Silicone collecting agent, method for collecting silicon, and hydrogenation treatment method

Abstract

To provide a silicon scavenger excellent in scavenging capacity of silicon of stock oil containing heavy coker cracked hydrocarbon oil, as well as a scavenging method of the silicon of the stock oil containing the heavy coker cracked hydrocarbon oil using the silicon scavenger and a hydrogenation treatment method of the stock oil containing the heavy coker cracked hydrocarbon oil using the silicon scavenger.SOLUTION: A silicon scavenger for stock oil containing heavy coker cracked hydrocarbon oil, contains alumina, and a content of alumina with respect to a total mass of the silicone scavenger is 50 mass% or more. The silicon scavenger of the stock oil containing the heavy coker cracked hydrocarbon oil, has pores with an average pore diameter of 7 to 13 nm and a pore volume of 0.55 to 0.75 mL / g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a silicon adsorbent, a method for adsorbing silicon, and a hydrogenation treatment method. [Background technology]

[0002] Due to the decline in demand for heavy oil, there is a need for technologies that can efficiently convert atmospheric distillation residue oil, which is the main base material for heavy oil and is obtained by processing crude oil with an atmospheric distillation unit, and vacuum distillation residue oil, which is obtained by processing the atmospheric distillation residue oil with a vacuum distillation unit, into light oil with high added value.

[0003] As a technology for converting heavy oil base to light oil, a process is known that utilizes fractions obtained by hydrothermal treatment (hydrodesulfurization) of coker cracking fractions, which are obtained by thermally cracking coker cracking residue oil in a heavy oil thermal cracking unit (hereinafter also referred to as a "coker unit"). Of the coker cracking fractions, the light fraction (coker cracked naphtha fraction) is treated in a catalytic reforming reactor after hydrothermal treatment to produce fractions containing high value-added basic chemicals. The heavy fraction (heavy coker cracked hydrocarbon oil) is treated in a fluid catalytic cracking unit after hydrothermal treatment to produce intermediate fractions such as gasoline, kerosene, and diesel fuel.

[0004] Incidentally, in coker units, silicon-based defoaming agents are used to suppress foaming in the reaction drum. As a result, silicon compounds derived from the defoaming agent are mixed into the fraction obtained by thermal decomposition in the coker unit. These silicon compounds are known to be poisoning substances for the hydrogenation catalyst used in the hydrogenation process. Furthermore, these silicon compounds are also known to be poisoning substances for the catalytic reforming catalyst packed into the catalytic reforming reactor.

[0005] Patent Document 1 describes that in the hydrogenation treatment of a coker-decomposed naphtha fraction containing silicon compounds, supplying 0.01 to 10 volume percent of water to the hydrogenation catalyst together with the coker-decomposed naphtha fraction improves the silicon collection ability of the hydrogenation catalyst. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 6,576,121 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] As described in Patent Document 1, extensive research has been conducted on silicon capture in the hydrogenation of coker-cracked naphtha fractions. On the other hand, research on silicon capture in the hydrogenation of heavy coker-cracked hydrocarbon oils has not progressed as much as research on silicon capture in the hydrogenation of coker-cracked naphtha fractions.

[0008] The present invention has been made in view of the above circumstances, and aims to provide a silicon adsorbent that has excellent silicon adsorption ability for raw oil containing heavy coker cracked hydrocarbon oil, a method for adsorbing silicon from raw oil containing heavy coker cracked hydrocarbon oil using the silicon adsorbent, and a method for hydrogenating raw oil containing heavy coker cracked hydrocarbon oil using the silicon adsorbent. [Means for solving the problem]

[0009] To solve the above problems, the present invention has the following embodiments. [1] A silicon adsorbent for raw oil containing heavy coker cracked hydrocarbon oil, wherein the silicon adsorbent contains alumina, the alumina content relative to the total mass of the silicon adsorbent is 50% by mass or more, and the silicon adsorbent has pores with an average pore diameter of 7 to 13 nm and a pore volume of 0.55 to 0.75 mL / g. [2] The silicon adsorbent according to [1], further comprising a hydrogenation active component, wherein the hydrogenation active component is supported on the alumina. [3] A feedstock oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 mass ppm is at a temperature of 300 to 410 °C, a pressure of 10 to 20 MPa, a hydrogen / oil ratio of 170 to 1400 m

[0011] , , , , , [Figure 1] / m 3 , and a liquid hourly space velocity of 0.1 to 2.0 h -1 and is sequentially contacted with the silicon scavenger and the hydrotreating catalyst described in [1] or [2]. A method for collecting silicon from a feedstock oil containing heavy coker cracked hydrocarbon oil. [4] A feedstock oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 mass ppm is at a temperature of 300 to 410 °C, a pressure of 10 to 20 MPa, a hydrogen / oil ratio of 170 to 1400 m 3 / m 3 , and a liquid hourly space velocity of 0.1 to 2.0 h -1 and is sequentially contacted with the silicon scavenger and the hydrotreating catalyst described in [1] or [2]. A hydrotreating method for a feedstock oil containing heavy coker cracked hydrocarbon oil. [5] A feedstock oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 mass ppm is at a temperature of 300 to 410 °C, a pressure of 10 to 20 MPa, a hydrogen / oil ratio of 170 to 1400 m 3 / m 3 , and a liquid hourly space velocity of 0.1 to 2.0 h -1 and is sequentially contacted with the silicon scavenger and the hydrotreating catalyst described in [1] or [2]. A method for producing a hydrotreated oil. [Advantages of the Invention]

[0010] According to the present invention, a silicon scavenger excellent in the ability to collect silicon from a feedstock oil containing heavy coker cracked hydrocarbon oil, a method for collecting silicon from a feedstock oil containing heavy coker cracked hydrocarbon oil using the silicon scavenger, and a hydrotreating method for a feedstock oil containing heavy coker cracked hydrocarbon oil using the silicon scavenger can be provided. [Brief Description of the Drawings]

[0011] [Figure 1]It is a diagram showing the relationship between the average pore diameter of the silicon collectors in Examples 1 to 6 and Comparative Examples 1 and 2, and the silicon deposition amount of the silicon collectors.

Mode for Carrying Out the Invention

[0012] Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to these contents, and can be implemented with modifications within the scope of the gist thereof.

[0013] <Definition> In this specification, "heavy coker cracked hydrocarbon oil" means the heaviest fraction among the distillates obtained by atmospheric distillation of the coker cracked fraction obtained mainly by thermally cracking vacuum distillation residue oil in a coker unit.The vacuum distillation residue oil is a residue oil obtained by further treating the atmospheric distillation residue oil obtained by treating crude oil in an atmospheric distillation unit with a vacuum distillation unit.As the properties of the heavy coker cracked hydrocarbon oil, for example, the density at 15 ° C is 0.91 to 1.00 g / mL, the sulfur content is 1.5 to 5.5 mass%, the nitrogen content is 0.01 to 0.6 mass%, the silicon concentration (in terms of element) is 0.1 to 15.0 mass ppm, the nickel content (in terms of element) is 0.1 to 1.5 mass ppm, the vanadium content (in terms of element) is 0.1 to 1.5 mass ppm, the 10% by volume distillation temperature is 230 to 440 ° C, the 50% by volume distillation temperature is 270 to 520 ° C, and the 90% by volume distillation temperature is 410 to 600 ° C. The density at 15 ° C can be measured in accordance with JIS K 2249-1 (2011) "Crude oil and petroleum products - Method for determining density - Part 1: Vibration method". The sulfur content can be measured in accordance with JIS K 2541-4 (2003) "Crude oil and petroleum products - Sulfur content test method - Part 4: Radiation excitation method". The nitrogen content can be measured in accordance with JIS K 2609 (1998) "Crude oil and petroleum products - Nitrogen content test method". The silicon concentration can be measured by inductively coupled plasma - atomic emission spectrometry (ICP - AES) or atomic absorption spectrometry (AAS). Nickel content can be measured by inductively coupled plasma emission spectroscopy (ICP-AES). The vanadium content can be measured by inductively coupled plasma emission spectroscopy (ICP-AES). The 10% volume distillation temperature, 50% volume distillation temperature, and 90% volume distillation temperature can be measured in accordance with JIS K2254 (2018) "Petroleum products - Method for determining distillation properties".

[0014] The elemental content of silicon adsorbents can be measured by inductively coupled plasma atomic emission spectrometry. The average pore diameter, pore volume, and pore distribution of silicon adsorbents can be measured by the mercury intrusion method. The specific surface area of ​​a silicon adsorbent is the BET specific surface area, which can be measured by the nitrogen adsorption method.

