Silica-alumina molded body and method for producing the same

Abstract

To provide a silica-alumina molded body having adequate mechanical strength and capable of exhibiting sufficient performance on the active surface without relying on zeolite, and a method for producing the same.SOLUTION: This molded body has a Broensted acid amount of 50 μmol / g or less and a Lewis acid amount of 150 μmol / g or less as measured by infrared spectroscopy through pyridine adsorption. The total pore volume based on pore size distribution measurement by mercury intrusion method is 0.65 to 0.85 ml / g, and the ratio of the pore volume of pores with diameters of 100 to 1000 nm to the total pore volume is 20% or less. The crushing strength of the silica-alumina molded body is 5.0 N / mm or more. The molded body has sufficient mechanical strength and activity as a fixed-bed catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a silica-alumina molded body for use in a hydrotreating catalyst, and a method for producing the same. [Background technology]

[0002] In recent years, research and development into new processes aimed at carbon neutrality, chemical recycling, and new energy generation has been progressing. One of the targets of such research and development is the use of catalysts. In particular, fixed-bed catalysts are used in a variety of applications, such as hydrorefining, cracking reactions, isomerization reactions, and deoxygenation. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-210207 [Patent Document 2] Special Publication No. 2017-518171 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-105649 Summary of the Invention [Problem to be solved by the invention]

[0004] For industrial use, fixed-bed catalysts are required to have both sufficient mechanical strength and the ability to produce the desired product in a high yield in the reaction system. For example, Japanese Patent Laid-Open Publication No. 2019-210207 (Patent Document 1) discloses a zeolite molded body containing zeolite, fibrous clay, silica sol, a water-soluble sodium salt, and a molding aid as a molded body with high abrasion resistance. Japanese Patent Laid-Open Publication No. 2017-518171 (Patent Document 2) discloses a hydrocracking catalyst containing a molecular sieve, alumina, and an amorphous silica-alumina support. Japanese Patent Laid-Open Publication No. 2017-105649 (Patent Document 3) discloses a zeolite kneaded product containing zeolite, kanbai powder, polyvinyl alcohol, and a silica-based additive, which can be molded well even after long-term storage.

[0005] Zeolites have a higher Bronsted acidity and higher cracking activity than amorphous silica-alumina, and are therefore used as hydrocracking catalysts, as in Patent Document 2. If a catalyst contains a large amount of zeolite, cracking activity improves, but excessive cracking or side reactions may occur, making it difficult to obtain the desired product. Furthermore, because the zeolite itself is bulky, it may not be possible to compact it densely, resulting in reduced mechanical strength. On the other hand, the molded body of Patent Document 1 has high abrasion resistance due to the above-mentioned configuration, but due to the presence of compositions other than zeolite and alkaline components, it has a low solid acidity, which may result in insufficient production of the desired product in high yield. Therefore, a molded body (catalyst) that can exhibit sufficient performance in terms of activity without relying on zeolite and has sufficient mechanical strength is needed. [Means for solving the problem]

[0006] To solve these problems, we have discovered the following silica-alumina molded body. This molded body has a Bronsted acid amount of 50 μmol / g or less and a Lewis acid amount of 150 μmol / g or less, as measured by infrared spectroscopy using pyridine adsorption. Furthermore, as measured by mercury intrusion porosimetry, the total pore volume is 0.65 to 0.85 ml / g, and the ratio of the pore volume with pore diameters of 100 to 1000 nm to the total pore volume is 20% or less. The crushing strength of this silica-alumina molded body is 5.0 N / mm or more.

[0007] Hereinafter, this silica-alumina molded body may be simply referred to as a "molded body" or a "catalyst." Furthermore, Bronsted acid may be simply referred to as a "B acid," and Lewis acid may be simply referred to as an "L acid."

[0008] This molded body has sufficient mechanical strength, appropriately adjusted Bronsted acid and Lewis acid amounts, and an appropriate pore distribution and volume for the reaction site, i.e., it exhibits sufficient mechanical strength and reaction performance that allows the desired product to be obtained in high yield without overreaction.

[0009] In order to obtain this molded body, the following manufacturing method was found.

[0010] First, silica alumina is prepared (first step). This is mixed with a silicon-containing binder to prepare a mixture (second step). Next, the water content of this mixture is adjusted to 43 to 58 mass % and this is molded to prepare a molded product (third step). Next, this molded product is heated to 100 to 700°C (fourth step).

[0011] The properties of the molded body obtained by this manufacturing method are similar to those of the molded body described above. [Effects of the Invention]

[0012] The molded article of the present invention exhibits sufficient mechanical strength as a fixed-bed catalyst and reaction performance capable of producing desired products in high yields without overreaction, and can be used in a variety of applications, such as hydrorefining, cracking reactions, isomerization reactions, and deoxygenation. DETAILED DESCRIPTION OF THE INVENTION

[0013] [Silica alumina compact] The molded article according to the present invention will now be described.

[0014] The molded article of the present invention is a molded article containing silica alumina. The molded article has a Bronsted acid amount of 50 μmol / g or less, as measured by infrared spectroscopy using pyridine adsorption. The Lewis acid amount is 150 μmol / g or less. The molded article has a total pore volume of 0.65 to 0.85 ml / g, as measured by mercury intrusion porosimetry for pore distribution. The ratio of the pore volume with a pore diameter of 100 to 1000 nm to the total pore volume is 20% or less. The molded article has a crushing strength of 5.0 N / mm or more.

