JP2023145850A - Silicon scavenger, scavenging method of silicon, and hydrogenation treatment method - Google Patents

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

The present invention relates to a silicon trapping agent, a silicon trapping method, and a hydrogenation treatment method.

Due to the decrease in demand for heavy oil, the main heavy oil base material, crude oil, is being treated with atmospheric distillation equipment to obtain atmospheric distillation residue oil, and the above-mentioned atmospheric distillation residue oil is being processed in vacuum distillation equipment. There is a need for technology that efficiently converts distillation residue oil into light oil with high added value.

As a technology for converting heavy oil base material into light oil, the coker cracked fraction obtained by thermally decomposing vacuum distillation residue oil in a heavy oil thermal cracker (hereinafter also referred to as "coker equipment") is hydrotreated. A process is known that utilizes the fraction obtained by (hydrodesulfurization). Among the coker cracked fractions, a light fraction (coker cracked naphtha fraction) is hydrotreated and then processed in a catalytic reforming reactor to produce a fraction containing high value-added basic chemicals. Ru. In addition, the heavy fraction (heavy coker cracked hydrocarbon oil) is hydrotreated and then processed in a fluid catalytic cracking apparatus to produce middle distillates such as gasoline, kerosene, and light oil.

Incidentally, in a coker device, a silicon-based foaming agent is used to suppress foaming within the reaction drum. Therefore, the silicon compound derived from the defoaming agent is mixed into the fraction obtained by thermal decomposition in the coker device. This silicon compound is known to be a poison for hydrotreating catalysts used in hydrotreating. It is also known that this silicon compound is a substance that poisons the catalytic reforming catalyst filled in the catalytic reforming reactor.

Patent Document 1 discloses that in the hydrogenation treatment of a coker-cracked naphtha fraction containing silicon compounds, 0.01 to 10% by volume of water is supplied to a hydrotreatment catalyst together with the coker-cracked naphtha fraction. It is described that the silicon-trapping ability of the catalyst is improved.

US Patent No. 6,576,121

As described in Patent Document 1, extensive research has been conducted on silicon capture in the hydrogenation treatment of coker-cracked naphtha fractions. On the other hand, the reality is that research on silicon collection in the hydroprocessing of heavy coker-cracked hydrocarbon oils has not progressed as much as silicon collection in the hydroprocessing of coker-cracked naphtha fractions.

The present invention has been made in view of the above-mentioned circumstances, and provides a silicone scavenger that has excellent silicone scavenging ability for feedstock oil containing heavy coker cracked hydrocarbon oil, as well as a heavy silicone scavenger using the silicone scavenger. It is an object of the present invention to provide a method for collecting silicon in feedstock oil containing coker cracked hydrocarbon oil and a method for hydrogenating feedstock oil containing heavy coker cracked hydrocarbon oil using the silicone scavenger.

In order to solve the above problems, the present invention has the following aspects.
[1] A silicone scavenger for feedstock oil containing heavy coker cracked hydrocarbon oil, wherein the silicone scavenger contains alumina, and the content of alumina is 50% by mass with respect to the total mass of the silicone scavenger. As above, the silicon scavenger is a heavy coker cracked hydrocarbon oil characterized by having pores with an average pore diameter of 7 to 13 nm and a pore volume of 0.55 to 0.75 mL/g. A silicone collector for raw oil containing
[2] The silicon collector according to [1], further comprising a hydrogenation active component, and the hydrogenation active component is supported on the alumina.
[3] Raw material oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 mass ppm is heated 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 a heavy coker cracked hydrocarbon, characterized in that it is brought into sequential contact with the silicon scavenger and the hydrotreating catalyst according to [1] or [2] at a liquid hourly velocity of 0.1 to 2.0 h ^-1 . A method for collecting silicon from raw oil containing oil.
[4] Raw material oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 mass ppm is heated 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 a heavy coker cracked hydrocarbon, characterized in that it is brought into sequential contact with the silicon scavenger and the hydrotreating catalyst according to [1] or [2] at a liquid hourly velocity of 0.1 to 2.0 h ^-1 . A method for hydrotreating feedstock oil containing oil.
[5] Raw material oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 mass ppm is heated 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 the production of hydrogenated oil, which is characterized by sequentially contacting the silicon scavenger and the hydrotreating catalyst according to [1] or [2] at a liquid hourly velocity of 0.1 to 2.0 h ^-1 . Method.

According to the present invention, there is provided a silicone scavenger that has an excellent ability to scavenge silicon from feedstock oil containing heavy coker-cracked hydrocarbon oil, and a silicone scavenger that uses the silicone scavenger to collect feedstock oil containing heavy coker-cracked hydrocarbon oil. It is possible to provide a method for collecting silicon and a method for hydrotreating feedstock oil containing heavy coker-cracked hydrocarbon oil using the silicon collecting agent.

FIG. 3 is a diagram showing the relationship between the average pore diameter of the silicon scavengers of Examples 1 to 6 and Comparative Examples 1 and 2 and the amount of silicon deposited in the silicon scavengers.

Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example of the embodiments of the present invention, and the present invention is not limited to these contents, and may be modified and implemented within the scope of the gist. can do.

<Definition>
In this specification, "heavy coker cracked hydrocarbon oil" refers to distillate oil obtained by atmospheric distillation of a coker cracked fraction obtained by thermally decomposing vacuum distillation residue oil in a coker device. means the heaviest fraction. The vacuum distillation residue oil is a residue oil obtained by further processing the atmospheric distillation residue oil obtained by treating crude oil with an atmospheric distillation apparatus using a vacuum distillation apparatus. The properties of the heavy coker cracked hydrocarbon oil include, for example, a density at 15°C of 0.91 to 1.00 g/mL, a sulfur content of 1.5 to 5.5% by mass, and a nitrogen content of 0.01 to 0. 6% by mass, silicon concentration (element equivalent) 0.1 to 15.0 mass ppm, nickel content (element equivalent) 0.1 to 1.5 mass ppm, vanadium content (element equivalent) 0.1 to 1 .5 mass ppm, 10 volume% distillation temperature is 230 to 440°C, 50 volume% distillation temperature is 270 to 520°C, and 90 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 - How to determine 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 testing 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".
Silicon concentration can be measured by inductively coupled plasma-emission spectroscopy (ICP-AES) or atomic absorption spectroscopy (AAS).
The 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 - How to determine distillation properties."