[0015] "Group 6 metals of the periodic table" (hereinafter sometimes referred to as "Group 6 metals"), "Group 9 metals of the periodic table" (hereinafter sometimes referred to as "Group 9 metals"), and "Group 10 metals of the periodic table" (hereinafter sometimes referred to as "Group 10 metals") refer to the Group 6 metals, Group 9 metals, and Group 10 metals of the long-period periodic table, respectively. Group 6, Group 9, and Group 10 metals are collectively referred to as "hydrogenation-active components."

[0016] ≪Silicone filtration agent≫ The silicon adsorbent for the raw material oil containing heavy coker-cracked hydrocarbon oil in this embodiment contains alumina. The alumina content relative to the total mass of the silicon adsorbent is 50% by mass or more. The silicon adsorbent has pores with an average pore diameter of 7 to 13 nm and a pore volume of 0.55 to 0.75 mL / g.

[0017] <Composition of the silicone filtration agent> (alumina) Various types of alumina can be used as the alumina contained in the silicon adsorbent, such as α-alumina, β-alumina, γ-alumina, and δ-alumina. However, porous alumina with a high specific surface area is preferred, and γ-alumina is more preferred among them. The purity of the alumina is preferably 98% by mass or higher, and more preferably 99% by mass or higher. Impurities in the alumina include SO4. 2- Cl - Examples of impurities include Fe2O3 and Na2O, but it is preferable that these impurities be as low as possible, preferably with a total amount of impurities of 2% by mass or less, and more preferably 1% by mass or less. Individually, SO4 2- less than 1.5% by mass, Cl - Preferably, the amounts of Fe2O3 and Na2O are 0.1% by mass or less. Silicon compounds in the feedstock oil, including heavy coker cracked hydrocarbon oil, react with hydroxyl groups on the alumina surface, thereby chemically adsorbing onto the alumina surface.

[0018] The alumina content (including the content of the impurities mentioned above) relative to the total mass of the silicon adsorbent is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass, and may be 100% by mass. The alumina content can be determined by measuring the aluminum element content in the silicon adsorbent using the method described above and calculating it as an oxide equivalent (Al2O3). Alternatively, if the silicon adsorbent contains substances other than alumina (as described later), the alumina content can be calculated by subtracting the content of these other substances from 100%.

[0019] Silicon adsorbents may contain substances other than alumina. Examples of substances other than alumina include substances containing zinc, substances containing phosphorus, substances containing silicon, and substances containing hydrogenation-active components.

[0020] (Substances containing zinc) Substances containing zinc include elemental zinc and zinc compounds. The silicon adsorbent may contain only elemental zinc or a zinc compound, or it may contain both. Examples of zinc compounds in the silicon adsorbent include zinc oxide, zinc nitrate, zinc sulfate, zinc carbonate, zinc phosphate, zinc aluminate, zinc titanate, and zinc molybdate, with zinc oxide and zinc aluminate being preferred. In addition to the above compounds, examples of zinc compounds in the silicon adsorbent include composite oxides and composite sulfides of zinc element and at least one element selected from the group consisting of aluminum element, phosphorus element, silicon element, group 6 metal elements, group 9 metal elements, and group 10 metal elements contained in the silicon adsorbent. The zinc-containing substance may exist as a mixture with alumina, or it may be supported on alumina. When the silicon adsorbent contains a zinc-containing substance, the content of the zinc-containing substance relative to the total mass of the silicon adsorbent is preferably 0.8 to 10% by mass, and more preferably 2 to 5% by mass, in terms of oxide (ZnO). The silicon adsorbent may contain only one type of zinc compound, or two or more types.

[0021] (Substances containing phosphorus) Substances containing phosphorus include elemental phosphorus and phosphorus compounds. The silicon adsorbent may contain only elemental phosphorus or phosphorus compounds, or it may contain both. Examples of phosphorus compounds in the silicon adsorbent include phosphorus oxide, molybd phosphoric acid, ammonium phosphate, aluminum phosphate, zinc phosphate, titanium phosphate, and nickel phosphate, with phosphorus oxide, molybd phosphoric acid, and nickel phosphate being preferred. In addition to the above compounds, other examples of phosphorus compounds in the silicon adsorbent include composite oxides and composite sulfides of phosphorus and at least one element selected from the group consisting of aluminum, zinc, silicon, group 6 metal elements, group 9 metal elements, and group 10 metal elements contained in the silicon adsorbent. The phosphorus-containing substance may exist as a mixture with alumina, or it may be supported on alumina. When the silicon adsorbent contains a phosphorus-containing substance, the content of the phosphorus-containing substance relative to the total mass of the silicon adsorbent is preferably 0.04 to 2% by mass, and more preferably 0.3 to 1.2% by mass, in terms of oxide (P2O5). The silicon adsorbent may contain only one type of phosphorus compound, or two or more types.

[0022] (Substances containing silicon) Examples of substances containing silicon include silicon compounds. Examples of silicon compounds in silicon adsorbents include silica. In addition to the above compounds, examples of silicon compounds in silicon adsorbents include composite oxides and composite sulfides of silicon and at least one element selected from the group consisting of aluminum, zinc, phosphorus, group 6 metal elements, group 9 metal elements, and group 10 metal elements contained in the silicon adsorbent. The silicon-containing substance may exist as a mixture with alumina, or it may be supported on alumina. When the silicon adsorbent contains a silicon-containing substance, the content of the silicon-containing substance relative to the total mass of the silicon adsorbent is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, and even more preferably 0.1 to 0.2% by mass, in terms of oxide equivalent (SiO2). It is preferable for the silicon adsorbent to contain a silicon-containing substance in order for the silicon adsorbent to satisfy the physical properties described later. The silicon compound in the silicon adsorbent may be just one type, or it may be two or more types.

[0023] (Substances containing hydrogenation-active components) When a silicon adsorbent contains a substance with hydrogenation-active components, it functions as both a silicon adsorbent and a hydrogenation catalyst. Hereinafter, a silicon adsorbent containing a substance with hydrogenation-active components will also be referred to as a "silicon adsorbent hydrogenation catalyst." Using a silicon adsorbent hydrogenation catalyst as a silicon adsorbent allows for more efficient use of space within the reactor. Although a silicon adsorbent hydrogenation catalyst possesses both silicon adsorbent ability and hydrogenation activity, in this specification it is defined as a "silicon adsorbent" and does not fall under the category of a "hydrogenation catalyst" as described later.

[0024] Examples of Group 6 metals include molybdenum, tungsten, and chromium, with molybdenum being preferred due to its high hydrogenation activity per unit mass. Substances containing Group 6 metals include elemental Group 6 metals and Group 6 metal compounds. The silicon adsorbent may contain only one of the two, or both. As the Group 6 metal compound in the silicon adsorbent, molybdenum compounds are preferred, including molybdenum trioxide, molybd phosphoric acid, ammonium molybdate, molybdenum sulfide, aluminum molybdate, nickel molybdate, zinc molybdate, and molybdic acid, with molybd phosphoric acid, molybdenum trioxide, nickel molybdate, and zinc molybdate being preferred. In addition to the above compounds, as the Group 6 metal compound in the silicon adsorbent, examples include composite oxides and composite sulfides of a Group 6 metal element and at least one element selected from the group consisting of zinc, phosphorus, silicon, Group 9 metal elements, and Group 10 metal elements contained in the silicon adsorbent. It is preferable that the substance containing the Group 6 metal is supported on alumina. When the silicon adsorbent contains a substance containing a Group 6 metal, the content of the substance containing the Group 6 metal relative to the total mass of the silicon adsorbent is preferably 10 to 30% by mass, and more preferably 10 to 25% by mass, in terms of oxide (e.g., MoO3). When calculating the content of the substance containing the Group 6 metal in terms of oxide, the Group 6 metal is calculated as a hexavalent metal. The silicon adsorbent may contain only one type of Group 6 metal compound, or two or more types.