[0015] The molded body contains silica-alumina. Taking into consideration moldability, solid acid properties such as the amounts of B acid and L acid, and properties related to pore distribution and pore volume, this silica-alumina is preferably amorphous silica-alumina. Specifically, it is preferable that the silica content is 50 to 97 mass% as SiO2, the alumina content is 3 to 50 mass% as Al2O3, and the SiO2 / Al2O3 molar ratio is 3 to 30.

[0016] When silica alumina is amorphous, the amount of B acid can be reduced compared to crystalline zeolite, and the amounts of B acid and L acid can be adjusted. This acid adjustment allows the design of a molded product tailored to the reaction to obtain the target product, such as suppressing excessive cracking activity.

[0017] When the SiO2 content of the molded body is within this range, it is easy to adjust the acid properties, pore structure, etc. to obtain the target product, and it is also easy to prepare the molded body.

[0018] If the SiO2 content of the molded body is less than 50% by mass, the amount of L acid and the amount of ammonia adsorbed may be excessive. Conversely, if it exceeds 97% by mass, it may be difficult to prepare the molded body. The SiO2 content is more preferably 65 to 95% by mass, and even more preferably 70 to 95% by mass.

[0019] Furthermore, when the Al2O3 content of the molded body is within this range, it is easy to adjust the acid properties, pore structure, etc. to obtain the target product, and it also becomes easy to prepare the molded body.

[0020] If the Al2O3 content of the molded body is less than 3 mass%, it may be difficult to prepare the molded body. Conversely, if it exceeds 50 mass%, it may not be possible to maintain the acidity and pore structure required to obtain the target product. The Al2O3 content is more preferably 5 to 35 mass%, and even more preferably 7 to 30 mass%.

[0021] Furthermore, when the SiO2 / Al2O3 molar ratio is within this range, it is easy to adjust the acid properties, pore structure, etc. to obtain the desired product.

[0022] If the SiO2 / Al2O3 molar ratio is less than 3, the acidity and pore structure required to obtain the target product may not be obtained. Conversely, if it exceeds 30, it may become difficult to prepare a molded product. The SiO2 / Al2O3 molar ratio is more preferably 3 to 25, and even more preferably 5 to 20.

[0023] Incidentally, the molded body may contain materials other than silica-alumina as long as they satisfy the above-mentioned characteristics related to the B acid amount, L acid amount, pore distribution and pore volume, and crushing strength. 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, and organic substances.

[0024] The amount of B acid measured by infrared spectroscopy using pyridine adsorption of the molded product is 50 μmol / g or less. When the amount of B acid is within this range, it becomes easy to control the reaction to obtain the desired product. For example, in the hydrocracking reaction of hydrocarbon oils, overcracking is suppressed, and the desired fraction product can be obtained in high yield. There is no particular lower limit for the amount of B acid, but when used for hydrocracking reactions, it is, for example, 5 μmol / g.

[0025] If the amount of acid B exceeds 50 μmol / g, the reaction cannot be controlled due to excessive solid acid properties, and excessive decomposition reaction may occur. The amount of acid B is preferably 5 to 50 μmol / g, more preferably 10 to 50 μmol / g, and even more preferably 10 to 40 μmol / g.

[0026] The L-acid amount measured by infrared spectroscopy using pyridine adsorption of the molded product is 150 μmol / g or less. When the L-acid amount is in this range, it becomes easy to control the reaction to obtain the desired product.

[0027] Here, if the amount of L acid exceeds 150 μmol / g, it may become difficult to control the progress of the hydrogenation reaction. There is no particular lower limit for the amount of L acid, but taking into consideration the amount of metal supported on the molded body and its dispersibility, it is, for example, 10 μmol / g. This amount of L acid is preferably 10 to 150 μmol / g, more preferably 30 to 150 μmol / g, and even more preferably 70 to 120 μmol / g.

[0028] The ratio of the amount of L acid to the amount of B acid is preferably 0.15 to 0.70. When the ratio of the amount of L acid to the amount of B acid is within this range, it becomes easy to control the reaction to obtain the desired product. This ratio is more preferably 0.20 to 0.70, and even more preferably 0.25 to 0.60.

[0029] The total pore volume of the molded body measured by mercury intrusion porosimetry is 0.65 to 0.85 ml / g. If the total pore volume is in this range, the raw material molecules can easily diffuse into the pores.

[0030] If the total pore volume is less than 0.65 ml / g, the raw material molecules may have difficulty diffusing through the pores. Conversely, if it exceeds 0.85 ml / g, the mechanical strength of the molded body may be insufficient. The total pore volume is preferably 0.65 to 0.80 ml / g, more preferably 0.70 to 0.80 ml / g.

[0031] The ratio of the volume of pores with a diameter of 100 to 1000 nm to the total volume of pores in the molded body is 20% or less. When this ratio is in this range, the pores in the molded body can be utilized for reaction. In addition, the mechanical strength of the molded body can be maintained.

[0032] If this ratio exceeds 20%, there is a risk of a decrease in mechanical strength. This ratio is preferably 15% or less, more preferably 12% or less, and even more preferably 10%.

[0033] The ratio of the volume of pores in the molded article having a diameter of more than 1000 nm to the total volume of pores is preferably 1% or less, more preferably 0%. There is no particular upper limit to the diameter of these pores, but it is, for example, about 1 mm.

