Molded article containing silica alumina and method for manufacturing the same

Abstract

To provide a molded article that can support a larger amount of active metal in high dispersion and obtain the desired product in high yield. To provide a silica-alumina molded article and a method for producing the same that have sufficient mechanical strength and exhibit sufficient performance in terms of activity without relying on zeolite. [Solution] This molded body contains silica alumina, and in the pore distribution measured by nitrogen gas adsorption, the total pore volume (PV(N2)) is 0.8 to 2.0 ml / g, and the ratio of the pore volume at a pore diameter of 10 to 100 nm to the total pore volume is 30 to 80%. Because this molded body has an appropriate pore distribution and sufficient pore volume, which are the reaction sites, a sufficient amount of active metal can be supported in high dispersion, and the desired product can be obtained in high yield without overreaction.

Description

[Technical Field]

[0001] The present invention relates to a molded article containing silica-alumina for hydrogenation catalysts and a method for producing the same. [Background technology]

[0002] In recent years, various research and development projects have been underway related to new processes aimed at carbon neutrality, chemical recycling, and the creation of new energy sources. Among these, fixed-bed catalysts are used in a variety of applications, such as hydrogenation, decomposition, isomerization, deoxygenation, and adsorption. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Special Publication No. 2017-518171 [Patent Document 2] Japanese Patent Publication No. 2023-081115 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Fixed-bed catalysts require optimization of pore structure, increased load of active metal, and high dispersion to efficiently advance the reaction. For example, Patent Document 1 discloses a base extruded material containing molecular sieves, alumina, and an amorphous silica-alumina support. This base extruded material is disclosed to have a nanopore volume of 0.5 to 0.9 cc / g in the range of 6 to 11 nm. Patent Document 2 also discloses a support for inorganic composite oxides for the hydrogenation of hydrocarbon oils, containing aluminum, silicon, and an amorphous inorganic composite oxide of element M (where element M is at least one of phosphorus, titanium, zirconium, and magnesium), and a zeolite. The pore volume of this support obtained by mercury intrusion is preferably 0.60 mL / g or more, and the examples disclose a support having a pore volume of 0.67 to 0.80 mL / g.

[0005] Zeolites have a higher Brønsted acid content and greater decomposition activity compared to amorphous silica-alumina, and are therefore used as hydrocracking catalysts, for example, as described in Patent Document 1. While a high concentration of zeolite in the catalyst improves decomposition activity, it can lead to excessive decomposition or side reactions, making it difficult to obtain the desired product. Furthermore, the bulkiness of zeolite itself can prevent dense molding, potentially reducing mechanical strength. On the other hand, the support material described in Patent Document 2 has insufficient pore volume, resulting in insufficient loading of active metals such as molybdenum, nickel, and cobalt, making it difficult to obtain the desired activity. Therefore, a molded body with an appropriate pore distribution and sufficient pore volume is needed, which can support a larger amount of active metal in high dispersion and obtain the desired product in high yield. [Means for solving the problem]

[0006] To address these challenges, we have discovered a molded body containing silica-alumina as described below. This molded body contains silica-alumina, and in the pore distribution measured by nitrogen gas adsorption, the total pore volume (PV(N2)) is 0.8 to 2.0 ml / g, and the ratio of the pore volume at pore diameters of 10 to 100 nm to the total pore volume is 30 to 80%.

[0007] Hereafter, this molded body containing silica-alumina may simply be referred to as a "molded body."

[0008] This molded body has an appropriate pore distribution and sufficient pore volume, which are the reaction sites. In other words, the desired product can be obtained in high yield without overreaction. [Effects of the Invention]

[0009] The molded body of the present invention can obtain desired products in high yield without overreacting as a fixed-bed catalyst. For example, it can be used in hydrogenation purification, decomposition reactions, isomerization reactions, deoxygenation reactions, and various other applications such as adsorption reactions. [Modes for carrying out the invention]

[0010] [Silica-alumina molded body] The molded body according to the present invention will be described.

[0011] The molded body of the present invention is a molded body containing silica-alumina. In pore distribution measurement by nitrogen gas adsorption method, the total pore volume (PV(N₂)) of the molded body is 0.8 to 2.0 ml / g. Further, the ratio of the pore volume with a pore diameter of 10 to 100 nm to the total pore volume of the molded body is 30 to 80%.

[0012] The silica-alumina contained in the molded body may be amorphous, crystalline, or a mixture of the two, as long as the properties as a molded body are satisfied. However, in consideration of moldability and properties related to pore distribution and pore volume, amorphous is preferred. Here, the term "amorphous" means that no diffraction peak having a half width of less than 1.0° in the range of 5° ≦ 2θ ≦ 50° is exhibited in an X-ray diffraction pattern.

[0013] The molded body may also contain materials other than silica-alumina. Examples of materials other than silica-alumina include: silicon compounds such as silica and diatomaceous earth; aluminas such as ρ-alumina, χ-alumina, γ-alumina, δ-alumina and θ-alumina; clay minerals such as kaolin and acid clay; inorganic oxides such as titania and zirconia; compounds containing sulfur or phosphorus; and organic substances.

[0014] It is preferable that the silica content of the molded body is 10 to 60% by mass in terms of SiO₂, and the alumina content is 40 to 90% by mass in terms of Al₂O₃.

[0015] When the silica content of the molded body is within this range, the adjustment of the pore structure, pore volume and the like for obtaining a target product is easy, and the preparation of the molded body is also facilitated.

[0016] Here, if the silica content is less than 10% by mass, there is a risk that the pore structure and the like for obtaining the target product cannot be maintained, and sufficient activity performance cannot be exhibited. Conversely, if the content exceeds 60% by mass, there is a risk that preparation of the molded article becomes difficult. This silica content is more preferably 20 to 55% by mass, still more preferably 30 to 50% by mass.

[0017] When the alumina content of the molded article falls within this range, it is easy to adjust the pore structure, pore volume and the like for obtaining the target product, and also facilitates preparation of the molded article.

[0018] Here, if the alumina content of the molded article is less than 40% by mass, there is a risk that sufficient pore volume cannot be satisfied, and sufficient activity performance cannot be exhibited. Conversely, if the content exceeds 90% by mass, there is a risk that the pore structure, pore volume and the like for obtaining the target product cannot be maintained. This alumina content is more preferably 45 to 80% by mass, still more preferably 50 to 70% by mass.

[0019] Meanwhile, the content of components (other components) other than "silica, alumina, and elements belonging to alkali metals and alkaline earth metals described later" contained in the molded article is preferably 1% by mass or less based on oxide. When the content of these "other components" falls within this range, it is possible to achieve both the desired pore structure and sufficient mechanical strength for use as a fixed bed catalyst.

[0020] In pore distribution measurement by the nitrogen gas adsorption method, when the total pore volume (PV(N₂)) of the molded article falls within this range, high retention ability for the target substance, high diffusibility of raw material molecules in the reaction, and high desorption property of the product can be obtained. For example, in a hydrorefining reaction, a sufficient amount of active metal can be supported, and the desired product can be obtained in a high yield.