[0025] Examples of Group 9 and Group 10 metals include nickel, palladium, platinum, cobalt, rhodium, and iridium. Among these, nickel and cobalt are preferred due to their high hydrogenation ability and low catalyst preparation costs, with nickel being more preferred. The silicon adsorbent may contain only substances containing Group 9 metals, only substances containing Group 10 metals, or both substances containing Group 9 and Group 10 metals. Examples of substances containing Group 9 metals and Group 10 metals include elemental Group 9 metals, elemental Group 10 metals, Group 9 metal compounds, and Group 10 metal compounds. When a silicon scavenger contains a substance containing a Group 9 metal, it may contain only one of the elemental Group 9 metal or a Group 9 metal compound, or both. When a silicon scavenger contains a substance containing a Group 10 metal, it may contain only one of the elemental Group 10 metal or a Group 10 metal compound, or both. Examples of Group 9 and Group 10 metal compounds in the silicon adsorbent include nickel or cobalt oxides, carbonates, nitrates, sulfates, phosphates, aluminates, titanates, and molybdates, with phosphates, titanates, and molybdates being preferred. In addition to the above compounds, examples of Group 9 and Group 10 metal compounds in the silicon adsorbent include composite oxides and composite sulfides of Group 9 and / or Group 10 metal elements and at least one element selected from the group consisting of zinc, phosphorus, silicon, and Group 6 metal elements contained in the silicon adsorbent. It is preferable that the substance containing the Group 9 metal or the substance containing the Group 10 metal be supported on alumina. When the silicon adsorbent contains a substance containing a Group 9 metal element or a substance containing a Group 10 metal element, the total content of the substance containing the Group 9 metal and the substance containing the Group 10 metal relative to the total mass of the silicon adsorbent is preferably 1 to 15% by mass, and more preferably 3 to 8% by mass, in terms of oxides (e.g., NiO). When calculating the amount of the substance containing the Group 9 metal or the substance containing the Group 10 metal in terms of oxides, the Group 9 metal or Group 10 metal is calculated as being in its divalent state. The silicon accumulator may contain only one type of Group 9 compound, or two or more types. The silicon accumulator may contain only one type of Group 10 compound, or two or more types.

[0026] <Physical properties of silicone filtration agents> The average pore size of the silicon adsorbent is 7 to 13 nm, preferably 8 to 12.5 nm, more preferably 9.2 to 11 nm, and particularly preferably 9.5 to 10.5 nm. When the average pore size is above the lower limit of the above range, the diffusion of the silicon compound into the pores improves. As a result, it is thought that the silicon compound penetrates deep into the pores and reacts efficiently with the hydroxyl groups on the alumina surface, thereby improving the silicon adsorption capacity. When the average pore size is below the upper limit of the above range, it tends to be above the lower limit of the specific surface area described later. As a result, it is thought that the number of hydroxyl groups on the alumina surface that react with the silicon compound becomes sufficient, improving the silicon adsorption capacity.

[0027] The pore volume of the silicon adsorbent is 0.55 to 0.75 mL / g, preferably 0.58 to 0.72 mL / g, and more preferably 0.60 to 0.70 mL / g. When the pore volume is above the lower limit of the above range, the diffusion of the silicon compound into the pores improves. As a result, it is thought that the silicon compound penetrates deep into the pores and reacts efficiently with the hydroxyl groups on the alumina surface, thereby improving the silicon adsorption capacity. When the pore volume is below the upper limit of the above range, it tends to be above the lower limit of the specific surface area described later. As a result, it is thought that the number of hydroxyl groups on the alumina surface that react with the silicon compound becomes sufficient, improving the silicon adsorption capacity.

[0028] In the silicon adsorbent, the pore distribution is preferably such that the ratio of the volume of pores with an average pore diameter of ±1.5 nm to the total pore volume is 30% or more, more preferably 35% or more, and even more preferably 40% or more. When the ratio is above the lower limit, there are a sufficient number of pores with a pore diameter suitable for silicon adsorption, and the silicon adsorption capacity is improved.

[0029] The specific surface area of ​​the silicon adsorbent is 150-300 m². 2 It is preferable that the amount be / g, and 190-290m 2 It is more preferable that the amount be / g, and 230-270m 2 It is even more preferable that the specific surface area is / g. If the specific surface area is above the lower limit of the above range, the number of hydroxyl groups on the alumina surface that react with the silicon compound will be sufficient, and it is thought that the silicon collection ability will be improved. If the specific surface area is below the upper limit of the above range, the average pore diameter is likely to be above the lower limit of the above range, and the diffusion of the silicon compound into the pores will be improved. As a result, it is thought that the silicon compound will penetrate into the interior of the pores and react efficiently with the hydroxyl groups on the alumina surface, thereby improving the silicon collection ability.

[0030] <Method for manufacturing silicone accumulating agent> The method for producing a silicon adsorbent includes a step of producing a molded body containing 50% by mass or more of alumina (hereinafter also referred to as "alumina molded body"). The alumina molded body can be used as a silicon adsorbent. If the silicon adsorbent is a silicon adsorption hydrogenation treatment catalyst, the method for producing the silicon adsorbent further includes a step of supporting a hydrogenation active component on the alumina molded body (a step of supporting a hydrogenation active component).

[0031] (Manufacturing process for alumina molded bodies) The manufacturing process for an alumina molded body includes, for example, an alumina gel preparation step for preparing an alumina gel, a kneading step for kneading the alumina gel to obtain a kneaded product, a molding step for molding the kneaded product to obtain a molded product, and a firing step for drying and firing the molded product to obtain a fired body (alumina molded body). If the silicon adsorbent contains the aforementioned zinc-containing substance, phosphorus-containing substance, or silicon-containing substance, it is preferable that the process includes a step of adding the zinc raw material, phosphorus raw material, or silicon raw material to one of the alumina gel, kneaded product, molded product, or calcined body.

[0032] The alumina raw materials for preparing alumina gel are not particularly limited as long as they contain aluminum, but aluminum salts such as aluminum sulfate, aluminum nitrate, sodium aluminate, and aluminum hydroxide are preferred. These alumina raw materials are usually provided as aqueous solutions, and their concentration is not particularly limited, but it is preferably 2 to 50% by mass, and more preferably 5 to 40% by mass, relative to the total mass of the aqueous solution.

[0033] For example, a slurry is prepared by mixing an aqueous sulfuric acid solution, sodium aluminate, and aluminum hydroxide in a stirring vessel. The obtained slurry is then subjected to water removal using a rotary cylindrical continuous vacuum filter and washed with pure water to obtain an alumina gel.

[0034] Next, the obtained alumina gel is placed in the filtrate with SO4 2- na + After washing until no traces are detected, the alumina gel is mixed with pure water to form a homogeneous slurry. The resulting alumina gel slurry is dehydrated until the moisture content is 60-90% by mass to obtain a cake.

[0035] Dewatering of the alumina gel slurry is preferably carried out by a compression filter. A compression filter is a device that filters a slurry by applying compressed air or pump pressure, and is generally also called a pressure filter. Compression filters come in two types: plate frame type and concave plate type. In a plate frame type compression filter, filter plates and filter frames are alternately fastened between end plates, and the slurry is injected under pressure into the filter frames for filtration. The filter plates have grooves that serve as filtrate passages, and filter cloth is stretched over the filter frames. On the other hand, in a concave plate type compression filter, filter cloth and concave plate-shaped filter plates are arranged alternately and fastened between end plates to form a filter chamber (Reference: Chemical Engineering Handbook, p. 715).

[0036] Dewatering the alumina gel slurry using a press filter can improve the surface condition of the resulting alumina molded body, and in the case of a silicon capture hydrogenation treatment catalyst, it can improve the degree of sulfidation of the hydrogenation active component. It is preferable to perform this dewatering step using a press filter after at least one of the alumina gel preparation step and the kneading step, and it may also be performed after both steps. In particular, it is more preferable to perform it after the alumina gel preparation step and before the kneading step.

[0037] In addition to the methods described above, other methods for preparing alumina gel include neutralizing an aqueous solution containing alumina raw materials with a neutralizing agent such as sodium aluminate, aluminic acid, or ammonia, and mixing it with a precipitating agent such as hexanemethylenetetramine or calcium carbonate. The amount of neutralizing agent used is not particularly limited, but 30 to 70% by mass is preferred relative to the total amount of the aqueous solution containing the alumina raw material and the neutralizing agent. The amount of precipitating agent used is not particularly limited, but 30 to 70% by mass is preferred relative to the total amount of the aqueous solution containing the alumina raw material and the precipitating agent.

[0038] When the zinc, phosphorus, and silicon raw materials are solid, it is preferable to add these raw materials to the alumina gel before performing the kneading step. When the zinc raw material, phosphorus raw material, and silicon raw material are dissolved in a liquid or solvent, it is preferable to add these raw materials to the alumina gel before performing the kneading step, to add these raw materials to the kneaded product before performing the molding step, to add these raw materials to the molded product before drying and firing, or to add these raw materials to the fired body, and it is more preferable to add these raw materials to the fired body.