[0034] Conversely, pores in the molded body having a pore diameter of less than 100 nm are utilized for the reaction, and therefore the ratio of the pore volume to the total pore volume is preferably more than 80%.

[0035] The water absorption capacity of the molded body is 0.66 to 0.86 ml / g. When the water absorption capacity is in this range, the raw material molecules can easily diffuse into the pores.

[0036] If the water absorption is less than 0.66 ml / g, the raw material molecules may have difficulty diffusing into the pores. Conversely, if it exceeds 0.86 ml / g, the mechanical strength of the molded body may be insufficient. The water absorption is preferably 0.66 to 0.81 ml / g, more preferably 0.71 to 0.81 ml / g.

[0037] The crushing strength of the molded body is 5.0 N / mm or more. If the crushing strength is in this range, the molded body has sufficient mechanical strength for use as a fixed bed catalyst.

[0038] If the crushing strength is less than 5.0 N / mm, it is difficult to pack the catalyst while maintaining its shape when used in a fixed-bed catalyst. Even if the catalyst can be packed, the packed bed may become uneven. In such a state, the raw material may flow unevenly during the reaction, or an over-reaction or an insufficient reaction may occur, making stable operation impossible.

[0039] The powdering rate of the molded body is preferably 5.0% or less. If the powdering rate is in this range, the molded body has sufficient mechanical strength for use as a fixed bed catalyst.

[0040] If the degree of powdering exceeds 5.0%, when used in a fixed-bed catalyst, it is difficult to pack the catalyst while maintaining its shape. Even if packing is possible, there is a risk of the packed bed becoming uneven. In such a state, a pressure difference occurs, which can cause uneven flow of raw materials during the reaction, or over-reaction or insufficient reaction, making stable operation impossible.

[0041] Molded body 29 In Si-NMR spectroscopy, the area Q1 of the peak appearing at a chemical shift of -78 to -88 ppm, the area Q2 of the peak appearing at a chemical shift of -88 to -98 ppm, the area Q3 of the peak appearing at a chemical shift of -98 to -108 ppm, and the area Q4 of the peak appearing at a chemical shift of -108 to -120 ppm preferably have a ratio (Q4 / ΣQ) × 100 of 30% or more, where ΣQ = Q1 + Q2 + Q3 + Q4.

[0042] The peak attributable to Q1 is due to one (-OSi) group and three (-OH) groups bonded to the Si atom; the peak attributable to Q2 is due to two (-OSi) groups and two (-OH) groups bonded to the Si atom; the peak attributable to Q3 is due to three (-OSi) groups and one (-OH) group bonded to the Si atom; and the peak attributable to Q4 is due to four (-OSi) groups bonded to the Si atom. If the (Q4 / ΣQ) ratio is within this range, the amount of silanol groups is high, the bonding strength with the Al atom is strong, and a relatively large amount of B acid is obtained. There is no specific upper limit for the (Q4 / ΣQ) ratio, but when used for hydrocracking reactions, it is, for example, 50%.

[0043] If the ratio of (Q4 / ΣQ) is less than 30%, the number of silanol groups will be small, which may result in a high degree of bonding with Al atoms and an excessive amount of acid B. The ratio of (Q4 / ΣQ) is more preferably 35% or more, and even more preferably 37% or more.

[0044] The amount of ammonia desorption from the molded body as measured by ammonia temperature programmed desorption (NH3-TPD) method is preferably 0.30 to 0.70 mmol / g. When the amount of ammonia desorption is in this range, the desired reaction product can be obtained by controlling the solid acid properties.

[0045] If the amount of ammonia desorption is less than 0.30 mmol / g, the amount of solid acid required to promote the desired reaction may be insufficient. Conversely, if it exceeds 0.70 mmol / g, the amount of solid acid may be excessive, resulting in an excessive cracking reaction. The amount of ammonia desorption is more preferably 0.35 to 0.70 mmol / g, and even more preferably 0.40 to 0.65 mmol / g.

[0046] The carbon (C) content of the molded body is preferably less than 8% by mass, since a carbon content within this range makes it easier to control the reaction to the desired level.

[0047] The carbon content of the compact can be measured using a carbon / sulfur analyzer. For example, the compact can be pulverized, dried, and the resulting powder is measured to determine the carbon content of the compact.

[0048] Here, if the carbon content is 8% by mass or more, there is a risk of water generation and elution of the supported metal when subjected to a reaction. There is no particular lower limit for the carbon content, but taking into consideration the moisture absorption of the molded body and catalysts on which metals such as molybdenum and nickel are supported, it is, for example, 0.1% by mass. This carbon content is more preferably 0.1 to 5.0% by mass, and even more preferably 0.1 to 3.0% by mass.

[0049] The compact may contain elements belonging to alkali metals and alkaline earth metals as impurities. If any one of these elements is present in large amounts, it may poison the solid acid sites of the compact, reducing the solid acidity and thereby reducing reaction performance. Furthermore, heating the compact may cause the pores of the compact to become clogged. The total content of elements belonging to alkali metals and alkaline earth metals, expressed as oxides, is preferably less than 5 mass%, more preferably less than 3 mass%, and even more preferably less than 2 mass% of the compact. Here, alkali metals refer to Li, Na, K, Rb, Cs, and Fr, and alkaline earth metals refer to Be, Mg, Ca, Sr, Ba, and Ra.