[0021] Here, if the total pore volume (PV(N2)) of the molded body is less than 0.8 ml / g, it may be difficult to support a sufficient amount of active metal. For example, as shown in Comparative Example 1 described later, in a molded body with a smaller pore volume than that of the present invention, when supporting a predetermined amount of active metal, it may not be possible to support the target amount in a single loading operation, and it may be difficult to support a sufficient amount of active metal without repeating this operation multiple times. Alternatively, even if the loading operation is repeated multiple times, the amount of metal that can be loaded may reach a so-called "plateau," and it may not be possible to support a sufficient amount of active metal. Furthermore, in the reaction, it may be difficult for the raw material molecules to diffuse into the pores and for the reaction products to desorb. Conversely, if it exceeds 2.0 ml / g, the mechanical strength of the molded body may be insufficient. This total pore volume is preferably 0.9 to 1.9 ml / g, more preferably 1.0 to 1.8 ml / g.

[0022] In pore distribution measurements using nitrogen gas adsorption, the ratio of pore volume with a pore diameter of 10-100 nm to the total pore volume of the molded body is 30-80%. When the pore volume ratio falls within this range, high retention capacity for the target substance, high diffusivity of the raw material molecules in the reaction, and high desorption of the product can be obtained. For example, in hydrogenation purification reactions, a sufficient amount of active metal can be supported, and the desired product can be obtained in high yield.

[0023] If the pore volume ratio is less than 30%, it becomes difficult to support a sufficient amount of active metal, and it may be difficult to obtain the desired product in high yield. Conversely, if it exceeds 80%, it becomes difficult to obtain the desired product in higher yield, and the mechanical strength of the molded article may be insufficient. The pore volume ratio is preferably 35-75%, more preferably 40-70%.

[0024] In pore distribution measurement by mercury intrusion, the total pore volume (PV(Hg)) of the molded body is preferably 1.0 to 1.9 ml / g. When the total pore volume (PV(Hg)) is within this range, high retention capacity of the target substance, high diffusivity of the raw material molecules in the reaction, and high desorption of the product can be obtained. For example, in a hydrogenation purification reaction, a sufficient amount of active metal can be supported, and the desired product can be obtained in high yield.

[0025] Here, if the total pore volume (PV(Hg)) of the molded body is less than 1.0 ml / g, it may be difficult to support a sufficient amount of active metal. As mentioned above, for example, in a molded body with a smaller pore volume than the present invention, as shown in Comparative Example 1 described later, when supporting a predetermined amount of active metal, it may not be possible to support the target amount in a single loading operation, and it may be difficult to support a sufficient amount of active metal unless this operation is repeated multiple times. Alternatively, even if the loading operation is repeated multiple times, the amount of metal that can be loaded may reach a so-called "plateau," and it may not be possible to support a sufficient amount of active metal. Furthermore, in the reaction, it may be difficult for the raw material molecules to diffuse into the pores. Conversely, if it exceeds 1.9 ml / g, the mechanical strength of the molded body may be insufficient. This total pore volume is preferably 1.1 to 1.9 ml / g, more preferably 1.2 to 1.8 ml / g.

[0026] In pore distribution measurements using the mercury intrusion method, the pore volume of a molded body with a pore diameter of 100-2000 nm is 0.3-0.9 ml / g relative to the total pore volume. When the pore volume is within this range, high retention capacity for the target substance, high diffusivity of the starting material molecules in the reaction, and high desorption of the product can be obtained. For example, in hydrogenation purification reactions, a sufficient amount of active metal can be supported, and the desired product can be obtained in high yield.

[0027] If this pore volume is less than 0.3 ml / g, it becomes difficult to support a sufficient amount of active metal, and it may be difficult to obtain the desired product in high yield. Conversely, if it exceeds 0.9 ml / g, it becomes difficult to obtain the desired product in higher yield, and the mechanical strength of the molded article may be insufficient. This pore volume is preferably 0.4 to 0.85 ml / g, more preferably 0.5 to 0.8 ml / g.

[0028] In pore distribution measurement by mercury intrusion, it is preferable that the ratio of pore volume in the pore diameter range of 2000 to 10000 nm to the total pore volume (PV(Hg)) of the molded body is 2% or less. When the ratio of pore volume is within this range, a sufficient amount of active metal can be supported, the desired product can be obtained in high yield, and sufficient mechanical strength can be obtained.

[0029] If the pore volume ratio exceeds 2%, the dispersibility of the active metal on the molded body decreases, which may make it difficult to obtain the desired product in high yield. It may also become difficult to obtain sufficient mechanical strength. The pore volume ratio is more preferably 1% or less, even more preferably 0.5%, and most preferably 0%.

[0030] The specific surface area of ​​the molded body, as measured by nitrogen gas adsorption, is 300-550 m². 2 It is preferable that the specific surface area is within this range. When the specific surface area is within this range, the active metal can be supported in a highly dispersed manner, and the desired product can be obtained in high yield.

[0031] Here, the specific surface area is 300 m². 2 If the amount is less than / g, the contact ratio with the substance is low, which may result in insufficient contact and reactivity with the target substance. Conversely, 550m 2 If the specific surface area exceeds 1 / g, the pore size may be too small, potentially resulting in insufficient retention of the target substance and poor diffusion of the starting material molecules during the reaction. This specific surface area is more preferably 350-500 m². 2 / g, more preferably 370-450m 2It is / g.

[0032] The water absorption of the molded body, as measured by the pore-filling method, is preferably 1.2 ml / g or more. When the water absorption is within this range, a large amount of active metal can be supported, and the diffusion of raw material molecules into the pores is facilitated, allowing the desired product to be obtained in high yield.

[0033] Here, if the water absorption is less than 1.2 ml / g, it may be difficult to support a sufficient amount of activated metal. As mentioned above, for example, in a molded body with a smaller pore volume than the present invention, as shown in Comparative Example 1 described later, when supporting a predetermined amount of activated metal, it may not be possible to support the target amount in a single loading operation, and it may be difficult to support a sufficient amount of activated metal unless this operation is repeated multiple times. Alternatively, even if the loading operation is repeated multiple times, the amount of activated metal may reach a so-called "plateau," and it may not be possible to support a sufficient amount of activated metal. Furthermore, in the reaction, it may be difficult for the raw material molecules to diffuse into the pores. The upper limit of water absorption is not particularly set as long as sufficient mechanical strength of the molded body is obtained, but for example, it is 2.5 ml / g. This water absorption is more preferably 1.3 to 2.2 ml / g, and even more preferably 1.4 to 2.2 ml / g.

[0034] The crush strength of the molded body is preferably 5.0 N / mm or higher. A crush strength within this range indicates that the molded body possesses sufficient mechanical strength for use as a fixed-bed catalyst.

[0035] If the crushing strength is less than 5.0 N / mm, it may be difficult to pack the catalyst while maintaining its shape when used in a fixed-bed catalyst. Furthermore, even if packing is possible, it may result in an unevenly packed bed. In such a state, uneven flow of raw materials may occur during the reaction, or over-reaction or insufficient reaction may occur, making stable operation impossible. The crushing strength is more preferably 6.0 N / mm or more, and even more preferably 7.0 N / mm or more.

[0036] A pulverization rate of 5.0% or less is preferable for the molded body. When the pulverization rate is within this range, the molded body possesses sufficient mechanical strength for use as a fixed-bed catalyst.

[0037] If the pulverization rate exceeds 5.0%, it becomes difficult to pack the catalyst while maintaining its shape when used in a fixed-bed catalyst. Furthermore, even if packing is possible, there is a risk of an uneven packed bed. In such a state, differential pressure will occur, which may lead to uneven flow of the raw materials in the reaction, or over-reaction or insufficient reaction, making stable operation impossible. The pulverization rate is more preferably 4.0% or less, and even more preferably 3.0% or less.