The content of elements contained in the silicon scavenger can be measured by inductively coupled plasma emission spectrometry.
The average pore diameter, pore volume, and pore distribution of the silicon scavenger can be measured by mercury intrusion method.
The specific surface area of the silicon scavenger is a BET specific surface area, and can be measured by a nitrogen adsorption method.

"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"), "Metals of group 9 of the periodic table""Group 10 metal" (hereinafter sometimes referred to as "Group 10 metal") means a Group 6 metal, a Group 9 metal, and a Group 10 metal in the long-period table, respectively.
Group 6 metals, Group 9 metals, and Group 10 metals are also collectively referred to as "hydrogenation active components."

≪Silicon scavenger≫
The silicon scavenger for feedstock oil containing heavy coker cracked hydrocarbon oil of this embodiment contains alumina. The content of alumina based on the total mass of the silicon scavenger is 50% by mass or more. The silicon scavenger has pores with an average pore diameter of 7 to 13 nm and a pore volume of 0.55 to 0.75 mL/g.

<Composition of silicone scavenger>
(alumina)
Various aluminas such as α-alumina, β-alumina, γ-alumina, and δ-alumina can be used as the alumina contained in the silicon collector, but alumina that is porous and has a high specific surface area is preferable. Among them, γ-alumina is more preferable.
The purity of alumina is preferably 98% by mass or more, more preferably 99% by mass or more. Impurities in alumina include SO ₄ ^2- , Cl ^- , Fe ₂ O ₃ , Na ₂ O, etc., but it is preferable that these impurities be as small as possible, and the total amount of impurities should be 2% by mass or less. The content is preferably 1% by mass or less, and more preferably 1% by mass or less. For each component, it is preferable that SO ₄ ^2- be 1.5% by mass or less, and Cl ⁻ , Fe ₂ O ₃ , and Na ₂ O each be 0.1% by mass or less.
Silicon compounds in the feedstock oil containing heavy coker cracked hydrocarbon oil are chemically adsorbed onto the alumina surface by reacting with the hydroxyl groups on the alumina surface.

The content of alumina (including the content of the above-mentioned impurities) with respect to the total mass of the silicon collector is 50% by mass or more, preferably 70% by mass or more, and preferably 90% by mass or more. The content is more preferably 95% by mass, and may be 100% by mass.
The content of alumina can be determined by measuring the content of aluminum element in the silicon scavenger by the method described above and calculating it in terms of oxide (Al ₂ O ₃ ). Furthermore, when the silicon scavenger contains a substance other than alumina, which will be described later, it can also be determined by subtracting the content of the substance other than alumina from 100%.

The silicon scavenger 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.

(Substances containing zinc)
Substances containing zinc include simple zinc and zinc compounds. The silicon scavenger may contain only one of zinc alone or a zinc compound, or may contain both.
Examples of zinc compounds in silicone collectors include zinc oxide, zinc nitrate, zinc sulfate, zinc carbonate, zinc phosphate, zinc aluminate, zinc titanate, zinc molybdate, etc. preferable. In addition to the above-mentioned compounds, the zinc compound in the silicon collector includes zinc element, aluminum element, phosphorus element, silicon element, group 6 metal element, group 9 metal element, and group 9 metal element contained in the silicon collector. Examples include composite oxides and composite sulfides with at least one element selected from the group consisting of Group 10 metal elements. The substance containing zinc may exist as a mixture with alumina or may be supported on alumina.
When the silicon scavenger contains a substance containing zinc, the content of the substance containing zinc relative to the total mass of the silicon scavenger may be 0.8 to 10% by mass in terms of oxide (ZnO). The content is preferably 2 to 5% by mass.
The number of zinc compounds in the silicon scavenger may be one, or two or more.

(Substances containing phosphorus)
Examples of substances containing phosphorus include simple phosphorus and phosphorus compounds. The silicon scavenger may contain only one of phosphorus alone or a phosphorus compound, or may contain both.
Phosphorus compounds in the silicon scavenger include phosphorus oxide, molybdophosphoric acid, ammonium phosphate, aluminum phosphate, zinc phosphate, titanium phosphate, nickel phosphate, etc. is preferred. In addition to the above-mentioned compounds, the phosphorus compounds in the silicon collector include phosphorus element, aluminum element, zinc element, silicon element, group 6 metal element, group 9 metal element, and group 9 metal element contained in the silicon collector. Examples include composite oxides and composite sulfides with at least one element selected from the group consisting of Group 10 metal elements. The substance containing phosphorus may exist as a mixture with alumina or may be supported on alumina.
When the silicon scavenger contains a substance containing phosphorus, the content of the substance containing phosphorus relative to the total mass of the silicon scavenger is 0.04 to 2% by mass in terms of oxide (P ₂ O ₅ ). The amount is preferably 0.3 to 1.2% by mass, and more preferably 0.3 to 1.2% by mass.
The number of phosphorus compounds in the silicon scavenger may be one, or two or more.

(Substances containing silicon)
Examples of substances containing silicon include silicon compounds.
Examples of the silicon compound in the silicon scavenger include silica. In addition to the above-mentioned compounds, silicon compounds in the silicon scavenger include silicon element, aluminum element, zinc element, phosphorus element, group 6 metal element, group 9 metal element, and group 9 metal element contained in the silicon scavenger. Examples include composite oxides and composite sulfides with at least one element selected from the group consisting of Group 10 metal elements. The silicon-containing substance may be present as a mixture with alumina or supported on alumina.
When the silicon scavenger contains a substance containing silicon, the content of the substance containing silicon relative to the total mass of the silicon scavenger must be 0.01 to 1% by mass in terms of oxide (SiO ₂ ). The amount is preferably 0.05 to 0.5% by mass, more preferably 0.1 to 0.2% by mass. In order for the silicon scavenger to satisfy the physical property values described below, it is preferable that the silicon scavenger contains a substance containing silicon.
The number of silicon compounds in the silicon scavenger may be one, or two or more.

