mL of distilled water and stirred with a stirrer to completely dissolve the CTAC. 14 mL of TEOS was added to this solution and stirred with a stirrer for 1 hour. A 2 mol / L aqueous ammonia (NH3) solution was added all at once to the solution containing CTAC and TEOS while continuing to stir until the pH reached 10. After confirming that the solution had gelled, stirring was stopped and the mixture was allowed to stand at room temperature (20°C to 25°C) for 5 hours, and then filtered. The obtained gel was washed with distilled water, and then the gel was dried at 60°C for 12 hours to obtain a mesoporous silica precursor. This mesoporous silica precursor was subjected to a first heat treatment in an electric furnace at 550°C for 3 hours in air to obtain mesoporous silica. The obtained mesoporous silica was confirmed to be mesoporous silica (BMS) with binary pores, as shown in the pore size distribution curve of mesoporous silica obtained by analyzing the adsorption side isotherm of the nitrogen adsorption isotherm measured by the method described later using the DH method, which showed that there was one or more peaks in the pore size range of 1 nm to 5 nm and in the pore size range of 10 nm to 50 nm.

[0057] The nitrogen adsorption isotherm of the manufactured BMS (catalyst carrier for Comparative Example 1) was measured as follows.

[0058] Measurement of nitrogen adsorption isotherms Nitrogen adsorption isotherms were measured for the manufactured BMS. A high-precision gas adsorption device (product name: BELSORP mini, manufactured by Microtrac-Bel Co., Ltd.) was used for the measurement. The measurement conditions were as follows: The sample was pretreated by heating at 10 Pa and 300°C for 2 hours before measurement. It was checked whether there was one peak each in the range of 1 nm to 5 nm and the range of 10 nm to 50 nm from the nitrogen adsorption isotherm. Furthermore, the pore size of the peak top in the range of 1 nm to 5 nm was defined as representative pore size D1, and the pore size of the peak top in the range of 10 nm to 50 nm was defined as representative pore size D2. Furthermore, the total integrated pore volume Va (mL / g) obtained by integrating the range from 1 nm to 100 nm, the integrated pore volume V1 (mL / g) obtained by integrating the range from 1 nm to 5 nm, and the integrated pore volume V2 (mL / g) obtained by integrating the range from 10 nm to 50 nm were measured in the pore size distribution curve obtained by analyzing the adsorption-side isotherm of the nitrogen adsorption isotherm used in the examples and comparative examples using the DH method, and Figure 2 shows the nitrogen adsorption isotherm used in the analysis. The nitrogen adsorption isotherm used in the analysis in Figure 2 was obtained by performing the same measurements as for the BMS (catalyst support of Comparative Example 1) produced above for the catalyst supports obtained in Examples 2, 5 and 13 described later. Measurement method: Constant volume gas adsorption method Adsorbent gas: Nitrogen Pre-treatment conditions for the device: Vacuum evacuation at 300°C for 2 hours at a pressure of 10 Pa or less. Analysis program: Adsorption / desorption isotherm measurement Measurement of pore size distribution curves using the DH method Measurement relative pressure range: P / P0 = 0.13~0.99 Quantity measured: 0.05g

[0059] [Table 1]

[0060] As shown in Figure 1, the mesoporous silica used in the examples and comparative examples is BMS, which is a mesoporous silica with binary pores, and in the pore size distribution curve of the exhaust gas purification catalyst obtained by analyzing the adsorption side isotherm of the nitrogen adsorption isotherm using the DH method, there is one peak each in the range of pore size from 1 nm to 5 nm and from 10 nm to 50 nm.