[0038] Molded body 29 In the waveforms separated by Si-NMR spectroscopy, it is preferable that (Q1 / ΣQ) × 100 is 10% or more in the peak area Q1 appearing at chemical shifts of -70 to -95 ppm, peak area Q2 appearing at chemical shifts of -80 to -100 ppm, peak area Q3 appearing at chemical shifts of -85 to -115 ppm, and peak area Q4 appearing at chemical shifts of -95 to -125 ppm. Here, ΣQ = Q1 + Q2 + Q3 + Q4.

[0039] The peaks assigned to Q1 represent Si atoms with one (-OSi) group and three (-OH) groups bonded to them, the peaks assigned to Q2 represent Si atoms with two (-OSi) groups and two (-OH) groups bonded to them, the peaks assigned to Q3 represent Si atoms with three (-OSi) groups and one (-OH) group bonded to them, and the peaks assigned to Q4 represent Si atoms with four (-OSi) groups bonded to them. If the ratio of (Q1 / ΣQ) is within this range, the bonding affinity with Al atoms is high, and a relatively large amount of Brønstedt acid (B acid) can be obtained. There is no specific upper limit set for the ratio of (Q1 / ΣQ), but when used for hydrogenation purification reactions, for example, it is 25%.

[0040] Here, if the ratio of (Q1 / ΣQ) is less than 10%, there will be fewer silanol groups and a higher bonding affinity with Al atoms, which may result in an excessive amount of B acid. The ratio of (Q1 / ΣQ) is more preferably 13% or more, and even more preferably 15% or more.

[0041] Molded body 27 In Al-NMR spectroscopy analysis, it is preferable that the ratio ((I5+I6) / I4) of the sum of the peak area representing the 5-coordinate structure (I5), which has a maximum chemical shift between 50.0 and 20.0 ppm, and the peak area representing the 6-coordinate structure (I6), which has a maximum chemical shift between 20.0 and -30.0 ppm, to the peak area representing the 4-coordinate structure (I4), which has a maximum chemical shift between 80.0 and 50.0 ppm, is between 3.5 and 6.0. If the ratio ((I5+I6) / I4) is within this range, the desired product can be obtained in high yield.

[0042] Here, if the ratio ((I5+I6) / I4) is less than 3.5, the silica-alumina bonding is too strong, which may lead to over-decomposition and make it difficult to obtain the desired product in high yield. Conversely, if it exceeds 6.0, the silica-alumina bonding is too weak, resulting in insufficient decomposition activity and making it difficult to obtain the desired product in high yield. The ratio ((I5+I6) / I4) is more preferably 3.5 to 5.5, and even more preferably 3.5 to 5.0.

[0043] The amount of nitric oxide adsorbed by the molded body is measured for molded bodies on which 16.0% by mass of molybdenum as MoO3 and 4.0% by mass of nickel as NiO are supported as active metals, or 24.0% by mass of molybdenum as MoO3 and 6.0% by mass of nickel as NiO are supported. More specifically, the molded bodies on which these active metals are supported are heated to 550°C, and then subjected to sulfidation treatment by passing a mixed gas of hydrogen sulfide and hydrogen (5% by volume of hydrogen sulfide + 95% by volume of hydrogen) at 360°C before measurement. Preferably, the amount of nitric oxide adsorbed is 6.0 ml / g or more for the molded body on which 16.0% by mass of molybdenum as MoO3 and 4.0% by mass of nickel as NiO are supported, and 7.0 ml / g or more for the molded body on which 24.0% by mass of molybdenum as MoO3 and 6.0% by mass of nickel as NiO are supported. If the amount of nitric oxide adsorbed is within this range, the active metal is highly dispersed on the molded body, increasing the reaction site and allowing the desired product to be obtained in high yield. There is no specific upper limit set for this amount of nitric oxide adsorbed, but for example, when used for the hydrochemical refining of hydrocarbon oils, if 16.0 mass% of molybdenum as MoO3 and 4.0 mass% of nickel as NiO are supported, the amount is, for example, 8.0 ml / g. If 24.0 mass% of molybdenum as MoO3 and 6.0 mass% of nickel as NiO are supported, the amount is, for example, 9.0 ml / g.

[0044] In a molded article containing 16.0% by mass of molybdenum as MoO3 and 4.0% by mass of nickel as NiO, if the nitric oxide adsorption amount is less than 6.0 ml / g, the dispersibility of the active metal on the molded article will be low, which may make it difficult to obtain the desired product in high yield. The nitric oxide adsorption amount is more preferably 6.0 to 8.0 ml / g, and even more preferably 7.0 to 8.0 ml / g.

[0045] Furthermore, in a molded article supporting 24.0% by mass of molybdenum as MoO3 and 6.0% by mass of nickel as NiO, if the amount of nitric oxide adsorbed is less than 7.0 ml / g, the dispersibility of the active metal on the molded article will be low, which may make it difficult to obtain the desired product in high yield. The amount of nitric oxide adsorbed is more preferably 7.0 to 9.0 ml / g, and even more preferably 8.0 to 9.0 ml / g.

[0046] Molded articles may contain elements belonging to alkali metals and alkaline earth metals as impurities. If even one of these elements is present in a large amount, heating the molded article may clog its pores. The total content of elements belonging to alkali metals and alkaline earth metals, when expressed as oxides, is preferably less than 0.1% by mass, more preferably less than 0.08% by mass, and even more preferably less than 0.05% by mass relative to the molded article. Alkali metals refer to Li, Na, K, Rb, Cs, and Fr, while alkaline earth metals refer to Be, Mg, Ca, Sr, Ba, and Ra.

[0047] The shape of the molded body is not particularly limited as long as it is used for fixed floors. Examples include cylindrical, prismatic, trilobed, quadrupedal pellets, spherical, tablet, and honeycomb shapes.

[0048] [Method for manufacturing molded products] The method for manufacturing a molded article according to the present invention is not particularly limited as long as it satisfies the aforementioned properties of the molded article. For example, a manufacturing method may include a first step of preparing silica alumina, a second step of mixing the silica alumina with a binder containing an aluminum element to produce a mixture, a third step of adjusting the moisture content of the mixture and molding it to produce a molded article, and a fourth step of heating the molded article.

[0049] The molded body produced in this manner contains silica-alumina and has an appropriate pore distribution and pore volume. It also possesses sufficient mechanical strength for use as a fixed-bed catalyst. Therefore, it can be used as a fixed-bed catalyst, and the desired product can be obtained in high yield without overreaction. Each step is described below.

[0050] [First step] First, silica-alumina is prepared. Here, as mentioned above, this silica-alumina may be amorphous, crystalline, or a mixture of both, as long as it satisfies the properties of a molded body, but amorphous is preferable. Amorphous silica-alumina has a higher bulk density than crystalline silica-alumina such as zeolite, resulting in higher moldability and higher mechanical strength as a molded body. As this silica-alumina, for example, the silica-alumina disclosed in the examples of Japanese Patent Application Publication No. 2023-137463 filed by the applicant of the present invention can be used.

[0051] This silica-alumina preferably contains 2 to 70% by mass of silica as SiO2 and 30 to 98% by mass of alumina as Al2O3.