(Substances containing hydrogenated active ingredients)
When the silicon scavenger contains a substance containing a hydrogenation active component, it functions both as a silicon scavenger and as a hydrogenation catalyst. Hereinafter, a silicon scavenger containing a substance containing a hydrogenation active component will also be referred to as a "silicon scavenging hydrogenation catalyst." When a silicon-trapping hydroprocessing catalyst is used as a silicon-trapping agent, the space within the reactor can be utilized more efficiently. Note that the silicon-trapping hydrotreating catalyst has both silicon-trapping ability and hydrotreating activity, but in this specification it is defined as a "silicon scavenger" and is referred to as a "hydro-treating catalyst" described later. is not applicable.

Examples of the Group 6 metal include molybdenum, tungsten, chromium, etc. Among them, molybdenum is preferred because of its high hydrogenation activity per unit mass.
Examples of substances containing Group 6 metals include simple Group 6 metals and Group 6 metal compounds. The silicon scavenger may contain only one of the Group 6 metal alone or the Group 6 metal compound, or may contain both.
As the Group 6 metal compound in the silicon collector, a molybdenum compound is preferable, and examples thereof include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, molybdenum sulfide, aluminum molybdate, nickel molybdate, zinc molybdate, molybdate, and the like. Among them, molybdophosphoric acid, molybdenum trioxide, nickel molybdate, and zinc molybdate are preferred. Group 6 metal compounds in the silicon scavenger include, in addition to the above compounds, group 6 metal elements, zinc elements, phosphorus elements, silicon, group 9 metal elements, and group 10 metal elements contained in the silicon scavenger. Examples include composite oxides and composite sulfides with at least one element selected from the group consisting of metal elements. The substance containing the Group 6 metal is preferably supported on alumina.
When the silicon scavenger contains a substance containing a Group 6 metal, the content of the substance containing a Group 6 metal with respect to the total mass of the silicon scavenger is 10 to 10% in terms of oxide (for example, MoO ₃ ). The amount is preferably 30% by weight, and more preferably 10 to 25% by weight. Note that when converting a substance containing a Group 6 metal into an oxide, the Group 6 metal is converted as a hexavalent substance.
The number of Group 6 metal compounds in the silicon scavenger may be one, or two or more.

Examples of Group 9 metals and Group 10 metals include nickel, palladium, platinum, cobalt, rhodium, iridium, etc. Among them, nickel and cobalt are preferred because they have high hydrogenation ability and low catalyst preparation costs, and nickel is more preferred. preferable. The silicon scavenger may contain only a substance containing a Group 9 metal, or may contain only a substance containing a Group 10 metal, or a substance containing a Group 9 metal and a Group 10 metal. Both substances including metals may be included.
Examples of the substance containing a Group 9 metal and the substance containing a Group 10 metal include an elemental Group 9 metal, an elemental Group 10 metal, a Group 9 metal compound, and a Group 10 metal compound. When a substance containing a Group 9 metal is contained in the silicon collecting agent, only one of the Group 9 metal alone or the Group 9 metal compound may be contained, or both may be contained. When a substance containing a Group 10 metal is contained in the silicon scavenger, only one of the Group 10 metal alone or the Group 10 metal compound may be contained, or both may be contained.
Group 9 metal compounds and Group 10 metal compounds in the silicon collector include nickel or cobalt oxides, carbonates, nitrates, sulfates, phosphates, aluminates, titanates, and molybdates. etc., with phosphates, titanates, and molybdates being preferred. In addition to the above-mentioned compounds, the Group 9 metal compound and Group 10 metal compound in the silicon scavenger include a Group 9 metal element and/or a Group 10 metal element, and a zinc element contained in the silicon scavenger. Composite oxides and composite sulfides with at least one element selected from the group consisting of phosphorus element, silicon element, and Group 6 metal elements are included. The substance containing a Group 9 metal or the substance containing a Group 10 metal is preferably supported on alumina.
When the silicon scavenger contains a substance containing a group 9 metal element or a substance containing a group 10 metal element, the substance containing a group 9 metal and the substance containing a group 10 metal relative to the total mass of the silicon scavenger The total content of is preferably 1 to 15% by mass, more preferably 3 to 8% by mass, in terms of oxides (for example, NiO). Note that when a substance containing a Group 9 metal or a substance containing a Group 10 metal is converted into an oxide, the Group 9 metal or the Group 10 metal is converted as a divalent value.
The number of Group 9 compounds in the silicon scavenger may be one, or two or more. The number of Group 10 compounds in the silicon scavenger may be one, or two or more.

<Physical properties of silicon scavenger>
The average pore diameter of the silicon scavenger is 7 to 13 nm, preferably 8 to 12.5 nm, more preferably 9.2 to 11 nm, and preferably 9.5 to 10.5 nm. Particularly preferred. When the average pore diameter is at least the lower limit of the above range, the diffusivity of the silicon compound into the pores is improved. As a result, the silicon compound penetrates into the pores and efficiently reacts with the hydroxyl groups on the alumina surface, thereby improving the silicon-trapping ability. When the average pore diameter is below the upper limit of the above range, it tends to be above the lower limit of the specific surface area described below. As a result, the number of hydroxyl groups on the alumina surface that reacts with silicon compounds becomes sufficient, and it is thought that the silicon trapping ability is improved.

The pore volume of the silicon scavenger is 0.55 to 0.75 mL/g, preferably 0.58 to 0.72 mL/g, and preferably 0.60 to 0.70 mL/g. More preferred. When the pore volume is at least the lower limit of the above range, the diffusivity of the silicon compound into the pores is improved. As a result, the silicon compound penetrates into the pores and efficiently reacts with the hydroxyl groups on the alumina surface, thereby improving the silicon-trapping ability. 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, which will be described later. As a result, the number of hydroxyl groups on the alumina surface that reacts with silicon compounds becomes sufficient, and it is thought that the silicon trapping ability is improved.

Regarding the pore distribution of the silicon scavenger, the ratio of the volume of pores having a pore diameter of ±1.5 nm to the total pore volume is preferably 30% or more, and preferably 35% or more. It is more preferable that it be present, and even more preferably that it is 40% or more. When the ratio is greater than or equal to the lower limit, there are sufficient pores with a pore diameter suitable for silicon collection, and the silicon collection ability is improved.