[0050] The shape of the molded body is not particularly limited as long as it is suitable for use in a fixed bed, and examples thereof include cylindrical, prismatic, trilobal, and quadrilobal pellets, spherical, tablet, and honeycomb shapes.

[0051] [Method of manufacturing silica alumina compact] The method for producing a molded body according to the present invention includes a first step of preparing silica alumina, a second step of mixing this silica alumina with a binder containing silicon to produce a mixture, a third step of adjusting the water content of this mixture to 43 to 58 mass % and molding this to produce a molded product, and a fourth step of heating this molded product to 100 to 700°C.

[0052] The molded product thus produced has an appropriate solid acidity and pore distribution. It also has sufficient mechanical strength for use in 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.

[0053] [First step] First, silica alumina is prepared. Here, the type and composition of the silica alumina are not particularly limited, but it is preferably amorphous. Amorphous silica alumina does not have a high B acid content compared to crystalline silica alumina such as zeolite, so it is relatively easy to adjust the acid content when forming a molded body. In addition, since the bulk density is low, it has high moldability and the mechanical strength of the molded body is high.

[0054] The silica alumina is preferably in the form of powder or particles with an average particle size of 50 μm or less. When the average particle size is in this range, the moldability is high and the gaps between the particles can be reduced, thereby improving the mechanical strength.

[0055] Here, if the average particle size exceeds 50 μm, the voids between the particles will become large, which may result in a decrease in mechanical strength. There is no particular lower limit for the average particle size, but it is, for example, 5 μm. If the average particle size is less than 5 μm, the voids between the particles will become small, which may reduce the pore volume of the molded body and make it difficult for the raw material molecules to diffuse within the pores. This average particle size is more preferably 5 to 30 μm, and even more preferably 10 to 25 μm.

[0056] [Second process] A mixture is prepared by mixing the silica alumina prepared in the first step with a binder containing silicon.

[0057] Here, examples of the silicon-containing binder include at least one selected from silicates, acidic silicic acid solutions, silica-based sols, and organic silicon compounds.

[0058] The silicate is preferably one or more silicates selected from alkali metal silicates, ammonium silicates, and silicates of organic bases. Examples of alkali metal silicates include sodium silicate and potassium silicate. Examples of organic bases include quaternary ammonium salts such as tetraethylammonium salts, and amines such as monoethanolamine, diethanolamine, and triethanolamine. Examples of ammonium silicates or silicates of organic bases include alkaline solutions in which ammonia, quaternary ammonium hydroxide, amine compounds, etc. are added to a silicic acid solution.

[0059] The acidic silicic acid solution can be obtained by removing the alkali by treating an aqueous alkali silicate solution with a cation exchange resin, and an acidic silicic acid solution having a pH of 2 to 4 is particularly preferred.

[0060] Examples of silica-based sols include silica sol and silica alumina sol.

[0061] Examples of organosilicon compounds include tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and 8-methacryloxyoctyltrimethoxysilane.

[0062] Organosilicon compounds with poor hydrophilicity are preferably hydrolyzed in advance to allow for uniform mixing in the reaction system. Well-known methods can be used for hydrolysis. When a basic catalyst such as an alkali metal hydroxide, aqueous ammonia, or an amine is used as a hydrolysis catalyst, the basic catalyst can be removed after hydrolysis, and the resulting solution can be used as an acidic solution. When an acidic catalyst such as an organic acid or inorganic acid is used to prepare a hydrolyzate, it is preferable to remove the acidic catalyst by ion exchange or the like after hydrolysis. The obtained hydrolyzate of the organosilicon compound is preferably used in the form of an aqueous solution. Here, "aqueous solution" refers to a state in which the hydrolyzate is transparent and not in a cloudy, gel-like state.

[0063] The amount of the "silicon-containing binder" to be mixed is preferably 5 to 50 parts by mass, on a dry basis, per 100 parts by mass of the silica-alumina prepared in the first step. When the amount of the silicon-containing binder is within this range, it is easy to adjust the acidity, pore structure, etc. to obtain the target product.

[0064] If the amount of silicon-containing binder is less than 5 parts by mass, it may be difficult to prepare a molded product. Conversely, if it exceeds 50 parts by mass, it may be difficult to adjust the acid properties, pore structure, etc. to obtain the desired product. The amount of this "silicon-containing binder" to be mixed is more preferably 10 to 40 parts by mass, and even more preferably 10 to 30 parts by mass.

[0065] In the second step, materials other than the silica-alumina and silicon-containing binder prepared in the first step may be mixed. These materials allow adjustment of the solid acid properties, pore size distribution, and mechanical strength of the molded body. However, the final molded body must satisfy the properties related to the B acid amount, L acid amount, pore size distribution, pore volume, and crushing strength.

[0066] Examples of materials other than silica-alumina and silicon-containing binders include silicon compounds such as silica and diatomaceous earth, aluminas such as ρ-alumina, χ-alumina, γ-alumina, δ-alumina, and θ-alumina, aluminum compounds such as sodium aluminate, aluminum sulfate, aluminum nitrate, and polyaluminum chloride, clay minerals such as kaolin and acid clay, and organic substances such as cellulose, methyl cellulose, cellulose ether, starch, polyvinyl alcohol, curdlan, citric acid, malic acid, oleic acid, and stearic acid. These materials can also be added when preparing a molded product in the third step described below.