[0052] When the SiO2 content of silica-alumina is within this range, it becomes easier to adjust the pore structure and pore volume to obtain the desired product when forming a molded article, and the preparation of the molded article becomes easier.

[0053] Here, if the SiO2 content is less than 2% by mass, the pore structure and other properties necessary to obtain the desired product may not be maintained when forming the molded article, and sufficient activity performance may not be achieved. Conversely, if it exceeds 70% by mass, the moldability will decrease, and it may become difficult to prepare the molded article. The SiO2 content is more preferably 10 to 65% by mass, and even more preferably 10 to 50% by mass.

[0054] When the Al2O3 content of silica-alumina is within this range, it becomes easier to adjust the pore structure and pore volume to obtain the desired product when forming a molded article, and the preparation of the molded article becomes easier.

[0055] Here, if the Al2O3 content of silica alumina is less than 30% by mass, the moldability will decrease, and it may become difficult to prepare the molded article. Also, the pore volume in the molded article may not be satisfactory, and it may not be able to exhibit sufficient activity. Conversely, if it exceeds 98% by mass, it may become impossible to maintain the pore structure and pore volume of the molded article necessary to obtain the desired product. The Al2O3 content is more preferably 35 to 90% by mass, and even more preferably 50 to 90% by mass.

[0056] The total content of alkali metals and alkaline earth metals in silica-alumina is preferably 0.1% by mass or less when expressed as an oxide. When the total content of alkali metals and alkaline earth metals is within this range, acid spot poisoning by acid B is suppressed. Furthermore, it facilitates the adjustment of impurities in the final molded product.

[0057] Here, if the total content of alkali metals and alkaline earth metals in silica alumina exceeds 0.1% by mass, there is a risk that the amount of B acid in the final molded body will be insufficient, or that heating the molded body may clog its pores. The total content of alkali metals and alkaline earth metals is more preferably 0.05% by mass or less, and even more preferably 0.03% by mass or less.

[0058] In pore distribution measurement by nitrogen gas adsorption, the total pore volume (PV(N2)) of the silica-alumina is preferably 1.0 to 2.2 ml / g. When the total pore volume is within this range, a sufficient amount of active metal can be supported in the molded article, and the desired product can be obtained in high yield.

[0059] Here, if the total pore volume (PV(N₂)) of silica-alumina is less than 1.0 ml / g, it may be difficult to support a sufficient amount of active metal in the molded article. Conversely, if the total pore volume exceeds 2.2 ml / g, there is a risk that moldability will decrease, making it difficult to prepare the molded article, or the mechanical strength of the molded article may become insufficient. This total pore volume is more preferably 1.3 to 2.0 ml / g, and still more preferably 1.4 to 1.9 ml / g.

[0060] In pore distribution measurement by the nitrogen gas adsorption method, the ratio of the pore volume in the pore diameter range of 10 to 100 nm to the total pore volume of silica-alumina is preferably 50% or more. When the ratio of this pore volume falls within this range, a sufficient amount of active metal can be supported on the molded article, and the desired product can be obtained in high yield. The upper limit of this pore volume ratio is not particularly limited as long as sufficient mechanical strength of the molded article can be obtained, and is, for example, 80%. This pore volume ratio is more preferably 55% or more, and still more preferably 60% or more.

[0061] The specific surface area of silica-alumina measured by the nitrogen gas adsorption method is 400 to 600 m 2 / g, which is preferable. When the specific surface area falls within this range, a molded article produced using this silica-alumina can highly disperse and support the active metal, and the desired product can be obtained in high yield.

[0062] Here, if the specific surface area is less than 400 m 2 / g, the contact ratio with the target substance is low, so the contact property and reactivity of a molded article produced using this silica-alumina to the target substance may be insufficient. Conversely, if it exceeds 600 m 2 / g, the pore diameter of the molded article produced using this silica-alumina is too small, which may lead to insufficient retention capacity for the target substance and insufficient diffusivity of raw material molecules during the reaction. This specific surface area is more preferably 400 to 550 m 2 / g, still more preferably 420 to 500 m 2 / g.

[0063] The silica-alumina is preferably in at least one form selected from powder, particulate, slurry, and colloidal. Furthermore, its average particle size is preferably 150 μm or less. When the average particle size is within this range, moldability is high, and the voids between particles can be reduced, thus improving mechanical strength.

[0064] Here, if the average particle diameter exceeds 150 μm, the voids between particles become larger, which may reduce the mechanical strength. There is no specific lower limit set for the average particle diameter, but for example, it is 0.1 μm. If the average particle diameter is less than 0.1 μm, the voids between particles become smaller, which may reduce the pore volume of the molded body and make it difficult for raw material molecules to diffuse into the pores. This average particle diameter is more preferably 0.5 to 130 μm, and even more preferably 1 to 110 μm.

[0065] [Second process] In the first step, a binder containing aluminum is mixed with silica-alumina to create a mixture. Here, examples of binders containing aluminum include at least one selected from alumina-based sols, aluminates, boehmite, pseudoboehmite, and aluminum compounds.

[0066] Examples of alumina-based sols include alumina sols and silica-alumina sols.

[0067] As the aluminate, one or more aluminates selected from alkali metal aluminates, ammonium aluminates, and organic base aluminates are preferred. Examples of alkali metal aluminates include sodium aluminate and potassium aluminate. Examples of organic bases include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. Ammonium aluminates or organic base aluminates also include alkaline solutions obtained by adding ammonia, quaternary ammonium hydroxide, amine compounds, etc., to an aluminic acid solution.

[0068] Examples of aluminum compounds include aluminum sulfate, aluminum nitrate, aluminum phosphate, polyaluminum chloride, and aluminum fatty acid.

[0069] Incidentally, the amount of "aluminum element binder" to be mixed is preferably 50% by mass or less on an oxide basis, relative to the total amount with silica-alumina prepared in the first step. When the amount of binder is within this range, it is easy to adjust the pore structure and pore volume, etc., to obtain the desired product.

[0070] Here, if the amount of binder containing aluminum exceeds 50% by mass, it may become difficult to adjust the pore structure and pore volume, etc., in order to obtain the desired product. There is no particular lower limit for the amount of binder as long as the properties of the molded article of the present invention are satisfied, but in order to more stably reproduce the mechanical strength, etc., of the molded article, it is, for example, 1% by mass. If it is less than 1% by mass, the effect of using the binder may not be realized. The amount of "binder containing aluminum" to be mixed is more preferably 1 to 30% by mass, and even more preferably 2 to 20% by mass.

[0071] In the second step, materials other than the silica-alumina and "binder containing aluminum elements" prepared in the first step described above may be mixed. These materials allow for adjustment of the pore distribution, pore volume, and mechanical strength of the molded body, but at a minimum, they should satisfy the characteristics related to the pore distribution and pore volume of the final molded body, as well as the crush strength necessary to maintain the molded body.

[0072] Other materials besides silica-alumina and the "binder containing aluminum element" include, for example, silicon compounds such as silica and diatomaceous earth, alumina such as ρ-alumina, χ-alumina, γ-alumina, δ-alumina, and θ-alumina, clay minerals such as kaolin and acid clay, inorganic oxides such as titania and zirconia, and organic substances such as cellulose, methylcellulose, cellulose ether, starch, polyvinyl alcohol, curdlan, citric acid, malic acid, oleic acid, and stearic acid. These materials can also be added when producing the molded product in the third step, which will be described later.