[0061] Example 1 The fabricated mesoporous silica (BMS) with binary pores was brought into contact with a liquid containing lanthanide (Ln) ions, specifically Ce ions, as the metal (M) ions. Based on the molar amount of SiO2 in the BMS, cerium nitrate (Ce(NO3)3) was dissolved in deionized water to obtain a liquid containing Ce ions, such that the molar ratio (Ln(Ce) / SiO2) of Ce ions in terms of metal equivalent was 0.02 mol%. BMS was immersed in a liquid containing Ce ions at room temperature (25°C ± 5°C) for 1 hour, the solvent water was removed by evaporation to dryness, and the BMS was dried at 60°C for 3 hours to obtain BMS with attached Ce. The Ce-attached BMS was heat-treated in an electric furnace at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) at 550°C for 3 hours to obtain the catalyst support of Example 1, which is BMS containing Ce with the molar ratio (M / SiO2) shown in Table 2. Table 2 also includes the mass percentage of Ce in metal equivalent (M / SiO2 (mass%)) when the mass of SiO2 in the BMS is taken as 100 mass%.

[0062] Examples 2 to 4 Examples 2 to 4, which are catalyst supports containing Ce with the molar ratio (M / SiO2) shown in Table 2, were obtained in the same manner as in Example 1, except that cerium nitrate (Ce(NO3)3) was dissolved in deionized water to create a liquid containing Ce ions, based on the molar amount of SiO2 in BMS, a mesoporous silica having binary pores, so that the molar ratio (Ln(Ce) / SiO2) of Ce ions in terms of metal equivalent (Ln(Ce) / SiO2) was the value shown in Table 2. Table 2 also includes the mass % of Ce in terms of metal equivalent (M / SiO2 (mass%)) when the mass of SiO2 in BMS is taken as 100% by mass.

[0063] Examples 5 to 8 Examples 5 to 8, which are catalyst supports containing La in a BMS (mesoporous silica) with a molar ratio (M / SiO2) shown in Table 2, were obtained in the same manner as in Example 1, except that lanthanum nitrate (La(NO3)3) was dissolved in deionized water to create a liquid containing La ions, based on the molar amount of SiO2 in the BMS, which is a mesoporous silica having a binary pore structure. Table 2 also includes the mass percentage (M / SiO2 (mass%)) of La in metal equivalent, when the mass of SiO2 in the BMS is taken as 100% by mass.

[0064] Examples 9 to 13 Examples 9 to 13, which are catalyst supports containing Zr in a BMS (mesoporous silica) with a molar ratio (M / SiO2) shown in Table 2, were obtained in the same manner as in Example 1, except that zirconium oxynitrate (ZrO(NO3)2) was dissolved in deionized water to create a liquid containing Zr ions, based on the molar amount of SiO2 in the BMS, which is a mesoporous silica having a binary pore structure, so that the molar ratio (Zr / SiO2) of Zr ions in terms of metal is the value shown in Table 2. Table 2 also includes the mass % of Zr in terms of metal (M / SiO2 (mass%)) when the mass of SiO2 in the BMS is taken as 100% by mass.

[0065] Examples 14 to 18 Examples 14 to 18, which are catalyst supports containing Al in a BMS (mesoporous silica) with a molar ratio (M / SiO2) shown in Table 2, were obtained in the same manner as in Example 1, except that aluminum nitrate (Al(NO3)3) was dissolved in deionized water to form a liquid containing Al ions, based on the molar amount of SiO2 in BMS, which is a mesoporous silica having a binary pore structure, so that the molar ratio (Al / SiO2) of Al ions in terms of metal is the value shown in Table 2. Table 2 also includes the mass percentage (M / SiO2 (mass%)) of Al in terms of metal, when the mass of SiO2 in BMS is taken as 100% by mass.

[0066] Comparative Example 1 The manufactured BMS was used as the catalyst support for Comparative Example 1, which does not contain the metal (M) element.

[0067] Heat resistance test Each catalyst support in the examples and comparative examples was heat-treated in an electric furnace at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) at 900°C for 3 hours, and then subjected to a heat resistance test.