[0039] As zinc raw materials, elemental zinc or various zinc compounds can be used, with examples including zinc oxide, zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, zinc acetate, zinc hydroxide, zinc oxalate, zinc phosphate, zinc aluminate, zinc titanate, and zinc molybdate. Among these, zinc oxide, zinc nitrate, zinc sulfate, and zinc aluminate are preferred, and zinc nitrate, zinc oxide, and zinc aluminate are particularly preferred.

[0040] If the zinc raw material is a solid such as zinc oxide, it is preferable to add the zinc raw material to the aluminum gel together with an acid such as nitric acid and then perform the kneading step.

[0041] In the case of a solution in which the zinc raw material is dissolved in a liquid or solvent (such as an aqueous solution of zinc nitrate), it is preferable to add the liquid or solution to the calcined body.

[0042] As phosphorus raw materials, elemental phosphorus or various compounds can be used, including orthophosphate, metaphosphate, pyrophosphate, triphosphate, tetraphosphate, and aluminum phosphate, with orthophosphate being preferred among them.

[0043] It is preferable to add a phosphorus raw material to the aluminum gel and then carry out the kneading process.

[0044] Examples of silicon raw materials include silica and silicon alkoxide, with silicon alkoxide being preferred among them.

[0045] It is preferable to add a silicon raw material to the aluminum gel and then perform the kneading step.

[0046] When the kneading process is performed after adding the above raw materials to the alumina gel, the above raw materials are added to the alumina gel obtained in the alumina gel preparation process and kneaded. Specifically, the above raw materials, heated to 15-90°C, are added to the moisture-adjusted alumina gel heated to 50-90°C. Then, the mixture is kneaded and stirred using a heated kneader or the like to obtain a kneaded product. As mentioned above, dewatering by a press filter may be performed after kneading and stirring the alumina gel and the above raw materials. As mentioned above, the above raw materials may be added as a solid, as a liquid, or as a liquid dissolved or suspended in a solvent.

[0047] The resulting mixture is then molded, dried, and fired to obtain a fired product. The mixture can be molded using various molding methods such as extrusion molding and pressure molding. The drying temperature of the resulting molded product is preferably 15 to 150°C, and more preferably 80 to 120°C. The drying time is preferably 30 minutes or more.

[0048] The firing temperature for the aforementioned firing can be set as appropriate as needed, but for example, the firing temperature for producing γ-alumina is preferably 450°C or higher.

[0049] When adding the above raw materials to the calcined body, known methods such as impregnation, coprecipitation, deposition, and ion exchange may be used. Examples of impregnation methods include the evaporation-to-drying method, in which the calcined body is immersed in an impregnation solution in excess of the total pore volume of the calcined body and then the solvent is completely dried to support the raw materials; the equilibrium adsorption method, in which the calcined body is immersed in an impregnation solution in excess of the total pore volume of the calcined body and then the raw materials are supported by solid-liquid separation such as filtration; and the pore-filling method, in which the calcined body is impregnated in an amount of impregnation solution approximately equal to the total pore volume of the calcined body and then the solvent is completely dried to support the raw materials. The method for impregnating the calcined body with the above multiple raw materials may be a batch impregnation method in which each of these raw materials is impregnated simultaneously, or a sequential impregnation method in which they are impregnated individually.

[0050] When the above raw materials are supported by the above impregnation method, it is generally preferable to remove a certain amount of moisture (to a loss on ignition of 50% or less) in a nitrogen stream, air stream, or vacuum at room temperature to 80°C, and then dry them in a drying oven in an air stream at 80 to 150°C for 10 minutes to 10 hours. Subsequently, it is preferable to perform firing in a firing oven in an air stream at 300 to 700°C, more preferably 500 to 650°C, for 10 minutes to 10 hours, more preferably 3 to 6 hours.

[0051] To satisfy the aforementioned physical properties of the silicon adsorbent, the conditions of each step in the alumina molding process should be adjusted. Such adjustment of the physical properties of the alumina molding can be carried out by methods known in this field. Furthermore, the physical properties of the silicon adsorbent hydrogenation treatment catalyst also reflect the physical properties of the alumina molding. For example, if the time (maturation time) between preparing the aqueous solution containing the alumina raw material in the alumina gel preparation process and adding the neutralizing agent or precipitating agent is increased, the specific surface area of ​​the alumina molded body tends to decrease, the average pore diameter and pore volume increase, and the pore distribution becomes sharper. Furthermore, increasing the pressure during the molding process tends to increase the specific surface area of ​​the alumina molded body, while decreasing the average pore diameter and pore volume. Furthermore, increasing the firing temperature during the firing process tends to reduce the specific surface area of ​​the alumina molded body, increase the average pore diameter and pore volume, and broaden the pore distribution.

[0052] (Process for loading hydrogenation active ingredients) The hydrogenation active component loading process involves loading the hydrogenation active component onto an alumina molded body.

[0053] As the Group 6 metal raw material to be supported on the alumina molded body, molybdenum compounds are preferred, including molybdenum trioxide, molybd phosphoric acid, ammonium molybdate, and molybdic acid, with molybd phosphoric acid, molybdenum trioxide, and ammonium molybdate being preferred.

[0054] Examples of Group 9 and Group 10 metal raw materials to be supported on the alumina molded body include nickel oxide, nickel carbonate, nickel acetate, nickel nitrate, nickel sulfate, nickel chloride, cobalt carbonate, cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt carbonate, and cobalt oxalate, with nickel nitrate, nickel carbonate, cobalt nitrate, and cobalt carbonate being preferred.

[0055] Methods for supporting Group 6 metal raw materials, Group 9 metal raw materials, and Group 10 metal raw materials (hereinafter also referred to as "hydrogenation active ingredient raw materials") on an alumina molded body may be known methods such as impregnation, coprecipitation, kneading, deposition, and ion exchange. Examples of impregnation methods include the evaporation-to-drying method, in which the hydrogenation active ingredient raw materials are supported by immersing the alumina molded body in an impregnation solution in excess of the total pore volume of the alumina molded body and then drying the solvent completely; the equilibrium adsorption method, in which the hydrogenation active ingredient raw materials are supported by immersing the alumina molded body in an impregnation solution in excess of the total pore volume of the alumina molded body and then separating the solid and liquid by filtration or other means; and the pore-filling method, in which the hydrogenation active ingredient raw materials are supported by impregnating the alumina molded body in an impregnation solution in an amount approximately equal to the total pore volume of the alumina molded body and then drying the solvent completely. Furthermore, the method for impregnating the alumina molded body with the above-mentioned multiple hydrogenation-active component raw materials may be a simultaneous impregnation method in which each component is impregnated at the same time, or a sequential impregnation method in which each component is impregnated individually.

[0056] The following are specific methods for supporting hydrogenation-active ingredient raw materials on an alumina molded body. First, an impregnation solution containing hydrogenation-active ingredient raw materials is prepared. During preparation, heating (30-100°C) or the addition of inorganic acids such as nitric acid and phosphoric acid, or organic acids such as citric acid, acetic acid, malic acid, and tartaric acid may be performed to promote the dissolution of these hydrogenation-active ingredient raw materials. In other words, in this embodiment, phosphorus may be separately supported on the alumina molded body when the hydrogenation-active ingredient raw materials are supported on the alumina molded body, in addition to the phosphorus contained in the alumina molded body.

[0057] When supporting hydrogenation active ingredient raw materials on an alumina molded body, examples of phosphorus compounds to be added separately include hydrogenation active ingredient raw materials containing phosphorus such as molybd phosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, with orthophosphoric acid being preferred. When phosphorus is added separately when supporting hydrogenation active ingredient raw materials on an alumina molded body, the dispersibility of the hydrogenation active ingredient in the resulting silicon capture hydrogenation treatment catalyst can be improved.

[0058] Next, the prepared impregnation solution is gradually added to the alumina molded body to impregnate it uniformly. The impregnation time is preferably 1 minute to 5 hours, and more preferably 5 minutes to 3 hours. The impregnation temperature is preferably 5 to 100°C, and more preferably 10 to 80°C. The impregnation atmosphere is not particularly limited, but air, nitrogen, and vacuum are suitable, respectively.

[0059] After supporting the hydrogenation active ingredient raw materials, it is preferable to first remove a certain amount of moisture (to a level where the Loss on Ignition (LOI) is 50% or less) from the impregnated material in a nitrogen stream, an air stream, or a vacuum at 15-80°C. Then, it is preferable to dry it in a drying oven in an air stream at 80-150°C for 10 minutes to 10 hours. Next, it is preferable to perform firing in a firing oven in an air stream. The firing temperature is preferably 300-700°C, and more preferably 500-650°C. The firing time is preferably 10 minutes to 10 hours, and more preferably 3 hours or more.