[0073] Incidentally, the amount of materials other than "silica alumina and 'binder containing aluminum elements'" to be mixed is preferably 10.0 parts by mass or less on a dry basis, relative to 100 parts by mass of the total of silica alumina and "binder containing aluminum elements" prepared in the first step. When the amount of this material is within this range, it is possible to achieve both good moldability and the formation of the desired pore structure.

[0074] Here, if the amount of materials other than "silica alumina and 'binder containing aluminum elements'" to be mixed exceeds 10.0 parts by mass, it may become difficult to form the molded article. There is no particular lower limit set for the amount of materials other than "silica alumina and 'binder containing aluminum elements'" to be mixed, as long as the properties of the molded article of the present invention are satisfied, but for example, it is 0.5 parts by mass. If it is less than 0.5 parts by mass, the effect of mixing the "material" may not be achieved. The amount of materials other than "silica alumina and 'binder containing aluminum elements'" to be mixed is more preferably 1.0 to 8.0 parts by mass, and even more preferably 2.0 to 5.0 parts by mass, based on the dry weight.

[0075] In order to reduce the content of impurities such as alkali metals and alkaline earth metals in the molded product, it is preferable to reduce the content of these impurities in the mixture.

[0076] The methods for achieving this include reducing the impurity content of the materials to be mixed beforehand through cleaning operations such as acid treatment or ion exchange, reducing the impurity content after mixing through cleaning operations such as acid treatment or ion exchange, or combining both. Of course, it is also possible to perform cleaning after the third step, which will be described later, but performing it in the second step is more production efficient.

[0077] [Third step] In this process, the moisture content of the mixture is adjusted, and then it is molded to produce a molded product.

[0078] In molding, conventionally known equipment such as extrusion molding machines and tablet molding machines can be used. In the case of tablet molding, it is preferable to use a method in which granular molding precursor is set in a tablet molding machine and a constant pressure is applied. The shape of the molded body obtained can be determined by the shape of the cylinder used in this process. In the case of extrusion molding, it is preferable to use a molding precursor with adjusted moisture content in, for example, a single-screw auger type extrusion molding machine or a disc pelletizer. The shape of the molded body obtained can be determined by the shape of the die used in this process.

[0079] The moisture content of the molding precursor is preferably 10 to 70% by mass. When the moisture content is within this range, a molded body with sufficient mechanical strength for use with a fixed-bed catalyst and the desired pore distribution is obtained.

[0080] Here, if the moisture content is less than 10% by mass, molding becomes difficult, and there is a risk that a molded product cannot be obtained. Conversely, if it exceeds 70% by mass, there is a risk that the molded product will not have sufficient mechanical strength and the desired pore distribution. This moisture content is more preferably 10 to 68% by mass, and even more preferably 10 to 66% by mass.

[0081] [Fourth step] In this step, the molded product is heated.

[0082] Conventional equipment such as box-type firing furnaces and rotary kilns can be used for heating. The heating temperature is preferably between 100 and 700°C. When the heating temperature is within this range, a molded body with sufficient mechanical strength for use as a fixed-bed catalyst is ultimately obtained.

[0083] Here, if the heating temperature is below 100°C, the mechanical strength of the molded body may be insufficient, or the pore structure necessary for the desired reaction may not be obtained. Conversely, if it exceeds 700°C, the pore structure and pore volume necessary for the desired reaction may not be obtained. The heating temperature is more preferably 350 to 700°C, and even more preferably 500 to 700°C.

[0084] The following describes embodiments of the present invention.

[0085] [Example 1] <Preparation of silica alumina (ASA1) (first step)> Silica alumina (ASA1) was prepared based on the method disclosed in Japanese Patent Application Publication No. 2023-137463, filed by the applicant of the present invention. Specifically, first, 120 kg of 50°C hot water was placed in a 200 L stainless steel tank with a steam jacket. While maintaining the temperature inside the tank at 50°C and stirring the hot water, 248 g of a 25% by mass sodium gluconate aqueous solution was added, followed by 1.77 kg of a sodium aluminate aqueous solution (manufactured by JGC Catalysts & Chemicals Co., Ltd., Al2O3 equivalent concentration 22% by mass). Subsequently, 2.95 kg of an aluminum sulfate aqueous solution (manufactured by JGC Catalysts & Chemicals Co., Ltd., Al2O3 equivalent concentration 7% by mass) was added to prepare a pseudoboehmite precursor slurry. While stirring this pseudoboehmite precursor slurry, 16.10 kg of sodium aluminate aqueous solution and 29.80 kg of aluminum sulfate aqueous solution were simultaneously added over 40 minutes to obtain a pseudoboehmite slurry. Next, while stirring the pseudo-boehmite slurry, 3.85 kg of sodium aluminate aqueous solution was added, and the mixture was heated at 50°C for 2 hours while stirring. Then, 0.53 kg of 15% by mass aqueous ammonia was added and stirred, and after dewatering with a plate filter, the filtration residue was washed with 60°C hot water to obtain a washing cake. This washing cake was reduced in slurry to a solid content concentration of 7.2% by mass to obtain a pseudo-boehmite washing slurry. Next, 0.27 kg of 15% by mass aqueous ammonia was added to 22.44 kg of this washing slurry and stirred, and then silica particles (average particle size 12 μm, BET specific surface area 480 m²) were added. 2 3.27 kg of a dispersion of (SiO2 equivalent concentration 33% by mass) of ( / g) was added and aged at 70°C for 2 hours while stirring. The resulting aged slurry was dispersed in a homogenizer and dried in a spray dryer with an inlet temperature of 270°C and an outlet temperature of 130°C to obtain ASA1. The properties of ASA1 are shown in Table 1.

[0086] <Manufacturing of molded products> Silica alumina (ASA1, Al2O3 equivalent concentration 57% by mass, average particle size 103 μm) and alumina sol (AP-1, manufactured by JGC Catalysts & Chemicals Co., Ltd.) as an "aluminum element binder" were mixed in a ratio of 90% by mass and 10% by mass based on oxide. Next, 3 parts by mass of organic matter were added to this mixture (100 parts by mass) as a molding aid and mixed. The organic matter used was 2 parts by mass of polyvinyl alcohol (manufactured by Nippon Vinegar Vinegar & Boval Co., Ltd.), 0.5 parts by mass of water-soluble cellulose ether (Metholose 14000, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.3 parts by mass of curdlan (Biopoly-P-3, manufactured by Takeda Pharmaceutical Company Limited), and 0.2 parts by mass of oleic acid (manufactured by Kanto Chemical Co., Ltd.) (second step). Next, this mixture was kneaded for 30 minutes in a double-arm kneader to adjust the moisture content of the molding precursor to 55% by mass. This was then molded into a cylindrical shape with a diameter of 1 / 16 inch using an extrusion molding machine (third step). Next, this molded product was heated to 100°C in a box-type dryer. Subsequently, this dried product was heated in a muffle furnace at 550°C for 3 hours to produce a molded body (fourth step).

[0087] The molded body was measured using the following method.

[0088] The characteristics of each manufacturing process of the molded product and the properties of the molded product are shown in Tables 2 and 3 (the same applies to the following examples and comparative examples).