[0068] Specific surface area maintenance rate (%) The specific surface area of ​​each catalyst support in the examples and comparative examples was measured using a gas adsorption analyzer (BELSORP mini, manufactured by Microtrac-Bel Co., Ltd.) before the heat resistance test. The specific surface area was determined by the BET multipoint method based on the nitrogen adsorption isotherm measured at a temperature of 77K using liquid nitrogen after degassing under reduced pressure at 300°C for 2 hours. The specific surface area of ​​each catalyst support in the examples and comparative examples after the heat resistance test described above was measured using the same apparatus as the one used to measure the specific surface area before the heat resistance test. After degassing each catalyst support under reduced pressure at 300°C for 2 hours, the specific surface area was measured using the BET multipoint method based on the nitrogen adsorption isotherm measured at a temperature of 77K using liquid nitrogen. The specific surface area of ​​the catalyst support before the heat resistance test was set to 100%, and the percentage of the specific surface area of ​​the catalyst support after the heat resistance test was calculated as the specific surface area retention rate (%). The results are shown in Table 2.

[0069] [Table 2]

[0070] Each catalyst support according to Examples 1 to 18 contains BMS, which is mesoporous silica having binary pores, and at least one M element selected from the group consisting of Al, Zr, and Ln elements, with a molar ratio (M / SiO2) of the amount of M element relative to the molar amount of SiO2 in BMS being in the range of 0.01 mol% to 15.0 mol%. Even after a heat resistance test involving heat treatment at 900°C for 3 hours, the specific surface area retention rate is 20% or more, the decrease in specific surface area is suppressed, and it exhibits heat resistance.

[0071] Each catalyst support in Examples 1 to 8 has an M element that is either Ce or La, and contains a molar ratio (Ln / SiO2) of Ln element relative to the molar amount of SiO2 in BMS within the range of 0.02 mol% to 3.0 mol%. Even after a heat resistance test involving heat treatment at 900°C for 3 hours, the specific surface area retention rate is 70% or more, indicating that the decrease in specific surface area is further suppressed and that it has high heat resistance. When the M element contained in the catalyst support is an Ln element, a relatively small molar ratio (Ln / SiO2) within the range of 0.05 mol% to 3.0 mol% tends to result in a higher specific surface area retention rate and higher heat resistance. The ionic radius of the Ln element is larger than that of the Si element constituting BMS, and it is presumed that it bonds to the hydroxyl groups present on or near the surface of BMS in a way that covers a wide area. It is presumed that, in order to stabilize BMS, the hydroxyl groups present on the surface undergo dehydration condensation due to temperature changes, preventing the collapse of the pore walls and suppressing a decrease in specific surface area. A relatively small molar ratio (Ln / SiO2) is preferable for the Ln element so as not to bind to the first and second pores of BMS and reduce the specific surface area.

[0072] Each catalyst support according to Examples 9 to 13 contains Zr as the M element, with a molar ratio (Zr / SiO2) of Zr relative to the molar amount of SiO2 in BMS within the range of 0.02 mol% to 6.0 mol%. Even after a heat resistance test involving heat treatment at 900°C for 3 hours, the specific surface area retention rate is 70% or higher, indicating that the decrease in specific surface area is further suppressed and that it has high heat resistance. When the M element contained in the catalyst support is Zr, a relatively large molar ratio (Zr / SiO2) within the range of 0.05 mol% to 6.0 mol% tends to result in a higher specific surface area retention rate and higher heat resistance, with particularly high heat resistance observed within the range of 3.0 mol% to 6.0 mol%. The Zr element has a larger ionic radius than the Si element that constitutes the BMS, and therefore has a larger coordination number. This is thought to prevent silanol group sites from being positioned adjacent to each other on or near the surface of the BMS, thereby suppressing dehydration condensation and preventing the collapse of pore walls. Furthermore, it is thought that the Zr element bonds to cover the hydroxyl groups present on the BMS surface, stabilizing the surface state of the BMS. This prevents dehydration condensation of the hydroxyl groups on the surface due to temperature changes, which would cause the pore walls to collapse, thus suppressing a decrease in specific surface area. Since the ionic radius of the Zr element is not as large as that of the Ln element, it bonds to cover the oxygen and hydroxyl groups present on the surface, so a relatively large molar ratio (Zr / SiO2) is preferable.