[0060] Method for collecting silicon from raw material oils containing heavy coker-cracked hydrocarbon oils. The silicon collection method for raw material oil containing heavy coker cracked hydrocarbon oil (hereinafter also referred to as the "silicon collection method") of this embodiment involves using raw material oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 ppm by mass, at a temperature of 300 to 410°C, a pressure of 10 to 20 MPa, and a hydrogen / oil ratio of 170 to 1400 m 3 / m 3 , and liquid space velocity 0.1~2.0h -1 The silicon adsorbent and hydrogenation catalyst of the present invention are then sequentially brought into contact with each other.

[0061] ≪Hydrogenation treatment method for feedstock oil containing heavy coker cracked hydrocarbon oil≫ The hydrogenation treatment method for raw material oil containing heavy coker cracked hydrocarbon oil in this embodiment (hereinafter also referred to as the "hydrogenation treatment method") involves treating raw material oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 ppm by mass at a temperature of 300 to 410°C, a pressure of 10 to 20 MPa, and a hydrogen / oil ratio of 170 to 1400 ml. 3 / m 3 , and liquid space velocity 0.1~2.0h -1 The silicon adsorbent and hydrogenation catalyst of the present invention are then sequentially brought into contact with each other. According to the hydrogenation treatment method of this embodiment, hydrogenated oil can be produced.

[0062] The following provides a detailed explanation of the silicon collection method and the hydrogenation treatment method.

[0063] <Raw oil> The raw material oil includes heavy coker cracked hydrocarbon oil. The content of heavy coker cracked hydrocarbon oil relative to the total volume of the raw material oil is preferably 50% by volume or more, more preferably 70% by volume or more, even more preferably 90% by volume or more, and may be 100% by volume. Examples of fractions other than heavy coker cracked hydrocarbon oil contained in the raw material oil include heavy cycle oil obtained from a fluid catalytic cracking unit and vacuum diesel oil obtained from an indirect hydrodesulfurization unit.

[0064] The density of the raw material oil at 15°C is preferably 0.91 to 1.00 g / mL, more preferably 0.915 to 0.99 g / mL, and even more preferably 0.92 to 0.985 g / mL.

[0065] The sulfur content relative to the total mass of the raw material oil is usually 1.5 to 5.5% by mass, but may also be 2.0 to 5.0% by mass, or 2.5 to 4.5% by mass. The nitrogen content relative to the total mass of the raw oil is usually 0.01 to 0.60% by mass, but may also be 0.03 to 0.45% by mass, or 0.05 to 0.25% by mass. The silicon content (elemental basis) relative to the total mass of the raw material oil is typically 0.1 to 15.0 ppm by mass, but may also be 0.1 to 13.0 ppm by mass, or 0.1 to 10.0 ppm by mass. The nickel content (elemental equivalent) relative to the total mass of the raw oil is usually 0.1 to 1.5 ppm by mass, but may also be 0.1 to 1.0 ppm by mass, or 0.1 to 0.5 ppm by mass. The vanadium content (elemental equivalent) relative to the total mass of the raw oil is usually 0.1 to 1.5 ppm by mass, but may also be 0.1 to 1.0 ppm by mass, or 0.1 to 0.5 ppm by mass.

[0066] It is known that silicon compounds contained in raw material oil are silicon compounds produced by the decomposition of silicon-based defoaming agents used in coker plants. Among such silicon compounds, compounds in which all hydrogen atoms bonded to silicon atoms of cyclic cyclopolysiloxanes are replaced with methyl groups (hereinafter also referred to as "cyclic silicon compounds") are known. The inventors of the present invention investigated the content of cyclic silicon compounds with 3 to 9 silicon atoms relative to the total mass of cyclic silicon compounds with 3 to 9 silicon atoms contained in the coker-cracked naphtha fraction described in Patent Document 1 above and the heavy coker-cracked hydrocarbon oil of this embodiment by gas chromatography-mass spectrometry (GC / MS). As a result, in the coker-cracked naphtha fraction, the total content of cyclic silicon compounds with 3 and 4 silicon atoms was 100% by mass, and no cyclic silicon compounds with 5 to 9 silicon atoms were detected. On the other hand, in heavy coker-cracked hydrocarbon oil, the total content of cyclic silicon compounds with 3 and 4 silicon atoms was approximately 17% by mass, and the total content of cyclic silicon compounds with 5 to 9 silicon atoms was approximately 83% by mass. It was also considered possible that cyclic silicon compounds with 10 or more silicon atoms were present. The total content of cyclic silicon compounds with 7 to 9 silicon atoms relative to the total mass of cyclic silicon compounds with 3 to 9 silicon atoms in the raw material oil is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. The silicon adsorbent of the present invention is particularly suitable for use in raw material oil containing cyclic silicon compounds of such composition.

[0067] The 10% volume distillation temperature of the raw material oil is preferably 230-440°C, more preferably 250-420°C, and even more preferably 270-400°C. The 50% volume distillation temperature of the raw material oil is preferably 270-520°C, more preferably 290-500°C, and even more preferably 310-480°C. The 90% volume distillation temperature of straight-run diesel fuel is preferably 410 to 600°C, more preferably 415 to 580°C, and even more preferably 420 to 560°C.

[0068] <Hydrogenation catalyst> As the hydrogenation catalyst packed downstream of the silicon adsorbent layer, a hydrogenation catalyst for feedstock oils containing heavy coker cracked hydrocarbon oil, known in this field, can be used. For example, a catalyst can be used in which the above-mentioned hydrogenation active component is supported on a porous inorganic oxide support containing alumina. The type of hydrogenation active component and the preferred range of its content are the same as in the case of the silicon capture hydrogenation catalyst described above. Furthermore, as mentioned above, the silicon capture hydrogenation catalyst also has hydrogenation activity. Alternatively, the hydrogenation catalysts described in Japanese Patent Publication No. 2019-178251 and Japanese Patent Publication No. 2004-074075 may be used.

[0069] <Silicon collection conditions, hydrogenation treatment conditions> The average temperature of the silicon adsorbent layer and the hydrogenation catalyst layer in the reactor is 300 to 410°C, preferably 310 to 410°C, and more preferably 320 to 410°C. When the temperature is above the lower limit of the above range, the hydrogenation treatment of the feedstock oil proceeds more easily. In addition, the silicon adsorption capacity of the silicon adsorbent is improved. When the temperature is below the upper limit of the above range, sintering of the hydrogenation active component in the hydrogenation catalyst is suppressed.

[0070] The pressure (partial pressure of hydrogen) is 10 to 20 MPa, preferably 13 to 18 MPa, and more preferably 14 to 17 MPa. If the pressure is above the lower limit of the above range, the performance degradation of the hydrogenation catalyst by heavy coker cracking hydrocarbon oil can be suppressed. While the upper limit of the pressure is not substantially limited, it is usually 20 MPa or less due to equipment design considerations.

[0071] The hydrogen / oil ratio is 170-1400m 3 / m 3 The range is 300-1375m. 3 / m 3 Preferably, 350-1350m 3 / m 3 It is preferable that it be so.

[0072] The liquid space velocity of the feedstock oil relative to the total volume of the silicon adsorbent layer and the hydrogenation catalyst layer is 0.1 to 2.0 hours. -1 Therefore, 0.3 to 1.5 hours -1 Preferably, this is the case, and the duration is 0.5 to 1.2 hours. -1 It is more preferable that the following conditions are met: If the liquid space velocity is above the lower limit of the range, the amount of raw material processed per unit time improves. If the liquid space velocity is below the upper limit of the range, the hydrogenation process proceeds more easily.

[0073] <Position and amount of silicone adsorbent filling> In this embodiment, the reactor is packed in the order of silicon adsorbent and hydrogenation catalyst. If the descaling catalyst described later is not packed in the reactor, the silicon adsorbent is preferably packed at the inlet side of the reactor. Specifically, the position of the silicon adsorbent is preferably 0 to 35 volume percent from the inlet of the catalyst layer relative to the total volume of the catalyst layer packed in the reactor (including the silicon adsorbent of the present invention and the descaling catalyst described later; the volume is the packing volume). It is more preferably 0 to 30 volume percent, and particularly preferably 0 to 25 volume percent. In this case, the silicon adsorbent collects silicon compounds in the feed oil, thereby suppressing poisoning of the hydrogenation catalyst packed later by silicon compounds. A descaling catalyst for removing scale from the feed oil may be packed further up from the silicon adsorbent. In this case, the amount of descaling catalyst packed is preferably 5 volume percent or less relative to the total volume of the catalyst layer (including the silicon adsorbent of the present invention and the descaling catalyst described later; the volume is the packing volume). The amount of silicon adsorbent packed is preferably 5 to 35 volume%, preferably 5 to 30 volume%, and preferably 5 to 25 volume%, relative to the total volume of the catalyst layer (including the silicon adsorbent of the present invention and the descaling catalyst described later; the volume is the packing volume). The amount of hydrogenation catalyst packed is preferably 65 to 95% by volume, preferably 70 to 95% by volume, and preferably 75 to 95% by volume, relative to the total volume of the catalyst layer (including the silicon adsorbent of the present invention and the descaling catalyst described later; the volume is the packing volume). The silicon adsorbent and hydrogenation catalyst packed into the reactor may each be of one type or two or more types.