The specific surface area of the silicon scavenger is preferably 150 to 300 m ² /g, more preferably 190 to 290 m ² /g, even more preferably 230 to 270 m ² /g. It is thought that when the specific surface area is at least the lower limit of the above range, the number of hydroxyl groups on the alumina surface that reacts with the silicon compound becomes a sufficient number, and the silicon trapping ability is improved. When the specific surface area is below the upper limit of the above range, the average pore diameter is likely to be above the above lower limit, and the diffusivity of the silicon compound into the pores is improved. As a result, the silicon compound penetrates into the pores and efficiently reacts with the hydroxyl groups on the alumina surface, thereby improving the silicon-trapping ability.

<Method for producing silicone scavenger>
The method for producing a silicon scavenger includes the process of producing a molded body containing 50% by mass or more of alumina (hereinafter also referred to as "alumina molded body"). Alumina molded bodies can be used as silicon collectors. When the silicon scavenger is a silicon scavenging hydrotreating catalyst, the method for producing a silicon scavenger further includes a step of supporting a hydrogenation active component on the alumina molded body (a step of supporting a hydrogenation active component). include.

(Manufacturing process of alumina molded body)
The manufacturing process of the alumina molded body includes, for example, an alumina gel preparation step of preparing an alumina gel, a kneading step of kneading the alumina gel to obtain a kneaded product, a molding step of molding the kneaded product to obtain a molded product, and a molding step of forming the kneaded product. It has a firing step of drying and firing the molded product to obtain a fired body (alumina molded body).
If the silicon scavenger contains the above-mentioned zinc-containing substance, phosphorus-containing substance, or silicon-containing substance, zinc raw material, phosphorus raw material, silicon It is preferable to include a step of adding raw materials.

The alumina raw material for preparing the alumina gel is not particularly limited as long as it contains 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 an aqueous solution, and the concentration thereof is not particularly limited, but it is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, based on the total mass of the aqueous solution. .

For example, a slurry is prepared by mixing an aqueous sulfuric acid solution, sodium aluminate, and aluminum hydroxide in a stirring pot. The resulting slurry is subjected to water removal using a rotating cylindrical continuous vacuum filter and washing with pure water to obtain alumina gel.

Next, the obtained alumina gel is washed until SO ₄ ^2- and Na ⁺ can no longer be detected in the filtrate, and then the alumina gel is turbid in pure water to form a uniform slurry. The obtained alumina gel slurry is dehydrated until the water content becomes 60 to 90% by mass to obtain a cake.

The alumina gel slurry is preferably dehydrated using a filter press. A press filter is a device that filters slurry by applying compressed air or pump pressure to the slurry, and is generally also called a press filter. There are two types of press filters: plate frame type and concave plate type. In the plate frame filter, filter plates and filter frames are alternately tightened between end plates, and slurry is forced into the filter frame and filtered. The filter plate has a groove that serves as a filtrate flow path, and the filter frame is covered with a filter cloth. On the other hand, in a concave filter, a filter cloth and a concave filter plate are alternately arranged and tightened together with an end plate to form a filter chamber (Reference: Chemical Engineering Handbook, p. 715).

By dehydrating the alumina gel slurry with a squeeze filter, the surface condition of the resulting alumina molded body can be improved, and in the case of a silicon-trapping hydrotreating catalyst, the sulfidity of the hydrogenation active component can be improved. I can do it. Note that this dehydration step using a filter press is preferably performed after at least one of the alumina gel preparation step and the kneading step, and may be performed after both steps. Among these, it is more preferable to carry out after the alumina gel preparation step and before the kneading step.

In addition to the above method, methods for preparing alumina gel include a method in which an aqueous solution containing an alumina raw material is neutralized with a neutralizing agent such as sodium aluminate, aluminic acid, or ammonia, or a precipitating agent such as hexamethylenetetramine or calcium carbonate. For example, a method of mixing with
The amount of the neutralizing agent used is not particularly limited, but is preferably 30 to 70% by mass based on the total amount of the aqueous solution containing the alumina raw material and the neutralizing agent. The amount of the precipitant used is not particularly limited, but is preferably 30 to 70% by mass based on the total amount of the aqueous solution containing the alumina raw material and the precipitant.

When the zinc raw material, phosphorus raw material, and silicon raw material are solid, it is preferable to perform the kneading step after adding these raw materials to the alumina gel.
When the zinc raw material, phosphorus raw material, and silicon raw material are dissolved in a liquid or solvent, the kneading step is performed after adding these raw materials to the alumina gel, and the molding step is performed after adding these raw materials to the kneaded product. It is preferable that these raw materials are added to the molded article and then dried and fired, or that these raw materials are added to the fired body, and it is more preferable that these raw materials are added to the fired body.

As raw materials for zinc, zinc alone or various zinc compounds can be used, including zinc oxide, zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, zinc acetate, zinc hydroxide, zinc oxalate, zinc phosphate, and aluminium. Examples include zinc oxide, zinc titanate, zinc molybdate, etc., among which zinc oxide, zinc nitrate, zinc sulfate, and zinc aluminate are preferred, and zinc nitrate, zinc oxide, and zinc aluminate are particularly preferred.

When the zinc raw material is a solid such as zinc oxide, the kneading step is preferably performed by adding the zinc raw material to the aluminum gel together with an acid such as nitric acid.

When the zinc raw material is a liquid or a solution dissolved in a solvent (such as an aqueous zinc nitrate solution), it is preferable to add the liquid or solution to the fired body.

As the phosphorus raw material, phosphorus alone or various compounds can be used, and examples include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, aluminum phosphate, etc. Among them, orthophosphoric acid is preferable.

It is preferable to perform the kneading step by adding a phosphorus raw material to the aluminum gel.

Examples of the silicon raw material include silica, silicon alkoxide, etc., and silicon alkoxide is particularly preferred.

It is preferable to perform the kneading step by adding a silicon raw material to the aluminum gel.

When performing the kneading step 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 step and kneaded. Specifically, the above raw material heated to 15 to 90°C is added to a water-adjusted alumina gel heated to 50 to 90°C. Then, the mixture is kneaded and stirred using a heating kneader or the like to obtain a kneaded product. Note that, as described above, dehydration using a press filter may be performed after kneading and stirring the alumina gel and the above-mentioned raw materials. As described above, the raw material may be added as a solid, a liquid, or a liquid obtained by dissolving or suspending the raw material in a solvent.