[0073] Each catalyst support according to Examples 14 to 18 contains Al as the M element, with a molar ratio (Al / SiO2) of Al (based on the molar amount of SiO2 in BMS) within the range of 0.02 mol% to 12.0 mol%, and maintains a specific surface area of ​​20% or more even after a heat resistance test involving heat treatment at 900°C for 3 hours, thus suppressing the decrease in specific surface area and exhibiting heat resistance. When the M element contained in the catalyst support is Al, a relatively small molar ratio (Al / SiO2) of preferably 0.02 mol% to 5.0 mol%, more preferably 0.03 mol% to 4.0 mol%, and even more preferably 0.05 mol% to 3.0 mol% tends to result in a higher specific surface area retention rate and higher heat resistance. The ionic radius of Al is close in size to that of Si, which constitutes BMS, resulting in high affinity and enabling more effective surface stabilization on or near the surface of BMS. It is hypothesized that the dehydration condensation of adjacent hydroxyl groups on the surface of the BMS is suppressed by the temperature change from room temperature (e.g., 25°C) to high temperature (e.g., 850°C or higher), preventing the collapse of the pore walls and suppressing the decrease in specific surface area. Since the ionic radius of the Al element replaces that of the Si element that constitutes the BMS, even a small amount of Al has the effect of preventing the collapse of the pore walls and suppressing the decrease in specific surface area, so a relatively small molar ratio (Al / SiO2) is preferable.

[0074] Each catalyst support in Comparative Example 1 is BMS, which is mesoporous silica having binary pores, and does not contain element M. Therefore, after a heat resistance test involving heat treatment at 900°C for 3 hours, the specific surface area retention rate is less than 10%, the specific surface area decreases, and it does not have heat resistance.

[0075] Example 19 Based on the molar amount of SiO2 in BMS, a mesoporous silica with binary pores, zirconium oxynitrate (ZrO(NO3)2) was dissolved in deionized water to obtain a liquid containing Zr ions, such that the molar ratio (Zr / SiO2) of Zr ions, in terms of metal equivalent, was 3.47 mol%. BMS was immersed in a Zr-containing liquid at room temperature (25°C ± 5°C) for 1 hour, the solvent water was removed by evaporation to dryness, and the BMS was dried at 60°C for 3 hours to obtain BMS with Zr attached. The Zr-attached BMS was heat-treated in an electric furnace at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) at 550°C for 3 hours to obtain the catalyst support of Example 19, which is BMS containing Zr with the molar ratio (M / SiO2) shown in Table 3. Table 3 also includes the mass % of Zr in metallic terms (M / SiO2 (mass%)) when the mass of SiO2 in the BMS is taken as 100 mass %.

[0076] Example 20 Based on the molar amount of SiO2 in BMS, a mesoporous silica with binary pores, potassium nitrate (KNO3) was dissolved in deionized water to obtain a liquid containing alkali metal (alk) ions, such that the molar ratio (alk / SiO2) was 0.077 mol% in terms of metal content. BMS was immersed in the liquid containing K ions at room temperature (25°C ± 5°C) for 1 hour, the solvent water was removed by evaporation to dryness, and the BMS was dried at 60°C for 3 hours to obtain BMS with attached K. The K-attached BMS was heat-treated in an electric furnace at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) for 3 hours at 550°C to obtain BMS containing K with the molar ratio (alk / SiO2) shown in Table 3. A BMS containing K was immersed in a Zr-containing liquid similar to that in Example 19, and in the same manner as in Example 19, a catalyst support for Example 20 was obtained, which was a BMS containing Zr in the molar ratio (M / SiO2) and K in the molar ratio (alk / SiO2) shown in Table 3. Table 3 also includes the mass % of K in terms of metal (alk / SiO2 (mass%)) when the mass of SiO2 in the BMS is taken as 100% by mass. Table 3 also indicates the contact sequence between the BMS, the alkali metal (alk) ion-containing liquid, and the metal (M) ion-containing liquid. If the BMS was contacted with the alkali metal (alk) ion-containing liquid, then heat-treated, and then contacted with the metal (M) ion-containing liquid, it is indicated in Table 3 as "alk, then M".