[0089] (1) Pore volume and pore distribution by nitrogen gas adsorption method Using a gas adsorption measurement device (BELSORP-mini Ver2.5.6, manufactured by Microtrac-Bel Co., Ltd.), pore volume and pore distribution were measured by nitrogen gas adsorption. Specifically, approximately 30 mL of the sample was first placed in a porcelain crucible (Type B-2), heated at 600°C for 2 hours, and then cooled to room temperature in a desiccator. After heat treatment at 500°C for 1 hour under vacuum evacuation, nitrogen gas was adsorbed, and the pore distribution was determined from the desorption side isotherm of the relative pressure (P / P0 = 0.99) using the BJH method. From this pore distribution, the pore volume of pores with a diameter of 2.4 to 192.4 nm was calculated as the total pore volume (PV(N2)). In addition, the pore volume (PV(N2, 10-100 nm)) for pores with a diameter of 10 to 100 nm was calculated. Furthermore, the ratio of the pore volume in the 10-100 nm range to the total pore volume was calculated.

[0090] (3) Specific surface area by nitrogen gas adsorption method Approximately 30 mL of the sample was placed in a porcelain crucible (Type B-2), heated at 600°C for 2 hours, and then cooled to room temperature in a desiccator. Next, 1 g of this sample was taken, and its specific surface area was measured using the BET method with a fully automated surface area analyzer (MultiSorb 12, Yuasa Ionics).

[0091] (4) Confirmation of amorphous silica alumina Measurements were performed using X-ray analysis (MiniFlex, Rigaku Corporation). The measurement conditions were as follows: the operating axis was 2θ / θ, CuKα was used as the heat source, and a continuous measurement method was used with a voltage of 40kV and a current of 15mA. From the starting angle (2θ=5°) to the ending angle (2θ=50°), the sampling width was 0.020° and the scan speed was 10.000° / min. The criterion for determining amorphous material was that no diffraction peaks with a full width at half maximum of less than 1.0° were shown in the range of 5°≦2θ≦50°.

[0092] (5) Particle size of silica alumina A silica-alumina powder sample was placed in the measurement bath of a particle size analyzer (LA-950v2, manufactured by Horiba, Ltd.) to achieve the appropriate transmittance, and the average particle size was measured after ultrasonic dispersion.

[0093] (6) Metal element content (aluminum, silicon, molybdenum, nickel) of molded articles and silica alumina Three g of the sample was placed in a 30 ml lidded zirconia container, heat-treated (200°C, 20 minutes), and then calcined (700°C, 5 minutes). Subsequently, two g of sodium peroxide (Na₂O₂) and one g of NaOH were added and melted for 15 minutes. Further, two 5 ml of H₂SO₄ and two 200 ml of water were added to dissolve the mixture, and then the sample was diluted with pure water to a volume of 500 ml. The content of each element was measured using an ICP instrument (Shimadzu Corporation ICPS-8100, analysis software ICPS-8000), and the values ​​were calculated based on oxide equivalents (Al₂O₃, SiO₂, MoO₃, NiO).

[0094] (7) Alkali metal and alkaline earth metal content of molded articles and silica alumina The sample was dissolved in hydrofluoric acid, heated to remove the hydrofluoric acid, and then pure water was added as needed. The resulting solution was then measured using an ICP inductively coupled plasma emission spectrometer (ICPM-8500, Shimadzu Corporation).

[0095] (8) Method for measuring pore volume and pore distribution using mercury intrusion method Pore ​​distribution was measured using the mercury intrusion method (Poremaster 60GT, manufactured by Anton Paar Japan Co., Ltd., with a mercury contact angle of 150 degrees and a surface tension of 480 dyn / cm). The total pore volume was defined as the pore volume (PV(Hg)) for pore diameters from 4 to 10000 nm. In addition, the pore volume (PV(Hg, 100-2000 nm)) for pore diameters from 100 to 2000 nm and the pore volume (PV(Hg, 2000-10000 nm)) for pore diameters from 2000 to 10000 nm were calculated. Furthermore, the ratio of the pore volume in the 2000-10000 nm range to the total pore volume was calculated.

[0096] (9) Water absorption amount The molded body was fired in an electric furnace at 500°C for 1 hour. 10g of this was taken as a sample and placed in a lidded container. Distilled water was slowly added dropwise using a burette, shaking after each addition. This dropping and shaking process was repeated until the samples became difficult to move and completely discolored. The water absorption per gram of sample was then determined.

[0097] (10) Crushing strength The molded body was placed on the sample stage of a Kiya-type hardness tester so that pressure was applied to its sides, and pressure was applied. The pressure at which the molded body collapsed was recorded and divided by the length of the molded body. The measured value was the average value (in N / mm) obtained by repeating this measurement 10 times.

[0098] (11) Powdering rate (abrasion strength) The pulverization rate (abrasion strength) of the molded body was measured according to ASTM D4058-81.

[0099] (12)Solid 29 Analysis of Si-NMR spectra As a pretreatment before measurement, the molded body was pulverized, calcined at 500°C for 1 hour, and then conditioned at 60% relative humidity for 24 hours. This powder sample was uniformly packed into a 5.0 mm diameter solid NMR sample tube and set in a 14.1T NMR spectrometer (Agilent Technologies, Inc., VNMRS-600, 1H resonance frequency 600 MHz), and rotated at 6 kHz with a magic angle (54.7°) relative to the external magnetic field. 29 The Si resonance frequency was 119.2 MHz. 29The Si-NMR pulse width was 6.0 μs at 1H 90°, the waiting time after FID was 400 s, and the number of FID integrations was 128. The polydimethylsilane peak (-34.44 ppm) was used as the secondary standard for chemical shift. The obtained spectra were approximated using a Gaussian function with Origin and waveform separation was performed, and the chemical shift and area ratio of each peak were calculated. The area of ​​the peak appearing in -95 to -125 ppm was assigned as Q4, the area of ​​the peak appearing in -85 to -115 ppm as Q3, the area of ​​the peak appearing in -80 to -100 ppm as Q2, and the area of ​​the peak appearing in -70 to -95 ppm as Q1. (Q1 / ΣQ) × 100 was calculated from the integral value of each peak, where ΣQ = Q1 + Q2 + Q3 + Q4.

[0100] (13)Solid 27 Analysis of Al-NMR spectra As a pretreatment before measurement, the molded body was pulverized, calcined at 500°C for 1 hour, and then conditioned at 60% relative humidity for 24 hours. This powder sample was uniformly packed into a 3.2 mm diameter solid NMR sample tube and set in a 14.1T NMR spectrometer (Agilent Technologies, Inc., VNMRS-600, 1H resonance frequency 600 MHz), and rotated at a high speed of 20 kHz with a magic angle (54.7°) relative to the external magnetic field. 27 The Al resonance frequency was 156.3 MHz. 27 For the Al-NMR chemical shift reference, the peak of a 1 mol / l Al(NO3)3 aqueous solution was set to 0 ppm, and the number of FID integrations was set to 256. The single-pulse method was used for the measurement, with the pulse flip angle set to 10° and the pulse repetition time set to 0.1 s. The obtained spectra were approximated using the Voigt function with Origin, and waveform separation was performed to determine the area ratio of each peak. The area of ​​the peak representing a 4-coordinate structure with a chemical shift maximum between 80.0 and 50.0 ppm was defined as I4, the area of ​​the peak representing a 5-coordinate structure with a chemical shift maximum between 50.0 and 20.0 ppm was defined as I5, and the area of ​​the peak representing a 6-coordinate structure with a chemical shift maximum between 20.0 and -30.0 ppm was defined as I6.