Then, the obtained kneaded product is molded, dried, and fired to obtain a fired body. The above-mentioned kneaded product can be formed by various forming methods such as extrusion molding and pressure molding. Further, the drying temperature of the obtained molded product is preferably 15 to 150°C, more preferably 80 to 120°C. The drying time is preferably 30 minutes or more.

The calcination temperature for the calcination can be appropriately set as necessary, but for example, the calcination temperature for producing γ-alumina is preferably 450° C. or higher.

When adding the above raw materials to the fired body, known methods such as an impregnation method, a coprecipitation method, a deposition method, an ion exchange method, etc. may be used. The impregnation method includes an evaporation to dryness method in which the above raw materials are supported by immersing the fired body in an impregnating solution in excess of the total pore volume of the fired body and then drying all the solvent; Equilibrium adsorption method in which the raw material is supported by solid-liquid separation such as filtration after being immersed in an impregnating solution in excess of the total pore volume of the body, and the fired body is impregnated in an amount approximately equal to the total pore volume of the fired body. An example is a pore-filling method in which the above raw materials are supported by impregnating a solution and drying all the solvent. Note that the method for impregnating the fired body with the plurality of 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 each of these raw materials is impregnated individually.

When the above-mentioned raw materials are supported by the above-mentioned impregnation method, they are generally supported at room temperature to 80°C in a nitrogen stream, an air stream, or in a vacuum so that the moisture content is reduced to a certain level (LOI <<Loss on ignition>> 50% or less). ) and dried in a drying oven in an air stream at 80 to 150°C for 10 minutes to 10 hours. Next, it is preferable to perform firing in a firing furnace in an air stream at 300 to 700°C, more preferably at 500 to 650°C, for 10 minutes to 10 hours, more preferably 3 hours to 6 hours.

In order to satisfy the physical property values of the silicon scavenger described above, the conditions of each step of forming the alumina molded body may be adjusted. The physical properties of such an alumina molded body can be adjusted by methods known in the art. Note that the physical properties of the silicon-trapping hydrogenation catalyst are also reflected in the physical properties of the alumina molded body.
For example, if the time (aging time) from preparing the aqueous solution containing the alumina raw material in the alumina gel preparation step to adding the neutralizing agent or precipitant is increased, the specific surface area of the alumina molded body becomes smaller. The average pore diameter and pore volume tend to become larger, and the pore distribution tends to become sharper.
Furthermore, when the pressure during the molding process is increased, the specific surface area of the alumina molded body tends to increase, and the average pore diameter and pore volume tend to decrease.
Furthermore, when the firing temperature during the firing step is increased, the specific surface area of the alumina molded body becomes smaller, the average pore diameter and pore volume become larger, and the pore distribution tends to become broader.

(Hydrogenation active component supporting step)
The step of supporting the hydrogenation active component is a step of supporting the hydrogenation active component on the alumina molded body.

The Group 6 metal raw material to be supported on the alumina molded body is preferably a molybdenum compound, and examples thereof include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, molybdate, etc., and molybdophosphoric acid, molybdenum trioxide, and ammonium molybdate are preferable.

Group 9 metal raw materials and Group 10 metal raw materials to be supported on the alumina compact include nickel oxide, nickel carbonate, nickel acetate, nickel nitrate, nickel sulfate, nickel chloride, cobalt carbonate, cobalt acetate, cobalt nitrate, cobalt sulfate, Examples include cobalt chloride, cobalt carbonate, cobalt oxalate, and nickel nitrate, nickel carbonate, cobalt nitrate, and cobalt carbonate are preferred.

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 component raw materials") on the alumina molded body include an impregnation method, a coprecipitation method, Known methods such as a kneading method, a deposition method, and an ion exchange method may be used. The impregnation method includes an evaporation drying method in which the alumina molded body is immersed in an impregnating solution in excess of the total pore volume of the alumina molded body and then all the solvent is dried to support the hydrogenated active ingredient raw material; Equilibrium adsorption method in which the alumina molded body is immersed in an impregnating solution in excess of the total pore volume of the alumina molded body, and then the hydrogenation active ingredient raw material is supported by solid-liquid separation such as filtration; An example is a pore-filling method in which the hydrogenated active ingredient raw material is supported by impregnating with an impregnating solution approximately equal to the total pore volume of the body and drying all the solvent. Note that the method for impregnating the alumina molded body with the plurality of hydrogenation active component raw materials may be a batch impregnation method in which these components are simultaneously impregnated, or a sequential impregnation method in which they are impregnated individually.

Specific methods for supporting the hydrogenated active component raw material on the alumina molded body include the following methods.
First, an impregnating solution containing hydrogenated active ingredient raw materials is prepared. During preparation, in order to promote the dissolution of these hydrogenated active ingredient raw materials, heating (30 to 100°C) and inorganic acids such as nitric acid and phosphoric acid, and organic acids such as citric acid, acetic acid, malic acid, and tartaric acid are applied. may be added. That is, in this embodiment, in addition to the phosphorus contained in the alumina molded body, phosphorus may be supported separately when the hydrogenation active component raw material and the like are supported on the alumina molded body.

Phosphorus compounds that are separately added when supporting hydrogenation active ingredient raw materials etc. on an alumina molded body include hydrogenation active ingredient raw materials containing phosphorus such as molybdophosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, and triphosphoric acid. , tetraphosphoric acid, and orthophosphoric acid is preferred. When supporting the hydrogenation active component raw material on the alumina molded body, if phosphorus is separately supported, the dispersibility of the hydrogenation active component in the resulting silicon-trapping hydrotreating catalyst can be improved.

Subsequently, the prepared impregnating solution is gradually added to the alumina molded body so as to be uniformly impregnated. The impregnation time is preferably 1 minute to 5 hours, more preferably 5 minutes to 3 hours. The impregnation temperature is preferably 5 to 100°C, more preferably 10 to 80°C. The impregnation atmosphere is not particularly limited, but air, nitrogen, and vacuum are each suitable.

After supporting hydrogenation active ingredient raw materials, etc., the impregnated body is first heated at 15 to 80°C in a nitrogen stream, an air stream, or in a vacuum to remove some moisture (so that the LOI <<Loss on ignition>> is 50% or less). ) is preferably removed. Thereafter, it is preferably dried in a drying oven at 80 to 150° C. for 10 minutes to 10 hours in an air stream. Next, it is preferable to perform firing in a firing furnace in an air stream. The firing temperature is preferably 300 to 700°C, more preferably 500 to 650°C. The firing time is preferably 10 minutes to 10 hours, more preferably 3 hours or more.