[0074] <Hydrogenated oil> The sulfur content of the hydrogenated oil produced by the hydrogenation treatment method of this embodiment is typically 0.1% by mass or less relative to the total mass. The silicon concentration (elemental basis) relative to the total mass of hydrogenated oil is typically less than 0.3 ppm by mass. The nickel content (elemental equivalent) relative to the total mass of hydrogenated oil is typically less than 0.1 ppm by mass. The vanadium content (elemental equivalent) relative to the total mass of hydrogenated oil is typically less than 0.1 ppm by mass.

[0075] The hydrogenation catalyst may be activated by sulfidation treatment in a reactor before use (i.e., prior to carrying out the hydrogenation treatment method of this embodiment). This sulfidation treatment can generally be carried out by passing petroleum distillates containing sulfur compounds, a mixture of petroleum distillates containing sulfur compounds and sulfiding agents such as dimethyl disulfide or carbon disulfide, or hydrogen sulfide through the hydrogenation catalyst at 200 to 400°C, preferably 250 to 350°C, under a hydrogen atmosphere at atmospheric pressure or a hydrogen partial pressure of at least that level.

[0076] According to the silicon collection method of this embodiment, poisoning of the hydrogenation catalyst packed downstream of the silicon adsorbent layer by silicon compounds can be suppressed. As a result, the hydrogenation treatment can proceed sufficiently, and sulfur compounds in the feed oil, including heavy coker cracked hydrocarbon oil, can be reduced over a long period of time.

[0077] To carry out the silicon collection method and hydrogenation treatment method on a commercial scale, the silicon collection agent and the catalyst layer of the hydrogenation treatment catalyst of this embodiment should be formed in a fixed bed within a reactor, the raw material oil should be introduced into this reactor, and the silicon collection and hydrogenation treatment should be carried out under the above conditions.

[0078] The hydrogenation treatment method may be a single-stage silicon collection method and hydrogenation treatment method in which a silicon collecting agent and a hydrogenation treatment catalyst are packed into a single reactor, or it may be a multi-stage continuous silicon collection method and multi-stage continuous hydrogenation treatment method in which multiple reactors are packed.

[0079] <Mechanism of Action> As mentioned above, extensive research has been conducted on silicon capture during the hydrogenation of coker-decomposed naphtha fractions. These studies suggest that silicon compounds are chemically adsorbed onto the alumina surface by reacting with hydroxyl groups on the alumina surface in the hydrogenation catalyst. Therefore, increasing the amount of hydroxyl groups on the alumina surface is considered important for improving silicon capture capacity. For example, in the aforementioned Patent Document 1, the number of hydroxyl groups on the hydrogenation catalyst surface is increased by supplying 0.01 to 10 volume percent of water to the hydrogenation catalyst along with the coker-decomposed naphtha fraction. In addition, increasing the specific surface area of ​​the hydrogenation catalyst is also considered effective in increasing the number of hydroxyl groups on the hydrogenation catalyst surface. On the other hand, as shown in the examples and comparative examples described later, in silicon capture during the hydrogenation treatment of feedstock oil containing heavy coker cracked hydrocarbon oil, silicon adsorbents with a large specific surface area tend to have lower silicon capture capacity (the silicon adsorbents in Comparative Examples 1 and 2, which had the largest specific surface area, were found to have the lowest silicon capture capacity). This is considered to be the exact opposite result to that observed in silicon capture during the hydrogenation treatment of coker cracked naphtha fractions. The reason for this result is thought to be as follows. As mentioned above, silicon compounds contained in coker-cracked naphtha fractions are silicon compounds with small molecular weights (molecular size), while silicon compounds contained in feedstock oils including heavy coker-cracked hydrocarbon oils are silicon compounds with large molecular weights (molecular size). In the case of silicon compounds with small molecular size, they can sufficiently diffuse into the pores of general hydrogenation catalysts, so the silicon collection ability depends on the number of hydroxyl groups (specific surface area), which are the adsorption sites of the silicon compounds. On the other hand, in the case of silicon compounds with large molecular size, the diffusivity into the pores decreases, making it difficult for the silicon compounds to penetrate deep into the pores. As a result, the hydroxyl groups, which are the adsorption sites of the silicon compounds, are not efficiently utilized, and the silicon collection ability is thought to depend on the diffusivity of the silicon compounds. In the present invention, by setting the average pore diameter of the silicon adsorbent to a certain level or higher, the diffusivity into the pores of silicon compounds with large molecular size is improved, and the hydroxyl groups, which are the adsorption sites, are efficiently utilized, which is thought to improve the silicon collection ability. In other words, for silicon compounds with large molecular sizes, simply increasing the specific surface area does not improve silicon collection capacity. It is considered important that the average pore size is appropriate to the molecular size of the silicon compound in order to improve silicon collection capacity. [Examples]

[0080] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0081] <Analysis Method for the Physical Properties and Composition of Silicone Adsorbent> [1] Analysis of physical properties (specific surface area, pore volume, average pore diameter, and pore distribution) (a) Measurement method and equipment used: The specific surface area was measured using the BET method with nitrogen adsorption. The nitrogen adsorption device used was a surface area measuring device (BELSORP-mini II) manufactured by Microtrac-Bel Co., Ltd. Pore ​​volume, average pore diameter, and pore distribution were measured by mercury intrusion. A porosimeter (AutoPore IV: Micromeritics) was used as the mercury intrusion apparatus.

[0082] (b) Measurement principle of the mercury intrusion method: The mercury intrusion method is based on the law of capillary action. In the case of mercury and cylindrical pores, this law is expressed by the following equation. That is, the volume of mercury entering the pores is measured as a function of the applied pressure P. The surface tension of the mercury in the catalyst pores was assumed to be 484 dyne / cm, and the contact angle was assumed to be 130°. D = -(1 / P)4γcosθ In the formula, D is the pore diameter, P is the applied pressure, γ is the surface tension, and θ is the contact angle. Pore ​​volume is the total volume of mercury that enters the pores per gram of silicon adsorbent. Average pore diameter is the average value of D, calculated as a function of P. The pore size distribution is the distribution of D calculated as a function of P.

[0083] (c) Measurement procedure: (1) Turn on the power to the vacuum heating degasser, set the temperature to 400°C and the vacuum degree to 5 × 10⁻¹⁰. -2 Verify that it is less than or equal to Torr. (2) Place the empty sample burette into the vacuum heating degasser. (3) Vacuum level 5 × 10 -2 After confirming that the value is below Torr, remove the sample burette from the vacuum heating degasser by closing its stopcock, let it cool, and then measure its weight. (4) Place the sample (silicone adsorbent) into the sample burette. (5) Place the sample burette containing the sample into a vacuum heating degasser until the vacuum level reaches 5 × 10 -2Maintain the Torr level below 1 / 2 for at least one hour. (6) Remove the sample burette containing the sample from the vacuum heating degasser, let it cool, and then measure its weight to determine the sample weight. (7) Place the sample into the AutoPore IV cell. (8) Measure using AutoPore IV.

[0084] [2] Analysis of composition The proportions of each element in the silicon adsorbent were confirmed to be in proportion to the amount of raw materials used, using the following method. Furthermore, the silicon content in the silicon adsorbent extracted after the hydrogenation treatment described later was also confirmed using the following method. (a) Analytical methods and equipment used: Elemental analysis of the silicon adsorbent was performed using an inductively coupled plasma atomic emission spectrometer (iCAP 6000: Thermo Scientific). Elemental quantification was performed using the absolute calibration curve method.