[0067] The amount of "materials other than silica alumina and silicon-containing binder" to be mixed is preferably 0.5 to 10 parts by mass, based on the dry weight, per 100 parts by mass of the total of silica alumina and silicon-containing binder 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 a desired pore structure.

[0068] Here, if the amount of "materials other than silica alumina and silicon-containing binder" is less than 0.5 parts by mass, it may be difficult to form into a molded article. Conversely, if it exceeds 10 parts by mass, it may also be difficult to form into a molded article. The amount of "materials other than silica alumina and silicon-containing binder" to be mixed is more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 7.0 parts by mass.

[0069] The carbon content of the compact can be adjusted by washing the mixture with warm water, etc. However, when more precise adjustment is required, it is preferable to adjust it by changing the heating temperature or heating atmosphere in the fourth step described below.

[0070] In order to reduce the content of impurities such as elements belonging to alkali metals and alkaline earth metals in the molded body, it is preferable to reduce the content of these impurities in the mixture.

[0071] As a method for this, it is possible to reduce the content of impurities in the materials to be mixed in advance by a washing operation such as acid treatment or ion exchange, to reduce the content of impurities in the materials to be mixed by a washing operation such as acid treatment or ion exchange after mixing, or to combine both. Of course, washing can be performed after the third step described below, but carrying out washing in the second step provides higher production efficiency.

[0072] [Third step] In this step, the mixture is adjusted to a water content of 43 to 58% by mass, and then molded to produce a molded product.

[0073] For molding, conventionally known devices such as an extruder or a tableting machine can be used.

[0074] The water content of the mixture during molding is 43 to 58% by mass. When the water content is within this range, a molded product having sufficient mechanical strength and a desired pore distribution for use as a fixed bed catalyst can be finally obtained.

[0075] If the water content is less than 43% by mass, molding may be difficult and a molded product may not be obtained. Conversely, if it exceeds 58% by mass, the molded product may not have sufficient mechanical strength or the desired pore distribution. The water content is preferably 43 to 56% by mass, more preferably 45 to 56% by mass.

[0076] [Fourth step] In this step, the molded product is heated to 100 to 700°C.

[0077] For heating, conventionally known devices such as a box-type firing furnace or a rotary kiln can be used.

[0078] The heating temperature is 100 to 700° C. When the heating temperature is within this range, a molded body having sufficient mechanical strength for use as a fixed bed catalyst can be finally obtained.

[0079] If the heating temperature is less than 100°C, the molded body may have insufficient mechanical strength or may not have the pore structure required for the desired reaction. Conversely, if the heating temperature exceeds 700°C, the solid acid properties required for the desired reaction may not be obtained. The heating temperature is preferably 350 to 700°C, more preferably 500 to 700°C.

[0080] The carbon content of the compact can be changed by changing the heating temperature. The carbon content can also be changed by supplying air or oxygen during heating, by supplying an inert gas such as nitrogen gas to reduce the oxygen partial pressure, or by heating in a water vapor atmosphere. These methods can be selected appropriately to obtain the desired physical properties of the compact.

[0081] Examples of the present invention will be described below.

[0082] [Example 1] <Production of Molded Product> Silica alumina (JGC Catalysts and Chemicals Co., Ltd., LA, 13% by mass as Al2O3, average particle size 60 μm) was wet-ground in a bead mill to an average particle size of 16 μm, and silica sol A (JGC Catalysts and Chemicals Co., Ltd., S-20L, concentration 20% by mass as SiO2) was mixed as a "silicon-containing binder" in a ratio of 80 parts by mass of silica alumina to 20 parts by mass of silica sol A on a dry basis. An organic substance was added to this mixture as a molding aid. This organic substance was added and mixed in such a way that the total amount of the organic substance was 5 parts by mass per 100 parts by mass of the "silica alumina" and "silicon-containing binder." The components were 3% by mass of polyvinyl alcohol (Nippon Acetate Bioval Co., Ltd.), 1% by mass of water-soluble cellulose ether (Metolose 14000, Shin-Etsu Chemical Co., Ltd.), 0.5% by mass of curdlan (Biopoly-P-3, Takeda Pharmaceutical Co., Ltd.), and 0.5% by mass of oleic acid (Kanto Chemical Co., Ltd.). This mixture was kneaded in a twin-arm kneader for 30 minutes, and the moisture content was adjusted to 49% by mass. This was molded into a cylindrical shape with a diameter of 1 / 16 inch using an extruder and dried at 100°C in a box dryer. The resulting dried product was heated in a muffle furnace at 550°C for 3 hours to produce a molded product.

[0083] The molded body was measured by the following method.

[0084] The characteristics of each manufacturing process of the molded body and the properties of the molded body are shown in Tables 1 and 2 (the same applies to the following Examples and Comparative Examples).