≪Method for collecting silicon from feedstock oil containing heavy coker cracked hydrocarbon oil≫
The method for collecting silicon from feedstock oil containing heavy coker cracked hydrocarbon oil (hereinafter also referred to as "silicon collection method") of the present embodiment has a silicon concentration of 0. 1 to 15.0 mass ppm of feedstock oil was heated 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 . The silicon scavenger of the invention and the hydrotreating catalyst are contacted sequentially.

≪Method for hydrotreating feedstock oil containing heavy coker cracked hydrocarbon oil≫
The method for hydrotreating feedstock oil containing heavy coker-cracked hydrocarbon oil (hereinafter also referred to as "hydro-treating method") of the present embodiment has a silicon concentration of 0.1 containing heavy coker-cracked hydrocarbon oil. In the present invention, feedstock oil of ~15.0 mass ppm was used 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 . of a silicon scavenger and a hydrotreating catalyst.
According to the hydrotreating method of this embodiment, hydrogenated oil can be produced.

The silicon collection method and hydrogenation treatment method will be specifically explained below.

<Raw oil>
The feedstock includes heavy coker cracked hydrocarbon oil. The content of the heavy coker cracked hydrocarbon oil relative to the total volume of the feedstock oil is preferably 50% by volume or more, more preferably 70% by volume or more, and even more preferably 90% by volume or more. , 100% by volume. Examples of fractions other than the heavy coker cracked hydrocarbon oil contained in the feedstock oil include heavy cycle oil obtained from a fluid catalytic cracker, vacuum gas oil obtained from an indirect hydrodesulfurization apparatus, and the like.

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 0.92 to 0.985 g/mL. It is even more preferable that there be.

The sulfur content based on the total mass of the feedstock oil is usually 1.5 to 5.5% by mass, may be 2.0 to 5.0% by mass, and may be 2.5 to 4.5% by mass. Good too.
The nitrogen content based on the total mass of the feedstock oil is usually 0.01 to 0.60% by mass, may be 0.03 to 0.45% by mass, and may be 0.05 to 0.25% by mass. Good too.
Silicon (in terms of element) relative to the total mass of the raw material oil is usually 0.1 to 15.0 mass ppm, and may be 0.1 to 13.0 mass ppm, and 0.1 to 10.0 mass ppm. It may be.
The nickel content (in elemental terms) relative to the total mass of the raw material oil is usually 0.1 to 1.5 mass ppm, and may be 0.1 to 1.0 mass ppm, and may be 0.1 to 0.5 mass ppm. It may be ppm.
The vanadium content (in elemental terms) relative to the total mass of the feedstock oil is usually 0.1 to 1.5 mass ppm, and may be 0.1 to 1.0 mass ppm, and 0.1 to 0.5 mass ppm. It may be ppm.

It is known that the silicon compound contained in the feedstock oil is a silicon compound produced by the decomposition of a silicon-based defoaming agent used in a coker device. As such a silicon compound, a compound in which all the hydrogen atoms bonded to the silicon atoms of a cyclic cyclopolysiloxane are replaced with methyl groups (hereinafter also referred to as a "cyclic silicon compound") is known. The inventors of the present application have discovered that cyclic silicon compounds having 3 to 9 silicon atoms contained in the coker-cracked naphtha fraction described in Patent Document 1 and the heavy coker-cracked hydrocarbon oil of the present embodiment. The content of each cyclic silicon compound having a number of silicon atoms (3 to 9) relative to the total mass was determined by gas chromatography mass spectrometry (GC/MS). As a result, the total content of cyclic silicon compounds with 3 and 4 silicon atoms was 100% by mass in the coker cracked naphtha fraction, and no cyclic silicon compounds with 5 to 9 silicon atoms were detected. Ta. On the other hand, in heavy coker cracked hydrocarbon oil, the total content of cyclic silicon compounds with 3 and 4 silicon atoms is about 17% by mass, and the total content of cyclic silicon compounds with 5 to 9 silicon atoms is about 17% by mass. The content was about 83% by mass. It was also considered that a cyclic silicon compound having 10 or more silicon atoms may be included. The total content of cyclic silicon compounds having 7 to 9 silicon atoms relative to the total mass of cyclic silicon compounds having 3 to 9 silicon atoms contained in the feedstock oil is preferably 30% by mass or more. , more preferably 40% by mass or more, and still more preferably 50% by mass or more. The silicon scavenger of the present invention is particularly suitably employed in raw oil containing a cyclic silicon compound having such a composition.

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

<Hydrotreating catalyst>
As the hydrotreating catalyst filled in the latter stage of the silicon scavenger layer, a hydrotreating catalyst for feedstock oil containing heavy coker cracked hydrocarbon oil known in the art can be used.
For example, a catalyst in which the above-mentioned hydrogenation active component is supported on a porous inorganic oxide carrier containing alumina can be used. The type of hydrogenation active component, the preferred range of content, etc. are the same as in the case of the silicon-trapping hydrogenation catalyst described above. Furthermore, as described above, the silicon-trapping hydrotreating catalyst also has hydrotreating activity. Further, hydrogenation catalysts described in JP-A No. 2019-178251 and JP-A No. 2004-074075 may be used.

<Silicon collection conditions, hydrogenation treatment conditions>
The average temperature of the silicon scavenger 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 equal to or higher than the lower limit of the above range, the hydrogenation treatment of the feedstock oil progresses more easily. Moreover, the silicon-trapping ability of the silicon-trapping agent is improved. When the temperature is below the upper limit of the range, sintering of the hydrogenation active component in the hydrogenation catalyst is suppressed.

The pressure (hydrogen partial pressure) is 10 to 20 MPa, preferably 13 to 18 MPa, and more preferably 14 to 17 MPa. When the pressure is equal to or higher than the lower limit of the above range, deterioration in performance of the hydrotreating catalyst due to heavy coker cracked hydrocarbon oil can be suppressed. Although the upper limit of the pressure is not substantially limited, it is usually 20 MPa or less due to equipment design issues.