[0077] Example 21 Except for immersing BMS, a mesoporous silica having binary pores, in a liquid containing Zr, drying, and heat treatment, and then immersing it in a liquid containing K, drying, and heat treatment, the catalyst support of Example 21 was obtained in the same manner as in Example 20, with Zr in the molar ratio (M / SiO2) and K in the molar ratio (alk / SiO2) shown in Table 3. When the BMS was contacted with a liquid containing metal (M) ions and then heat-treated, and then contacted with a liquid containing alkali metal (alk) ions, it was indicated as "M, then alk" in Table 3.

[0078] Example 22 Based on the molar amount of SiO2 in BMS, a mesoporous silica composed of binary elements, zirconium oxynitrate (ZrO(NO3)2) was dissolved in deionized water so that the molar ratio of Zr ions (Zr / SiO2) was 3.47 mol% in terms of metal equivalent, and potassium nitrate (KNO3) was dissolved so that the molar ratio of alkali metal (alk) ions (alk / SiO2) was 0.077 mol% in terms of metal equivalent, to obtain a liquid containing Zr and K ions. BMS was immersed in this liquid containing Zr and K ions at room temperature (25°C ± 5°C) for 1 hour, the solvent water was removed by evaporation to dryness, and the liquid was dried at 60°C for 3 hours to obtain BMS with Zr and K attached. BMS coated with Zr and K was heat-treated in an electric furnace at 550°C for 3 hours at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) to obtain the catalyst support of Example 22, which is a BMS containing Zr in the molar ratio (M / SiO2) and K in the molar ratio (alk / SiO2) shown in Table 3. When the BMS was heat-treated after contact with a liquid containing metal (M) ions and alkali metal (alk) ions, it is indicated as "M and alk simultaneously" in Table 3.

[0079] Comparative Example 2 Based on the molar amount of SiO2 in BMS, a mesoporous silica having binary pores, potassium nitrate (KNO3) was dissolved in deionized water to obtain a liquid containing alkali metal (alk) ions, such that the molar ratio (alk / SiO2) was 0.077 mol% in terms of metal content. BMS was immersed in the liquid containing K ions at room temperature (25°C ± 5°C) for 1 hour, the solvent water was removed by evaporation to dryness, and the BMS was dried at 60°C for 3 hours to obtain BMS with attached K. The BMS with attached K was heat-treated in an electric furnace at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) for 3 hours at 550°C to obtain a catalyst support for Comparative Example 2, which contains K in the molar ratio (alk / SiO2) shown in Table 3 and does not contain element M.

[0080] Heat resistance test Each catalyst support in the examples and comparative examples was heat-treated in an electric furnace at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) for 3 hours at 1,000°C to perform a heat resistance test. The specific surface area of ​​each catalyst support before and after the heat resistance test was measured in the same manner as in Examples 1 to 18, and the specific surface area retention rate was measured. The results are shown in Table 3.

[0081] [Table 3]

[0082] Each catalyst support according to Examples 19 to 22 maintained a specific surface area retention rate of 20% or more even after a more severe heat resistance test than heat treatment at 1,000°C for 3 hours, indicating suppressed reduction in specific surface area and demonstrating heat resistance. Each catalyst support according to Examples 20 to 22, containing alk element in a molar ratio (alk / SiO2) of 0.01 mol% to 0.5 mol%, exhibits a higher specific surface area retention rate and higher heat resistance than the catalyst support according to Example 19, which does not contain alk element.