[0101] <Manufacturing of hydrogenation catalysts> To evaluate the reaction performance of the molded body as a fixed-bed catalyst, a catalyst was prepared for hydrogenation desulfurization applications as follows (the same applies to the following examples and comparative examples).

[0102] 214 g of molybdenum trioxide and 97 g of nickel carbonate were suspended in 700 ml of deionized water. This suspension was heated at 90°C for 5 hours using a reflux apparatus to prevent volume reduction, and then 134 g of citric acid was added to dissolve it and prepare impregnation solution 1.

[0103] Next, impregnation solution 1 was used to impregnate 1000g of molded body so that 16% by mass of molybdenum trioxide and 4.0% by mass of nickel oxide were supported on it. After that, it was heated to 200°C, and then heated in an electric furnace at 550°C for 1 hour to obtain hydrogen desulfurization catalyst system 1 (hereinafter also simply referred to as "catalyst system 1").

[0104] In addition, 320 g of molybdenum trioxide and 145 g of nickel carbonate were suspended in 700 ml of deionized water. This suspension was heated at 90°C for 5 hours using a reflux apparatus to prevent volume reduction, and then 200 g of citric acid was added to dissolve it and prepare impregnation solution 2.

[0105] Next, impregnation solution 2 was used to impregnate 1000g of molded body so that 24% by mass of molybdenum trioxide and 6.0% by mass of nickel oxide were supported on it. After that, it was heated to 200°C, and then heated in an electric furnace at 550°C for 1 hour to obtain hydrogen desulfurization catalyst system 2 (hereinafter also simply referred to as "catalyst system 2").

[0106] The reaction performance of this catalyst was evaluated as follows. The properties of the catalyst and the evaluation results of its reaction performance are shown in Table 4 (the same applies to the following examples and comparative examples).

[0107] (14) Method for measuring the amount of nitric oxide adsorbed Using a fully automated catalyst gas adsorption amount measuring device (R6015, manufactured by Okura Riken Co., Ltd.), a mixed gas of helium and nitric oxide (10% vol. nitric oxide concentration) was pulsed into sulfurized hydrogenation catalysts (catalyst system 1 and catalyst system 2), and the amount of nitric oxide molecules adsorbed per gram of hydrogenation catalyst was measured. Specifically, approximately 0.02 g of catalyst, pulverized to 60 mesh or less, was weighed and packed into a quartz cell. The catalyst in the cell was heated to 360°C, and sulfurization treatment was performed by passing a gas mixture of 5% vol. 1 hydrogen sulfide and 95% vol. 1 hydrogen sulfide at a flow rate of 0.2 liters / min for 1 hour. After that, the cell was maintained at 340°C for 1 hour to discharge the physically adsorbed hydrogen sulfide from the system. Subsequently, a mixed gas of helium and nitric oxide was introduced into the cell, which was maintained at 50°C, to adsorb nitric oxide molecules onto the sulfurized catalyst, and the amount of adsorption was measured. The dispersibility of the active metal supported on the catalyst is higher the amount of nitric oxide molecules adsorbed per gram of catalyst.

[0108] (15) Evaluation of catalyst reaction performance The reaction performance of the catalysts (catalyst system 2) in the examples and comparative examples was evaluated. The evaluation method involved first filling a flow-through fixed-bed reactor with the catalyst and performing a preliminary sulfidation treatment to activate it by removing oxygen atoms. This preliminary sulfidation treatment was carried out by flowing feedstock oil containing sulfur compounds through the fixed-bed reactor filled with the catalyst at 200-400°C under a hydrogen pressure atmosphere of atmospheric pressure to 100 MPa. Next, the hydrogen partial pressure was 4.5 MPa and the liquid space velocity was 1.0 h. -1 The hydrogen-to-oil ratio is 250 Nm³. 3 The raw material is vacuum diesel (density at 15°C: 0.9111 g / cm³) per kiloliter. 3Hydrodesulfurization treatment was performed by supplying 2.18% by mass of sulfur and 0.063% by mass of nitrogen at a rate of 150 ml / hour, followed by hydropurification. For the evaluation of catalyst activity, the activity (desulfurization rate) of the catalyst of Comparative Example 1 at a reaction temperature of 370°C was used as the baseline (100%), and the relative activity values ​​of each catalyst are shown. Here, the desulfurization rate is calculated as ("sulfur content removed by hydropurification" / "sulfur content in the raw material oil") × 100 (%). Note that the catalysts of Examples 8 and 9 differ in size due to different molding methods, as will be described later. In order to reduce the influence of the size difference between the catalysts of other examples and comparative examples when evaluating reaction performance, the catalysts of Examples 8 and 9 were coarsely pulverized before being filled into the above-mentioned reactor to adjust the catalyst diameter to approximately 1.59 mm (1.57~1.61 mm) before being filled.

[0109] [Example 2] In the production of the molded article, the molded article and catalyst were prepared in the same manner as in Example 1, except that the proportion of silica alumina (ASA1) was set to 80% by mass, the proportion of the binder containing aluminum element was set to 20% by mass, and the moisture content of the molding precursor was adjusted to 57% by mass.

[0110] [Example 3] In the production of the molded article, the molded article and catalyst were prepared in the same manner as in Example 1, except that the proportion of silica alumina (ASA1) was set to 70% by mass, the proportion of the binder containing aluminum element was set to 30% by mass, and the moisture content of the molding precursor was adjusted to 59% by mass.

[0111] [Example 4] <Preparation of silica alumina (ASA2) (first step)> ASA2 was prepared in the same manner as ASA1, except that the amount of pseudo-boehmite washing slurry (solid content concentration 7.2% by mass) was 33.75 kg and the amount of silica particle dispersion was 0.82 kg. The properties of ASA2 are shown in Table 1.

[0112] <Manufacturing of molded products> A molded body and catalyst were prepared in the same manner as in Example 1, except that ASA2 (Al2O3 equivalent concentration 85% by mass, average particle size 100 μm) was used for silica alumina, and the moisture content of the molding precursor was adjusted to 54% by mass.

[0113] [Example 5] <Preparation of silica alumina (ASA3) (first step)> ASA3 was prepared in the same manner as ASA1, except that the amount of pseudo-boehmite washing slurry (solid content concentration 7.2% by mass) was 15.00 kg and the amount of silica particle dispersion was 4.91 kg. The properties of ASA3 are shown in Table 1.

[0114] <Manufacturing of molded products> A molded article and catalyst were prepared in the same manner as in Example 1, except that ASA3 (Al2O3 equivalent concentration 40% by mass, average particle size 105 μm) was used for silica alumina, and the moisture content of the molding precursor was adjusted to 53% by mass.

[0115] [Example 6] <Preparation of silica alumina (ASA4) (first step)> In preparing ASA1 used in Example 1, a pseudo-boehmite slurry was obtained in the same manner as for ASA1, except that hot water was heated to 60°C in a 200L stainless steel tank with a steam jacket, and while maintaining the temperature in the tank at 60°C and stirring, 48g of a 25% by mass sodium gluconate aqueous solution was added. Next, a pseudo-boehmite washing slurry was obtained in the same manner as for the preparation of ASA1, except that 3.85kg of sodium aluminate was added to this pseudo-boehmite slurry and then heated at 60°C for 2 hours while stirring. Then, ASA4 was obtained in the same manner as for the preparation of ASA1, except that 0.08kg of 15% aqueous ammonia was added to 22.4kg of this washing slurry, and the mixture was aged at 50°C after adding a dispersion of silica particles. The properties of ASA4 are shown in Table 1.