The hydrogen/oil ratio is 170 to 1400 ^{m 3} /m ³ , preferably 300 to 1375 m ³ /m ³ , and more preferably 350 to 1350 m ³ /m ³ .

The liquid space velocity of the feedstock oil relative to the total volume of the silicon scavenger layer and the hydrotreating catalyst layer is 0.1 to 2.0 hr ⁻¹ , preferably 0.3 to 1.5 hr ⁻¹ . , more preferably 0.5 to 1.2 hr ⁻¹ . When the liquid hourly space velocity is equal to or higher than the lower limit of the above range, the throughput of feedstock oil per unit time is improved. When the liquid hourly space velocity is less than or equal to the upper limit of the above range, the hydrogenation treatment progresses more easily.

<Filling position and amount of silicone scavenger>
In this embodiment, the reactor is filled with a silicon scavenger and a hydrogenation catalyst in this order. If the reactor is not filled with a descaling catalyst, which will be described later, the silicon scavenger is preferably filled at the closest point to the entrance of the reactor. Specifically, the filling position of the silicon scavenger is determined by the total volume of the catalyst layer filled in the reactor (including the silicon scavenger of the present invention and the descaling catalyst described below. The volume is the filling volume). On the other hand, the position is preferably 0 to 35% by volume from the entrance of the catalyst layer, more preferably 0 to 30% by volume, and particularly preferably 0 to 25% by volume. In this case, the silicon scavenger captures silicon compounds in the feedstock oil, thereby making it possible to suppress poisoning of the hydrogenation catalyst filled in the latter stage by the silicon compounds. Note that a descaling catalyst for removing scale in the raw oil may be filled in a stage further upstream of the silicon collector. In this case, the filling amount of the descaling catalyst should be 5% by volume or less with respect to the total volume of the catalyst layer (including the silicon collector of the present invention and the descaling catalyst described below. The volume is the filling volume). preferable.
The filling amount of the silicon scavenger may be 5 to 35% by volume based on the total volume of the catalyst layer (including the silicon scavenger of the present invention and the descaling catalyst described below. The volume is the filling volume). It is preferably 5 to 30% by volume, more preferably 5 to 25% by volume.
The filling amount of the hydrotreating catalyst may be 65 to 95% by volume based on the total volume of the catalyst layer (including the silicon scavenger of the present invention and the descaling catalyst described below. The volume is the filling volume). It is preferably 70 to 95% by volume, more preferably 75 to 95% by volume.
The number of silicon collectors and hydrogenation catalysts filled in the reactor may be one, or two or more.

<Hydrogenated oil>
The sulfur content based on the total mass of the hydrogenated oil produced by the hydrotreating method of this embodiment is usually 0.1% by mass or less.
The silicon concentration (in terms of element) relative to the total mass of the hydrogenated oil is usually less than 0.3 mass ppm.
The nickel content (in terms of element) based on the total mass of the hydrogenated oil is usually less than 0.1 mass ppm.
The vanadium content (in terms of element) based on the total mass of the hydrogenated oil is usually less than 0.1 mass ppm.

The hydrotreating catalyst may be activated by sulfidation treatment in a reactor before use (ie, prior to performing the hydrotreating method of this embodiment). This sulfiding treatment is generally carried out at 200 to 400°C, preferably from 250 to 350°C, under a hydrogen atmosphere at a hydrogen partial pressure of normal pressure or higher, on a petroleum distillate containing sulfur compounds, and dimethyl disulfide or disulfide. Hydrotreating can be carried out by adding a sulfurizing agent such as carbon or by flowing hydrogen sulfide through a hydrotreating catalyst.

According to the silicon collection method of the present embodiment, it is possible to suppress poisoning of the hydrogenation catalyst filled in the latter stage of the silicon collection agent layer by silicon compounds. As a result, the hydrogenation treatment progresses sufficiently, and it becomes possible to reduce sulfur compounds in the feedstock oil containing heavy coker cracked hydrocarbon oil over a long period of time.

In order to carry out the silicon collection method and the hydrogenation treatment method on a commercial scale, a fixed bed catalyst layer of the silicon collection agent and the hydrogenation catalyst of this embodiment is formed in a reactor, and Raw material oil may be introduced, and silicon collection and hydrogenation treatment may be performed under the above conditions.

The hydrogenation method may be a one-step silicon collection method and hydrogenation method in which a silicon collector and a hydrogenation catalyst are filled in a single reaction device, or a one-stage silicon collection method and hydrogenation method in which a silicon collection agent and a hydrogenation catalyst are filled in a single reaction device. A multi-stage continuous silicon collection method and a multi-stage continuous hydrogenation treatment method may be used.

<Mechanism of action>
As mentioned above, extensive research has been conducted on silicon capture in the hydrotreatment of coker cracked naphtha fractions. According to these studies, silicon compounds are thought to chemically adsorb onto the alumina surface by reacting with hydroxyl groups on the alumina surface in the hydrogenation catalyst. Therefore, it is considered important to increase the amount of hydroxyl groups on the alumina surface in order to improve the silicon trapping ability. For example, in the above-mentioned Patent Document 1, the number of hydroxyl groups on the surface of the hydrotreating catalyst is increased by supplying 0.01 to 10% by volume of water to the hydrotreating catalyst together with the coker cracked naphtha fraction. Furthermore, increasing the specific surface area of the hydrotreating catalyst is also considered effective in increasing the number of hydroxyl groups on the surface of the hydrotreating catalyst.
On the other hand, as shown in the Examples and Comparative Examples described later, in the silicon collection in the hydrogenation treatment of feedstock oil containing heavy coker cracked hydrocarbon oil, a silicon collection agent with a large specific surface area has a rather poor silicon collection ability. It has been confirmed that the silicon scavengers of Comparative Examples 1 and 2, which have the largest specific surface area, have the lowest silicon scavenging ability. This is considered to be a completely opposite result to the silicon collection in the above-mentioned hydrogen treatment of the coker cracked naphtha fraction. The reason for this result is thought to be as follows.
As mentioned above, the silicon compounds contained in the coker-cracked naphtha fraction are silicon compounds with a small molecular weight (molecular size), whereas the silicon compounds contained in the feedstock oil containing heavy coker-cracked hydrocarbon oil have a small molecular weight (molecular size). It is a silicon compound with a large molecular size). In the case of silicon compounds with small molecular sizes, they can sufficiently diffuse into the pores of common hydrogenation catalysts, so the silicon trapping ability depends on the number of hydroxyl groups (specific surface area) that are adsorption points for silicon compounds. That will happen. On the other hand, in the case of a silicon compound having a large molecular size, the diffusibility into pores is reduced, making it difficult for the silicon compound to penetrate into the pores. As a result, it is thought that the hydroxyl groups, which are adsorption points for silicon compounds, are not efficiently utilized, and the silicon trapping ability depends on the diffusivity of the silicon compounds. In the present invention, by setting the average pore diameter of the silicon scavenger to a certain level or more, the diffusibility of silicon compounds with large molecular sizes into the pores is improved, and the hydroxyl groups, which are adsorption points, are efficiently used. This is thought to have improved the silicon trapping ability. In other words, in the case of a silicon compound with a large molecular size, simply increasing the specific surface area does not improve the silicon trapping ability, but the silicon trapping ability is improved by having an average pore diameter that corresponds to the molecular size of the silicon compound. This is considered to be important for improving the