[0085] (1) Method for measuring Lewis acidity and Bronsted acidity 33 mg of the molded product was packed into a disk with an inner diameter of 20 mm and placed in a measuring device (FT-IR4600 manufactured by JASCO Corporation). The atmosphere of the measurement sample was evacuated to a vacuum at 500 °C for 1 hour, and then cooled to 30 °C. The temperature was then raised again to 150 °C, pyridine was adsorbed onto the sample, and a pyridine adsorption spectrum was obtained. The measurement atmosphere was further evacuated at 250 °C, and a spectrum after pyridine desorption was obtained. The difference spectrum before and after pyridine adsorption was then taken, and the peak at 1450 cm -1The amount of Lewis acid was calculated from the peak value of the absorption band around 1550 cm. -1 The Bronsted acid amount was calculated from the peak value of the absorption band around 1000. Each measurement was carried out three times, and the average values ​​were used as the Lewis acid amount and Bronsted acid amount of the molded body.

[0086] (2) Measurement method of average pore diameter and pore volume Measurement was performed by mercury intrusion porosimetry (mercury contact angle 150 degrees, surface tension 480 dyn / cm). The pore volume was defined as the volume of pores with a diameter of 4 to 10,000 nm. In the present invention, the ratio of the volume of pores with a diameter of 100 to 10,000 nm to the total pore volume was calculated.

[0087] (3) Water absorption amount The compact was pre-baked in an electric furnace at 500°C for 1 hour. 10 g of this was placed in a container with a lid, and distilled water was slowly added dropwise from a burette, with the container being shaken after each addition. This dropping and shaking process was repeated until the samples became difficult to move and completely discolored, marking the end point, and the amount of water absorbed per 1 g of sample was calculated.

[0088] (4) Method for measuring particle size of silica alumina A silica alumina powder sample is placed in the measurement bath of a particle size measuring device (LA-950v2 manufactured by Horiba Ltd.) so as to have an appropriate transmittance, and the average particle size is measured after ultrasonic dispersion.

[0089] (5) Crushing strength The compact was placed on the sample stage of a Kiya hardness tester so that pressure was applied to the side, and the pressure when the sample collapsed was recorded and divided by the length of the compact. The measured value is the average value (unit: N / mm) obtained by repeating this measurement 10 times.

[0090] (6) Powdering rate (abrasion strength) The powdering rate (abrasion resistance) of the molded body was measured according to ASTM D4058-81.

[0091] (7) Metal element (aluminum, silicon, molybdenum, nickel) content of the compact 3 g of the compact was placed in a 30 ml zirconia container with a lid, heated (200°C for 20 minutes), and then calcined (700°C for 5 minutes). 2 g of sodium peroxide (Na2O2) and 1 g of NaOH were then added and melted for 15 minutes. 25 ml of H2SO4 and 200 ml of water were added and dissolved, and the mixture was then diluted to 500 ml with pure water. The resulting sample was measured for the content of each element using an ICP apparatus (Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000) and calculated in terms of oxide (Al2O3, SiO2, MoO3, NiO).

[0092] (8) Alkali metal and alkaline earth metal content of the compact The alkali metal and alkaline earth metal contents of the molded body were measured by dissolving the molded body in hydrofluoric acid, heating to remove the hydrofluoric acid, adding pure water as needed, and then measuring the resulting solution using an ICP inductively coupled plasma optical emission spectrometer mass spectrometer (ICP-8500, manufactured by Shimadzu Corporation).

[0093] (9) Measurement of solid-state 29Si-NMR spectrum solid 29 The Si-NMR spectrum was measured using an Agilent VNMRS-600 (14.1T, 1 The H resonance frequency (600 MHz) was used. The measurement sample was crushed in a mortar and filled into a 5 mm solid-state NMR sample tube to make it uniform, and then rotated at 6 kHz at the magic angle (54.7°) to the external magnetic field. 29 The Si resonance frequency was 119.2 MHz. 29 Si CPMAS NMR 1The H 90° pulse width was 5.7 μs, the contact time was 7 ms, the waiting time after FID was 5 s, and the FID integration count was 10,000. The polydimethylsilane peak at -34.44 ppm was used as the secondary standard for chemical shifts. The obtained spectrum was subjected to waveform separation using Origin with a Gaussian function approximation, and the chemical shifts and area ratios of each peak were calculated. The peak from -108 to -120 ppm was assigned to Q4, the peak from -98 to -108 ppm to Q3, the peak from -88 to -98 ppm to Q2, and the peak from -78 to -88 ppm to Q1. The integrals of each component were used to calculate (Q4 / ΣQ) × 100, where ΣQ = Q1 + Q2 + Q3 + Q4.

[0094] (10) Ammonia desorption amount by NH3-TPD method 0.2 g of compacts were placed in the sample chamber of a temperature-programmed desorption (TPD) apparatus (Microtrackbell, BELCATB). The sample chamber was heated to 500°C for 1 hour, evacuated, and then cooled to 100°C. Ammonia gas was adsorbed onto the compact over 0.5 hours while the sample chamber was maintained at 100°C. The sample chamber was then evacuated for 0.5 hours while the temperature was maintained at 100°C. The compact was then heated from 100°C to 700°C at a rate of 10°C / min under a flow of helium gas at a rate of 50 ml / min. The amount of ammonia desorbed from the compact during the heating period from 100°C to 700°C was measured.

[0095] (11) Carbon content The carbon content of the compact was measured by burning it in a high-frequency furnace of a carbon analyzer (EMIA-320V manufactured by Horiba, Ltd.).

[0096] <Production of Hydrotreating Catalyst> In order to evaluate the reaction performance of the molded body as a fixed-bed catalyst, a catalyst was prepared for hydrocracking as follows (the same applies to the following Examples and Comparative Examples).