[0116] <Manufacturing of molded products> A molded body and catalyst were prepared in the same manner as in Example 1, except that ASA4 (Al2O3 equivalent concentration 58% by mass, average particle size 107 μm) was used as silica alumina, with a ratio of 50% by mass of silica alumina and a ratio of 50% by mass of the binder containing aluminum element, and the moisture content of the molding precursor was adjusted to 61% by mass.

[0117] [Example 7] In the production of the molded article, ASA1 (Al2O3 equivalent concentration 57% by mass, average particle size 103 μm) was used as silica alumina, with a ratio of 60% by mass, and the ratio of the binder containing aluminum element was set to 40% by mass. The moisture content of the molding precursor was adjusted to 63% by mass. The molded article and catalyst were prepared in the same manner as in Example 1. In this case, the binder containing aluminum element was prepared by mixing the alumina sol used in Example 1 with silica sol (S-20L manufactured by JGC Catalysts & Chemicals Co., Ltd., SiO2 equivalent concentration 20% by mass) at a ratio of 83% on an oxide basis relative to the total amount of alumina sol and silica sol.

[0118] [Example 8] In the production of the molded body, ASA1 as silica alumina and aluminum stearate (manufactured by Kanto Chemical Co., Ltd.) as an aluminum element binder were mixed in a ratio of 98% by mass and 2% by mass, respectively, on an oxide basis. The moisture content of the resulting molding precursor was adjusted to 12% by mass, and the precursor was molded into a cylindrical shape of 3.2 mmφ-3.2 mmH at a molding pressure of 50 kgf using a tablet press (HT-AP15SS-II, manufactured by Hata Iron Works Co., Ltd.). The resulting material was then heated in a muffle furnace at 600°C for 3 hours to produce the molded body. The catalyst was prepared using the molded body obtained here, in the same manner as in Example 1.

[0119] [Example 9] In the manufacturing of the molded body, the molded body and catalyst were prepared in the same manner as in Example 8, except that the molding pressure was changed to 20 kgf.

[0120] [Example 10] In the production of the molded article, the proportion of ASA1 used as silica alumina was set to 98% by mass, the proportion of the binder containing aluminum element was set to 2% by mass, and the proportion of organic matter as a molding aid was changed to 8 parts by mass per 100 parts by mass of the mixture, and the moisture content of the molding precursor was adjusted to 70% by mass. The molded article and catalyst were prepared in the same manner as in Example 1. Here, the molding aids were used in the same proportions as each organic matter in Example 1.

[0121] [Example 11] In the production of the molded article, the proportion of ASA4 used as silica alumina was set to 98% by mass, the proportion of the binder containing aluminum element was set to 2% by mass, the organic material as a molding aid was changed to 4 parts by mass, and the moisture content of the molding precursor was adjusted to 57% by mass. The molded article and catalyst were prepared in the same manner as in Example 1. Here, the molding aids were used in the same proportions as the organic materials in Example 1.

[0122] [Comparative Example 1] In the production of the molded body, HA (manufactured by JGC Catalysts & Chemicals Co., Ltd., Al2O3 equivalent concentration 28% by mass, average particle size 65 μm) was used as silica alumina, with a ratio of 85% by mass and a binder containing aluminum element ratio of 15% by mass. The moisture content of the molding precursor was adjusted to 62% by mass. Except for these differences, the molded body and catalyst system 1 were produced in the same manner as in Example 1. Regarding the amount of active metal in catalyst system 2, since the molded body could not be impregnated with impregnation liquid 2 in a single operation, 80% of impregnation liquid 2 was first impregnated and fired at 550°C for 1 hour. Then, the remaining 20% ​​of impregnation liquid 2 was impregnated, and fired again at 550°C for 1 hour to produce catalyst system 2.

[0123] [Table 1]

[0124] [Table 2]

[0125] [Table 3]

[0126] Table 4

Claims

1. Contains silica alumina, In the pore distribution measured by the nitrogen gas adsorption method, the total pore volume (PV(N)) ２ A molded article characterized in that the concentration is 0.8 to 2.0 ml / g, and the ratio of the pore volume at a pore diameter of 10 to 100 nm to the total pore volume is 30 to 80%.

2. The molded article according to claim 1, characterized in that the total pore volume (PV(Hg)) is 1.0 to 1.9 ml / g in the pore distribution measured by the mercury intrusion method.

3. The molded article according to claim 1 or 2, characterized in that, in the pore distribution measured by the mercury intrusion method, the pore volume at pore diameters of 100 to 2000 nm is 0.3 to 0.9 ml / g.

4. Specific surface area of ​​300-550 m² ２ The molded article according to claim 1 or 2, characterized in that it is / g.

5. The molded article according to claim 1 or 2, characterized in that the amount of water absorbed, as measured by the pore-filling method, is 1.2 ml / g or more.

6. ２９ In Si-NMR spectroscopy analysis, the Q of silicon atoms appears in the chemical shift range of -70 to -125 ppm. １ ~Q ４ Q is the chemical shift that appears at -70 to -95 ppm relative to the sum of the areas of each peak representing the structure. １ The molded article according to claim 1 or 2, characterized in that the proportion of the area of ​​peaks representing the structure is 10% or more.

7. ２７ In analysis by Al-NMR spectroscopy, the area of a peak representing a 4-coordinate structure having a maximum chemical shift at 80.0 to 50.0 ppm (I ４ ), the area of a peak representing a 5-coordinate structure having a maximum chemical shift at 50.0 to 20.0 ppm (I ５ ) and the area of a peak representing a 6-coordinate structure having a maximum chemical shift at 20.0 to -30.0 ppm (I ６ ), a ratio of the total of said areas to the aforementioned area ((I ５ +I ６ ) / I ４ ) is 3.5 to 6.0, the molded body according to claim 1 or 2.

8. The molded article according to claim 1 or 2, characterized in that the silica-alumina is amorphous.

9. The silica content is SiO ２ The alumina content is 10-60% by mass. ２ O ３ The molded article according to claim 1 or 2, characterized in that it is 40 to 90% by mass.

10. The molded article according to claim 1 or 2, characterized in that the content of alkali metals and alkaline earth metals is less than 0.1% by mass on an oxide basis.

11. The molded article according to claim 1 or 2, characterized in that the crushing strength is 5.0 N / mm or more.

12. The first step in preparing silica alumina, A second step involves mixing the silica alumina with a binder to produce a mixture, A third step involves molding the mixture, which has been adjusted to have a moisture content of 10 to 70% by mass, to produce a molded product. A fourth step involves heating the molded product to 100 to 700°C, A method for manufacturing a molded article containing [the specified ingredient].

13. In the pore distribution of the aforementioned silica-alumina, as measured by the nitrogen gas adsorption method, Total pore volume (PV(N) ２ )) is 1.0 ml / g or more, The method for manufacturing a molded article according to claim 12, characterized in that the ratio of the pore volume in the pore diameter range of 10 to 100 nm to the total pore volume is 50% or more.

14. The method for manufacturing a molded article according to claim 12, characterized in that the binder contains an aluminum element.

15. The method for producing a molded article according to claim 12 or 14, characterized in that the amount of the binder is 1 to 30% by mass on an oxide basis relative to the total amount of the binder and the silica alumina.

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