[0085] (b) Measurement procedure: (1) 0.05 g of silicone adsorbent, 1 mL of hydrochloric acid (50% by mass), one drop of hydrofluoric acid, and 1 mL of pure water were added to Uniseal and heated to dissolve. (2) After dissolution, the solution was transferred to a polypropylene volumetric flask (50 mL), pure water was added, and the total volume was weighed to 50 mL. (3) This solution was measured using the inductively coupled plasma emission spectrometer described above.

[0086] <Method for collecting silicon from raw material oil (hydrogenation treatment method for raw material oil)> Hydrogenation treatment was carried out on feedstock oil with properties listed in Table 1, containing 93% by volume of heavy coker cracked hydrocarbon oil, according to the following procedure. In Table 1, "average" refers to the average properties of the feedstock oil over the entire reaction period, "maximum" refers to the maximum properties of the feedstock oil over the entire reaction period, and "minimum" refers to the minimum properties of the feedstock oil over the entire reaction period. Also, T10 represents a 10% by volume distillation temperature, T50 represents a 50% by volume distillation temperature, and T90 represents a 90% by volume distillation temperature.

[0087] A high-pressure flow reactor was filled from the reactor inlet side in the following order: silicon adsorbent (including silicon adsorbent hydrogenation treatment catalyst) followed by a hydrogenation treatment catalyst. The hydrogenation treatment catalyst used was alumina supported with molybdenum, nickel, and cobalt. The volume ratio of silicon adsorbent to hydrogenation treatment catalyst was 25:75. Pretreatment was then carried out under the following conditions. Next, a mixed fluid of feedstock oil containing heavy coker cracked hydrocarbon oil and hydrogen-containing gas was introduced from the top of the reactor (reactor inlet) and hydrogenation treatment was carried out under the reaction conditions shown in Table 2. The mixed fluid of the produced oil and gas was discharged from the bottom of the reactor (reactor outlet), and the produced oil was separated using a gas-liquid separator. In Table 2, "liquid space velocity" refers to the liquid space velocity of the feedstock oil relative to the total volume of the silicon adsorbent layer and the hydrogenation treatment catalyst layer. Furthermore, "average" refers to the average reaction conditions over the entire reaction period, "maximum" refers to the maximum reaction conditions over the entire reaction period, and "minimum" refers to the minimum reaction conditions over the entire reaction period. Temperature refers to the average temperature across all layers, including the silicon adsorbent layer and the hydrogenation catalyst layer. The temperature was adjusted so that the sulfur content relative to the total mass of the hydrogenated oil was 0.1% by mass.

[0088] Catalyst pretreatment conditions: Dried at atmospheric pressure at 120°C for 3 hours. Pre-sulfurization of the catalyst was carried out using reduced-pressure diesel fuel at a hydrogen partial pressure of 10.3 MPa and 370°C for 12 hours. Afterward, the catalyst was switched to the feedstock oil used for activity evaluation.

[0089] [Table 1]

[0090] [Table 2]

[0091] [Example 1] (Manufacturing of alumina molded products) 10 kg of a 5% by mass sodium aluminate aqueous solution was heated to 60°C, and then 2.8 kg of a 25% by mass aluminum sulfate aqueous solution was slowly added until the pH of the solution was 7. The temperature of the solution was maintained at 60°C during this process. The alumina slurry produced by the above procedure was filtered, and the filtered alumina gel was repeatedly washed with a 0.3% by mass ammonia aqueous solution. 5 kg of water was added to the washed alumina gel, and then a 10% by mass ammonia aqueous solution was added to adjust the pH of the aqueous dispersion of the gel to 11. Next, the aqueous dispersion of the gel was heated to 90°C and aged for 40 hours while stirring and refluxing. After that, a 5N nitric acid aqueous solution was added to adjust the pH to 2, and the mixture was stirred for 15 minutes. Furthermore, a 10% by mass ammonia aqueous solution was added to adjust the pH to 11. After filtering the resulting aqueous dispersion of the gel, water was added at room temperature to adjust the moisture content to a viscosity that was easy to mold. The water content of the alumina gel after moisture adjustment was 70% by mass. Subsequently, silica particles were added and kneaded uniformly in a kneader. The kneaded cake was placed in an extruder to produce a four-leaf clover-shaped extruded product with a major diameter of 1.3 mm and a minor diameter of 1.1 mm. This product was dried at 110°C for 10 hours, and then fired by adjusting the firing temperature and firing time to obtain an alumina molded body A containing silica, with the physical properties of silicon adsorbent A as described in Table 3. The amount of silica particles added was adjusted to match the composition shown in Table 3.

[0092] (Supporting of hydrogenation-active components) A molybdenum-nickel aqueous solution was prepared by dissolving ammonium paramolybdate and nickel nitrate in 100 g of deionized water. The amounts of ammonium paramolybdate and nickel nitrate were set according to the composition shown in Table 3. The molybdenum-nickel aqueous solution was impregnated into an alumina molded body A in a round-bottom flask to obtain an impregnated body. The impregnated body was dried, and then fired at 550°C for 3 hours under an air atmosphere to obtain silicon adsorbent A. Table 3 shows the content of each element in silicon adsorbent A in terms of oxides, as well as the specific surface area, pore volume, average pore diameter, and the ratio of the volume of pores with an average pore diameter of ±1.5 nm to the total pore volume of silicon adsorbent A (the same applies to silicon adsorbents B to H below). In Table 3, "pore distribution" means "the ratio of the volume of pores with an average pore diameter of ±1.5 nm to the total pore volume."

[0093] The raw oil was subjected to hydrogenation treatment for 1000 days using silicon adsorbent A. After that, silicon adsorbent A was removed from the reactor, and the silicon content was measured using the method described above. By subtracting the silicon content derived from the silica originally contained in silicon adsorbent A, the amount of silicon deposited in the removed silicon adsorbent A (on an elemental basis) was calculated. The results are shown in Table 3 (the same applies to Examples 2-6 and Comparative Examples 1 and 2 below).

[0094] [Example 2] (Manufacturing of alumina molded products) 10 kg of a 5% by mass sodium aluminate aqueous solution was heated to 60°C, and then 2.8 kg of a 25% by mass aluminum sulfate aqueous solution was slowly added until the pH of the solution was 7. The temperature of the solution was maintained at 60°C during this process. The alumina slurry produced by the above procedure was filtered, and the filtered alumina gel was repeatedly washed with a 0.3% by mass ammonia aqueous solution. 5 kg of water was added to the washed alumina gel, and then a 10% by mass ammonia aqueous solution was added to adjust the pH of the aqueous dispersion of the gel to 11. Next, the aqueous dispersion of the gel was heated to 90°C and aged for 40 hours while stirring and refluxing. After that, a 5N nitric acid aqueous solution was added to adjust the pH to 2, and the mixture was stirred for 15 minutes. Furthermore, a 10% by mass ammonia aqueous solution was added to adjust the pH to 11. After filtering the resulting aqueous dispersion of the gel, water was added at room temperature to adjust the viscosity to a level suitable for molding. The water content of the alumina gel after moisture adjustment was 70% by mass. Subsequently, silica particles, zinc oxide particles, and phosphoric acid were added and kneaded uniformly in a kneader. The kneaded cake was placed in an extruder to produce a four-leaf clover-shaped extruded product with a major diameter of 1.3 mm and a minor diameter of 1.1 mm. This product was dried at 110°C for 10 hours, and then fired at an adjusted temperature and time to obtain an alumina molded body B containing silica, zinc oxide, and phosphoric acid, with the properties of silicon adsorbent B as described in Table 3. The amounts of silica particles, zinc oxide particles, and phosphoric acid added were adjusted to match the composition shown in Table 3.

[0095] (Supporting of hydrogenation-active components) Except for using alumina molded body B instead of alumina molded body A, and adjusting the amounts of ammonium paramolybdate and nickel nitrate to achieve the composition shown in Table 3, the hydrogenation active component was supported in the same manner as in Example 1 to obtain silicon adsorbent B.

[0096] The raw oil was subjected to hydrogenation treatment for 1000 days using silicon adsorbent B. After that, silicon adsorbent B was removed from the reactor, and its silicon content was measured using the method described above. By subtracting the silicon content derived from the silica originally contained in silicon adsorbent B, the amount of silicon deposited in the removed silicon adsorbent B (on an elemental basis) was calculated.

[0097] [Example 3] (Manufacturing of alumina molded products) Alumina molded body C was obtained in the same manner as in Example 2, except that the amounts of silica particles, zinc oxide particles, and phosphoric acid added were adjusted to achieve the composition shown in Table 3, and the firing temperature and firing time of the alumina molded product were changed.