[0097] 267 g of molybdenum trioxide and 121 g of nickel carbonate were suspended in 700 ml of ion-exchanged water, and the suspension was heated at 90°C for 5 hours using an appropriate reflux device so as not to reduce the volume of the liquid. 167 g of citric acid was then added and dissolved to prepare an impregnation solution.

[0098] Thereafter, 1000 g of the molded body was impregnated with the above impregnation solution containing 20 mass % of molybdenum trioxide and 5 mass % of nickel carbonate, dried at 200°C, and further calcined in an electric furnace at 500°C for 1 hour to obtain a hydrocracking catalyst (hereinafter also simply referred to as "catalyst").

[0099] The reaction performance of this catalyst was evaluated as follows: The properties of the catalyst and the evaluation results of the reaction performance of the catalyst are shown in Table 3 (the same applies to the following Examples and Comparative Examples).

[0100] <Method for measuring the amount of adsorbed nitric oxide> Nitric oxide adsorption was measured using an automated catalyst gas adsorption analyzer (R6015, manufactured by Ohkura Riken Co., Ltd.) by pulse-feeding a mixture of helium and nitric oxide (10% by volume) onto the sulfided hydrotreating catalyst. The adsorption of nitric oxide molecules per gram of the catalyst was measured. Specifically, approximately 0.02 g of catalyst crushed to 60 mesh or less was weighed and loaded into a quartz cell. The catalyst was heated to 360°C and sulfided for 1 hour by passing a 5% by volume hydrogen sulfide / 95% by volume hydrogen gas through the cell at a flow rate of 0.2 L / min. The catalyst was then maintained at 340°C for 1 hour, and the physically adsorbed hydrogen sulfide was purged. Nitric oxide molecules were then adsorbed with a mixture of helium and nitric oxide at 50°C, and the adsorption of nitric oxide molecules was measured. The performance is judged by the amount of mixed gas adsorbed per 1 g of catalyst, and the higher the adsorption amount, the better the dispersibility of molybdenum and the improved decomposition performance. Here, the range of the nitric oxide adsorption amount is preferably 5.0 to 8.0, more preferably 6.0 to 8.0, and even more preferably 7.0 to 8.0, and the performance is judged to be good or bad.

[0101] <Evaluation of catalyst reaction performance> The reaction performance of each catalyst was evaluated using vacuum gas oil (VGO) obtained by processing a typical Middle Eastern crude oil as the feedstock. The feedstock had nickel and vanadium contents of less than 0.2 ppm each, sulfur content of approximately 3%, and a density of 0.91 to 0.93 g / ml.

[0102] When evaluating this reaction performance, a fixed-bed flow reactor was filled with a hydrotreating catalyst (NCH-91-8B, manufactured by JGC Catalysts and Chemicals Co., Ltd.) and then a hydrocracking catalyst of the present invention in a 50:50 ratio to pretreat the feedstock prior to the hydrocracking reaction using the catalyst of the present invention. Prior to the introduction of the feedstock, the catalyst was presulfided to desorb oxygen atoms and activate it. This presulfidation treatment was carried out by flowing a liquid (kerosene) containing sulfur compounds through a controlled reaction vessel at temperatures of 200°C to 400°C and under a hydrogen atmosphere of atmospheric pressure to 100 MPa.

[0103] The hydrogenolysis reaction was carried out under a hydrogen partial pressure of 13 MPa and a liquid hourly space velocity of 0.5 h -1 , hydrogen-oil ratio is 1000Nm 3 The reaction temperature was varied within the range of 350 to 420°C, and the temperature at which the cracking rate of the refined oil reached 80 mass% and the yield of middle distillates (kerosene and diesel) in the resulting refined oil were calculated using the following formulas (1) and (2). The catalytic activity was evaluated based on the cracking rate and the middle distillate yield. The cutoff temperature for middle distillates (kerosene and diesel) was 145 to 360°C.

[0104] Cracking rate (mass%) = (fraction (mass%) in feed oil with a boiling point higher than 360°C - fraction (mass%) in product oil with a boiling point higher than 360°C) / (fraction (mass%) in feed oil with a boiling point higher than 360°C) × 100 Equation (1) Middle distillate yield (mass%) = ((fraction of refined oil with a boiling point of 145 to 360°C (mass%)) × (100 - (C1 to C5 gas content in refined oil (mass%))) / 100 Equation (2)

[0105] Here, the lower the temperature at which the cracking rate of the refined oil reaches 80 mass %, the higher the cracking performance. Also, the higher the middle distillate yield, the higher the performance.

[0106] [Example 2] A molded body and a catalyst were produced in the same manner as in Example 1, except that the proportion of silica alumina was 90 parts by mass and the proportion of silica sol A was 10 parts by mass.

[0107] [Example 3] A molded body and a catalyst were produced in the same manner as in Example 1, except that the proportion of silica alumina was 70 parts by mass and the proportion of silica sol A was 30 parts by mass.

[0108] [Example 4] A molded body and a catalyst were produced in the same manner as in Example 1, except that silica alumina was wet-pulverized in a bead mill to have an average particle size of 30 μm.

[0109] [Example 5] A molded body and a catalyst were prepared in the same manner as in Example 1, except that the silica alumina was replaced with another type (HA manufactured by JGC Catalysts and Chemicals Co., Ltd., 28 mass% as Al2O3, average particle size 60 μm), which was wet-ground in a bead mill to an average particle size of 23 μm.