[0083] In a catalyst support, the alk element increases the amount of hydroxyl groups present on the BMS surface by cleaving oxygen bonds on the BMS surface, thereby increasing the electron density of oxygen atoms near the BMS surface and making it easier for them to bond with the M element. Furthermore, by including the alk element in the catalyst support, changes in temperature from room temperature (25°C) to high temperature (1,000°C) simultaneously cause changes in the Si-O-Si network due to dehydration condensation of BMS, and hydrolysis occurs, thereby suppressing the decrease in specific surface area due to the collapse of pore walls. In Example 20, the catalyst support, in which the alk element breaks the oxygen bonds on the surface of the BMS, increasing the amount of hydroxyl groups present on the surface of the BMS and increasing the electron density of oxygen atoms near the surface of the BMS, thereby facilitating bonding with the M element, was brought into contact with a liquid containing K ions before a liquid containing M ions, followed by drying and heat treatment. This resulted in a higher specific surface area retention rate for the catalyst support in Example 20 than for the catalyst support in Example 21. Furthermore, the catalyst support in Example 22, in which the BMS was brought into contact with a liquid containing both K and M ions, followed by drying and heat treatment, also showed a higher specific surface area retention rate than for the catalyst support in Example 20 or 21.

[0084] The catalyst support in Comparative Example 2 contains BMS and the element alk, but does not contain the element M. Therefore, after a heat resistance test involving heat treatment at 1,000°C for 3 hours, the specific surface area retention rate is less than 10%, indicating a decrease in specific surface area and a lack of heat resistance.

[0085] Examples 23, 24 In Example 13, platinum (Pt) was loaded onto a catalyst support, which was a Zr-containing BMS, by impregnation so that the amount of platinum loaded was 1% by mass. Specifically, the catalyst support was immersed in an aqueous solution of diaminedinitroplatinum(II) (Pt(NH3)2(NO3)2) to deposit 1% by mass of platinum onto the catalyst support. The solvent water was removed by evaporation to dryness, and the support was dried at 60°C for 3 hours to obtain a catalyst support with Pt attached. The catalyst support with Pt attached was heat-treated in an electric furnace at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) for 3 hours at 600°C to obtain a catalyst containing Zr and Pt in the molar ratio (M / SiO2) shown in Table 4. Table 4 also includes the mass percentage of Zr in metallic terms (M / SiO2 (mass%)) when the mass of SiO2 in the BMS is set to 100% by mass.

[0086] Comparative Examples 3 and 4 A catalyst containing platinum (Pt) was obtained by impregnation, similar to Examples 23 and 24, on the catalyst support, which is BMS of Comparative Example 1, so that the amount of platinum (Pt) supported was 1% by mass.

[0087] Heat resistance test Each catalyst in the examples and comparative examples was heat-treated in an electric furnace at atmospheric pressure (0.101 MPa) in an air atmosphere (oxygen content of 20 vol%) at 900°C for 3 hours, and then subjected to a heat resistance test.