[0098] (Supporting of hydrogenation-active components) Except for using alumina molded body C instead of alumina molded body A, and adjusting the amounts of ammonium paramolybdate and nickel nitrate to achieve the composition shown in Table 3, the hydrogenation active component was supported in the same manner as in Example 1 to obtain silicon adsorbent C.

[0099] The raw oil was subjected to hydrogenation treatment for 1000 days using silicon adsorbent C. After that, silicon adsorbent C was removed from the reactor, and its silicon content was measured using the method described above. By subtracting the silicon content derived from the silica originally contained in silicon adsorbent C, the amount of silicon deposited in the removed silicon adsorbent C (on an elemental basis) was calculated.

[0100] [Example 4] (Manufacturing of alumina molded products) Alumina molded body D was obtained in the same manner as in Example 2, except that the amounts of silica particles, zinc oxide particles, and phosphoric acid added were adjusted to achieve the composition shown in Table 3, and the firing temperature and firing time of the alumina molded product were changed.

[0101] (Supporting of hydrogenation-active components) Except for using alumina molded body D instead of alumina molded body A, and adjusting the amounts of ammonium paramolybdate and nickel nitrate to achieve the composition shown in Table 3, the hydrogenation active component was supported in the same manner as in Example 1 to obtain silicon adsorbent D.

[0102] The raw oil was subjected to hydrogenation treatment for 1000 days using silicon adsorbent D. After that, silicon adsorbent D was removed from the reactor, and its silicon content was measured using the method described above. By subtracting the silicon content derived from the silica originally contained in silicon adsorbent D, the amount of silicon deposited in the removed silicon adsorbent D (on an elemental basis) was calculated.

[0103] [Example 5] (Manufacturing of alumina molded products) Alumina molded body E was obtained in the same manner as in Example 1, except that the amount of silica particles added was adjusted to achieve the composition shown in Table 3, and the firing temperature and firing time of the alumina molded product were changed.

[0104] (Supporting of hydrogenation-active components) Except for using alumina molded body E instead of alumina molded body A, and adjusting the amounts of ammonium paramolybdate and nickel nitrate to achieve the composition shown in Table 3, the hydrogenation active component was supported in the same manner as in Example 1 to obtain silicon adsorbent E.

[0105] The raw oil was subjected to hydrogenation treatment for 1000 days using silicon adsorbent E. After that, silicon adsorbent E was removed from the reactor, and its silicon content was measured using the method described above. By subtracting the silicon content derived from the silica originally contained in silicon adsorbent E, the amount of silicon deposited in the removed silicon adsorbent E (on an elemental basis) was calculated.

[0106] [Example 6] (Manufacturing of alumina molded products) Alumina molded body F was obtained in the same manner as in Example 1, except that the amount of silica particles added was adjusted to achieve the composition shown in Table 3, and the firing temperature and firing time of the alumina molded product were changed.

[0107] (Supporting of hydrogenation-active components) Except for using alumina molded body F instead of alumina molded body A, and adjusting the amounts of ammonium paramolybdate and nickel nitrate to achieve the composition shown in Table 3, the hydrogenation active component was supported in the same manner as in Example 1 to obtain silicon adsorbent F.

[0108] The raw oil was subjected to hydrogenation treatment for 1000 days using silicon adsorbent F. After that, silicon adsorbent F was removed from the reactor, and its silicon content was measured using the method described above. By subtracting the silicon content derived from the silica originally contained in silicon adsorbent F, the amount of silicon deposited in the removed silicon adsorbent F (on an elemental basis) was calculated.

[0109] [Comparative Example 1] (Manufacturing of alumina molded products) Alumina molded body G was obtained in the same manner as in Example 1, except that the amount of silica particles added was adjusted to achieve the composition shown in Table 3, and the firing temperature and firing time of the alumina molded product were changed.

[0110] (Supporting of hydrogenation-active components) Except for using alumina molded body G instead of alumina molded body A, and adjusting the amounts of ammonium paramolybdate and nickel nitrate to achieve the composition shown in Table 3, the hydrogenation active component was supported in the same manner as in Example 1 to obtain silicon adsorbent G.

[0111] The raw oil was subjected to hydrogenation treatment for 1000 days using silicon adsorbent G. After that, silicon adsorbent G was removed from the reactor, and its silicon content was measured using the method described above. By subtracting the silicon content derived from the silica originally contained in silicon adsorbent G, the amount of silicon deposited in the removed silicon adsorbent G (in terms of elements) was calculated.

[0112] [Comparative Example 2] (Manufacturing of alumina molded products) Alumina molded body H was obtained in the same manner as in Example 1, except that the amount of silica particles added was adjusted to achieve the composition shown in Table 3, and the firing temperature and firing time of the alumina molded product were changed. The alumina molded body H was used as the silicon adsorbent H.

[0113] The raw oil was subjected to hydrogenation treatment for 1000 days using silicon adsorbent H. After that, silicon adsorbent H was removed from the reactor, and its silicon content was measured using the method described above. By subtracting the silicon content derived from the silica originally contained in silicon adsorbent H, the amount of silicon deposited in the removed silicon adsorbent H (on an elemental basis) was calculated.

[0114] [Table 3]

[0115] The silicon adsorbents of Examples 1 to 6 of the present invention were found to have a larger silicon deposition amount and superior silicon adsorption capacity compared to the silicon adsorbent of Comparative Example 1, which had an average pore diameter of less than 7 nm and a pore volume of less than 0.55 mL / g, and the silicon adsorbent of Comparative Example 2, which had an average pore diameter of less than 7 nm.

[0116] Figure 1 shows the relationship between the average pore size of the silicon adsorbent in Examples 1-6 and Comparative Examples 1 and 2, and the amount of silicon deposited in the silicon adsorbent. As shown in Figure 1, a correlation was found between the average pore size and the amount of silicon deposited. The silicon adsorbent in Examples 1 and 2, which had an average pore size of around 10 nm, was found to have particularly excellent silicon adsorption capacity. Furthermore, although the silicon adsorbent in Examples 1-6 and Comparative Example 1 contains a hydrogenation active component, and the silicon adsorbent in Comparative Example 2 does not contain a hydrogenation active component, as shown in Figure 1, a correlation between the average pore size and the amount of silicon deposited was observed in all of the silicon adsorbent in Examples 1-6 and Comparative Examples 1 and 2. In other words, the presence or absence of a hydrogenation active component does not affect (or is hardly affected by) the silicon adsorption capacity, and it was considered that the pore structure of the silicon adsorbent is important. [Industrial applicability]

[0117] The silicon adsorbent according to the present invention is useful in hydrogenation treatment methods for heavy hydrocarbon oils because it has excellent silicon adsorption capacity for raw material oils, including heavy coker cracked hydrocarbon oil.

Claims

1. A silicon adsorbent for raw material oils containing heavy coker cracked hydrocarbon oil, The aforementioned silicon adsorbent contains alumina, The alumina content relative to the total mass of the aforementioned silicon adsorbent is 50% by mass or more. The silicon adsorbent for raw materials containing heavy coker-cracked hydrocarbon oil is characterized in that it has pores with an average pore diameter of 8 to 13 nm and a pore volume of 0.55 to 0.75 mL / g, and the ratio of the volume of pores having a pore diameter of ±1.5 nm to the pore volume is 30% or more.

2. Specific surface area of ​​150-300 m² ２ The silicon adsorbent according to claim 1, wherein the amount is / g.

3. The silicon adsorbent according to Claim 1, wherein the specific surface area is 230 to 300 m² / g.

4. The silicon adsorbent according to any one of claims 1 to 3, further comprising a hydrogenation active component, wherein the hydrogenation active component is supported on the alumina.

5. A raw material oil containing heavy coker-cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 ppm by mass is subjected to a temperature of 300 to 410°C, a pressure of 10 to 20 MPa, and a hydrogen / oil ratio of 170 to 1400 ml. ３ / m ３ , and liquid space velocity 0.1 to 2.0 h －１ A method for collecting silicon from a raw material oil containing heavy coker cracked hydrocarbon oil, characterized by sequentially contacting the silicon collecting agent and hydrogenation catalyst described in any one of claims 1 to 3.

6. A raw material oil containing heavy coker-cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 ppm by mass is subjected to a temperature of 300 to 410°C, a pressure of 10 to 20 MPa, and a hydrogen / oil ratio of 170 to 1400 ml. ３ / m ３ , and liquid space velocity 0.1 to 2.0 h －１ A method for hydrogenating a raw material oil containing heavy coker cracked hydrocarbon oil, characterized by sequentially contacting it with a silicon adsorbent and a hydrogenation catalyst according to any one of claims 1 to 3.

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