[0110] [Example 6] A molded body and a catalyst were prepared in the same manner as in Example 1, except that silica sol A was changed to silica sol B (SI-550 manufactured by JGC Catalysts and Chemicals Co., Ltd., concentration as SiO2: 20 mass%) as the "silicon-containing binder."

[0111] [Example 7] A molded body and a catalyst were prepared in the same manner as in Example 1, except that the proportion of silica sol A was 10 parts by mass, and 10 parts by mass of alumina sol (AP-1 manufactured by JGC Catalysts and Chemicals Co., Ltd., concentration: 70% by mass as Al2O3) was added and mixed.

[0112] [Example 8] A molded body and a catalyst were produced in the same manner as in Example 1, except that the moisture content during molding was 45% by mass.

[0113] [Example 9] A molded body and a catalyst were produced in the same manner as in Example 1, except that the moisture content during molding was set to 56% by mass.

[0114] [Example 10] A molded body and a catalyst were produced in the same manner as in Example 1, except that the dried product was heated to 100°C in a muffle furnace.

[0115] [Example 11] A molded body and a catalyst were produced in the same manner as in Example 1, except that the heating temperature of the dried product in the muffle furnace was set to 680°C.

[0116] [Comparative Example 1] An attempt was made to produce a molded product in the same manner as in Example 1 except that the water content during molding was set to 41% by mass, but molding was not possible.

[0117] Comparative Example 2 A molded body and a catalyst were produced in the same manner as in Example 1, except that silica alumina (LA, manufactured by JGC Catalysts and Chemicals Co., Ltd.) having an average particle size of 60 μm was used without being crushed.

[0118] Comparative Example 3 A molded body and a catalyst were prepared in the same manner as in Example 1, except that 45 parts by mass of alumina sol (AP-1 manufactured by JGC Catalysts and Chemicals Co., Ltd.) was used in place of silica sol A, which is a "silicon-containing binder," and the proportion of silica alumina was 55 parts by mass.

[0119] Comparative Example 4 A molded body and a catalyst were prepared in the same manner as in Example 1, except that the proportion of silica alumina was 75 parts by mass, the proportion of silica sol A was 20 parts by mass, and 5 parts by mass of ultrastable Y-type zeolite (USY) with a SiO2 / Al2O3 molar ratio of 5 was added and mixed.

[0120] Comparative Example 5 A molded body and a catalyst were produced in the same manner as in Example 1, except that silica sol A was replaced with water glass (AGC Si-Tech Co., Ltd., No. 3 sodium silicate, concentration 24 mass% as SiO2) as the "silicon-containing binder."

[0121] Comparative Example 6 A molded body and a catalyst were produced in the same manner as in Example 1, except that the moisture content during molding was set to 60 mass %.

[0122] Comparative Example 7 A molded body and a catalyst were produced in the same manner as in Example 1, except that the drying temperature in the box dryer was set to 40° C. and the subsequent heating in the muffle furnace was not carried out.

[0123] [Comparative Example 8] A molded body and a catalyst were produced in the same manner as in Example 1, except that the heating temperature in the muffle furnace was set to 750°C.

[0124] [Table 1]

[0125] [Table 2]

[0126] [Table 3]

Claims

1. a Bronsted acid amount of 50 μmol / g or less and a Lewis acid amount of 150 μmol / g or less, as measured by infrared spectroscopy using pyridine adsorption; a total pore volume of 0.65 to 0.85 ml / g as measured by mercury intrusion porosimetry, and a ratio of the pore volume of pores with diameters of 100 to 1000 nm to the total pore volume of 20% or less; Crushing strength is 5.0 N / mm or more, A silica-alumina molded body characterized by:

2. The silica content is SiO ２ 50 to 97 mass % as alumina, and the content of alumina is Al ２ O ３ 3 to 50 mass% as SiO ２ / Al ２ O ３ 2. The silica-alumina molded body according to claim 1, wherein the molar ratio is 3 to 30.

3. 3. The silica-alumina molded body according to claim 1, wherein the silica-alumina is amorphous.

4. ２９ In Si-NMR analysis, the chemical shift of silicon atom appears in the range of -78 to -120 ppm. １ ~Q ４ Q appears at a chemical shift of -108 to -120 ppm relative to the sum of the areas of the peaks representing the structure ４ 3. The silica-alumina molded body according to claim 1, wherein the area ratio of the peak representing the structure is 30% or more.

5. 3. The silica-alumina molded body according to claim 1, wherein the amount of ammonia desorbed by an ammonia temperature-programmed desorption method is 0.30 to 0.70 mmol / g.

6. 3. The silica-alumina molded body according to claim 1, wherein the total content of at least one oxide of an alkali metal element and an alkaline earth element is less than 5 mass %.

7. A first step of preparing silica alumina; a second step of mixing the silica-alumina with a binder containing silicon to prepare a mixture; a third step of molding the mixture having a water content adjusted to 43 to 58% by mass to produce a molded product; a fourth step of heating the molded product to 100 to 700°C; A method for producing a silica-alumina molded body, comprising:

8. A method for producing a silica alumina molded body as described in claim 7, characterized in that at least one material selected from silicon compounds, aluminum compounds, clay minerals, and organic substances is added in at least one of the second step and the third step.

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