[0088] Evaluation of catalytic activity After conducting a heat endurance test on each catalyst in the examples and comparative examples, the catalytic activity was measured. The heat endurance test was conducted using a quartz tube furnace, through which a gas consisting of 0.5 volume% oxygen (O2), 0.11 volume% propylene (C3H6), 10 volume% water vapor (H2O), and the remainder being nitrogen (N2) was circulated at 850°C for 15 hours through the catalyst placed in the aforementioned tubular furnace. For the catalytic activity measurement test, a fixed-bed flow reactor at atmospheric pressure was used. 0.1 g of each catalyst sample, sized to a particle size of 355 μm to 600 μm, was packed into a quartz glass reaction tube and fixed with quartz wool. As test gas, a composition of propylene (C3H6), carbon monoxide (CO), and nitrogen monoxide (NO) (C3H6-CO-NO) or pentane (C5H 12 ) with an air-fuel ratio (A / F) of 14.6, a composition of carbon monoxide (CO) and nitrogen monoxide (NO) (C5H 12 -CO-NO), a model gas as described below, was circulated so that the total flow rate was 1,000 cm 3 / min. The temperature of the gas flowing into the catalyst was gradually increased from 100 °C to 600 °C at a rate of 10 °C / min, and the catalytic activity at each temperature from 100 °C to 600 °C was evaluated. From the time when the introduction of the test gas into the reaction tube was started, the measurement of the CO2 concentration in the outlet gas after the test gas contacted the catalyst (after passing through the catalyst) was started, and the concentration of all propylene (C3H6) in the test gas was pentane (C5H 12 ) was measured by Fourier transform infrared spectroscopy (FT-IR), and the purification rate was determined based on the following formula (1). Purification rate = (X - Y) / X × 100 (1) (In the above formula (1), X represents the concentration of propylene (C3H6) or pentane (C5H 12 ) in the test gas when no catalyst is placed in the reaction tube, and Y represents the concentration of propylene (C3H6) or pentane (C5H 12 ) in the test gas when a catalyst is placed in the reaction tube.) The gas temperature at the inlet of the reaction tube when the purification rate reached 50% was measured as the light-off temperature T50 (°C). T50 (°C) was measured during the temperature increase. The results are shown in Table 4. [C3H6-CO-NO model gas] A model gas containing 3,000 volume ppm of carbon monoxide (CO), 1,500 volume ppmC of propylene (C3H6), 500 volume ppm of nitrogen monoxide (NO), 0.35 volume % of oxygen (O2), 14 volume % of carbon dioxide (CO2), 10 volume % of water vapor (H2O), and the balance being nitrogen (N2). [C5H 12 -CO-NO model gas] A model gas containing 3,000 volume ppm of carbon monoxide (CO), pentane (C5H12 A model gas consisting of 1,400 vol. ppm C, 500 vol. ppm nitric oxide (NO), 0.35 vol.% oxygen (O2), 14 vol.% carbon dioxide (CO2), 10 vol.% water vapor (H2O), and nitrogen (N2) as the remainder.

[0089] [Table 4]

[0090] The catalysts in Examples 23 and 24 had lower T50 temperatures than the catalysts in Comparative Examples 3 and 4, which used catalyst supports that did not contain element M. It was confirmed that they exhibited high heat resistance, with suppressed reduction in specific surface area even under harsh thermal environments of 850°C or higher. [Industrial applicability]

[0091] The catalyst support or catalyst according to this disclosure can maintain its pore structure and improve catalytic activity and further enhance heat resistance even when subjected to harsh thermal environments. Therefore, the catalyst support or catalyst according to this disclosure can be suitably used to purify exhaust gases emitted from internal combustion engines such as automobiles and motorcycles powered by gasoline or diesel engines. Furthermore, since the catalyst support or catalyst according to this disclosure has the characteristic of high heat resistance, it can be suitably used as a support for catalysts that react at high temperatures for long periods of time. Examples of suitable catalytic reactions include hydrogenation and dehydrogenation of hydrocarbons, oxidation treatment of organic solvents, high-temperature steam reforming, flameless combustion, and high-temperature denitrification of flue gas.

Claims

1. At least one metallic (M) element selected from the group consisting of aluminum, zirconium, and lanthanide elements, It contains mesoporous silica, The mesoporous silica, in the pore size distribution curve of the mesoporous silica obtained by analyzing the adsorption-side isotherm of the nitrogen adsorption isotherm by the DH method, has one or more peaks in the range of pore size between 1 nm and 5 nm and between 10 nm and 50 nm, respectively. The SiO of the aforementioned mesoporous silica ２ The molar ratio (M / SiO) of the molar amount of the metal (M) element, based on the molar amount of the aforementioned metal (M) ２ A catalyst support having a concentration of 0.01 mol% or more and 15.0 mol% or less.

2. The aforementioned metal (M) element includes aluminum (Al) element, and the mesoporous silica contains SiO ２ The molar ratio of the molar amount of aluminum (Al) element (Al / SiO2) is based on the molar amount of the above. ２ The catalyst carrier according to claim 1, wherein the amount is in the range of 0.02 mol% or more and 5.0 mol% or less.

3. The aforementioned metal (M) element includes the element zirconium (Zr), and the mesoporous silica contains SiO ２ The molar ratio of the molar amount of zirconium (Zr) element (Zr / SiO2) is based on the molar amount of the above. ２ The catalyst carrier according to claim 1, wherein the amount is in the range of 0.02 mol% or more and 6.0 mol% or less.

4. The metal (M) element comprises at least one selected from the group consisting of lanthanide (Ln) elements, and the mesoporous silica contains SiO ２ The molar ratio of the molar amounts of the lanthanide (Ln) element (Ln / SiO2) is based on the molar amount of the lanthanide (Ln) element. ２ The catalyst carrier according to claim 1, wherein the amount is in the range of 0.02 mol% or more and 3.0 mol% or less.

5. A catalyst carrier according to claim 1, comprising an alkali metal element.

6. Based on the molar amount of SiO of the mesoporous silica, the molar ratio (alk / SiO ２ ) of the molar amount of the alkali metal (alk) element is within the range of 0.01 mol% or more and 0.5 mol% or less. The catalyst support according to claim 5. ２ ​

7. A catalyst comprising a catalyst carrier according to any one of claims 1 to 6 and a noble metal.

8. The pore size distribution curve of mesoporous silica obtained by analyzing the adsorption-side isotherm of the nitrogen adsorption isotherm using the DH method has one or more peaks in the range of pore size from 1 nm to 5 nm and from 10 nm to 50 nm, respectively. The mesoporous silica is brought into contact with a liquid containing at least one metal (M) ion selected from the group consisting of aluminum ions, zirconium ions, and lanthanide ions. A method for producing a catalyst carrier, comprising: heat-treating the mesoporous silica, which has been in contact with a liquid containing the metal (M) ions, at a temperature of 400°C to 700°C to obtain a catalyst carrier comprising the metal (M) element consisting of the metal (M) ions and the mesoporous silica.

9. A method for producing a catalyst carrier according to claim 8, comprising contacting the mesoporous silica with a liquid containing alkali metal (alk) ions.

10. A method for producing a catalyst carrier according to claim 9, comprising contacting the mesoporous silica with a liquid containing alkali metal (alk) ions before performing the heat treatment.

11. The metal (M) ions are calculated based on the molar amount of SiO2 in the mesoporous silica that is brought into contact with the liquid, and the molar ratio of the metal (M) ions (M / SiO2) is calculated accordingly. ２ A method for producing a catalyst carrier according to claim 8, wherein the liquid contains ) in an amount of 0.01 mol% or more and 15.0 mol% or less.

12. The alkali metal (alk) ions come into contact with the SiO of the mesoporous silica that is brought into contact with the liquid. ２ Based on the molar amount of the above alkali metal (alk) ions, the molar ratio (alk / SiO) on a metal basis is calculated. ２ A method for producing a catalyst carrier according to claim 9, wherein the carrier is contained in the liquid in an amount of 0.01 mol% or more and 0.5 mol% or less.

13. The method for producing a catalyst carrier according to claim 8, wherein the metal ion includes a zirconium (Zr) ion.

14. The method for producing a catalyst carrier according to claim 9, wherein the alkali metal ion includes potassium (K) ions.

15. A method for producing a catalyst carrier according to claim 8, comprising drying the mesoporous silica that has been in contact with the liquid at a temperature of 20°C to 200°C, after contacting it with the liquid and before the heat treatment.

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