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Method for analyzing physical properties and composition of silicon scavenger>
[1] Analysis of physical properties (specific surface area, pore volume, average pore diameter, and pore distribution)
(a) Measuring method and equipment used:
The specific surface area was measured by the BET method using nitrogen adsorption. As the nitrogen adsorption device, a surface area measuring device (BELSORP-mini II) manufactured by Microtrac Bell Co., Ltd. was used.
Pore volume, average pore diameter, and pore distribution were measured by mercury intrusion method. As a mercury intrusion device, a porosimeter (AutoPore IV: manufactured by Micromeritics) was used.

(b) Measurement principle of mercury porosimetry:
The mercury intrusion method is based on the law of capillarity. In the case of mercury and cylindrical pores, this law is expressed as: That is, the volume of mercury entering the pores as a function of the applied pressure P is measured. Note that the surface tension of the pore mercury of the catalyst was 484 dyne/cm, and the contact angle was 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 scavenger. The average pore size is the average value of D calculated as a function of P.
The pore distribution is the distribution of D calculated as a function of P.

(c) Measurement procedure:
(1) Turn on the vacuum heating deaerator and confirm that the temperature is 400°C and the degree of vacuum is 5 x 10 ^-2 Torr or less.
(2) Place the empty sample buret on a vacuum heating deaerator.
(3) After confirming that the degree of vacuum is 5×10 ⁻² Torr or less, the sample burette is removed from the vacuum heating deaerator with its cock closed, and after cooling, the weight is measured.
(4) Put the sample (silicon collector) into the sample burette.
(5) Place the sample burette containing the sample in a vacuum heating deaerator and hold it for at least 1 hour after the degree of vacuum becomes 5×10 ⁻² Torr or less.
(6) Remove the sample buret containing the sample from the vacuum heating deaerator, and after cooling, measure the weight to determine the sample weight.
(7) Place the sample into the AutoPore IV cell.
(8) Measured by AutoPore IV.

[2] Analysis of composition It was confirmed by the following method that the content of each element in the silicon scavenger was in a proportion based on the amount of raw materials charged. Furthermore, the silicon content in the silicon scavenger extracted after the hydrogenation treatment described below was also confirmed by the following method.
(a) Analysis method and equipment used:
Elemental analysis of the silicon scavenger was performed using an inductively coupled plasma emission spectrometer (iCAP 6000: manufactured by Thermo Scientific).
Quantification of elements was performed using the absolute calibration curve method.

(b) Measurement procedure:
(1) 0.05 g of silicone scavenger, 1 mL of hydrochloric acid (50% by mass), 1 drop of hydrofluoric acid, and 1 mL of pure water were put into Uniseal and heated to dissolve them.
(2) After dissolution, the mixture was transferred to a polypropylene volumetric flask (50 mL), and pure water was added to weigh the volume to 50 mL.
(3) This solution was measured using the above-mentioned inductively coupled plasma emission spectrometer.

<Silicon collection method for feedstock oil (method for hydrogenation treatment of feedstock oil)>
A feedstock oil having the properties listed in Table 1 containing 93% by volume of heavy coker cracked hydrocarbon oil was hydrogenated in the following manner. In Table 1, "average" indicates the average properties of the feedstock oil during the entire reaction period, "maximum value" indicates the maximum properties of the feedstock oil during the entire reaction period, and "minimum value" Shows the minimum properties of the feedstock during the entire reaction period. Further, T10 represents a 10 volume % distillation temperature, T50 represents a 50 volume % distillation temperature, and T90 represents a 90 volume % distillation temperature.

A high-pressure flow reactor was filled with a silicon scavenger (including a silicon scavenging hydrotreating catalyst) and a hydrotreating catalyst in this order from the reactor inlet side. As the hydrogenation catalyst, a hydrogenation catalyst in which molybdenum, nickel, and cobalt were supported on alumina was used. The volume ratio of silicon scavenger:hydrogenation catalyst was 25:75. Then, pretreatment was performed under the following conditions. Next, a mixed fluid of feedstock oil containing heavy coker cracked hydrocarbon oil and hydrogen-containing gas is introduced from the upper part of the reactor (inlet of the reactor) and hydrogenated under the reaction conditions shown in Table 2. A mixed fluid of produced oil and gas was discharged from the lower part of the reactor (reactor outlet), and produced oil was separated in a gas-liquid separator. In Table 2, "liquid hourly space velocity" means the liquid hourly hourly velocity of the feedstock oil relative to the total volume of the silicon scavenger layer and the hydrotreating catalyst layer. Furthermore, "average" indicates the average reaction condition during the entire reaction period, "maximum value" indicates the maximum reaction condition during the entire reaction period, and "minimum value" indicates the minimum reaction condition during the entire reaction period. shows. Temperature is the average temperature in all layers, including the silicon scavenger layer and the hydrogenation catalyst layer. The temperature was adjusted so that the sulfur content was 0.1% by mass based on the total mass of the hydrogenated oil.

Pretreatment conditions for the catalyst: Drying at 120° C. for 3 hours under normal pressure.
Presulfurization of the catalyst was carried out using vacuum gas oil at a hydrogen partial pressure of 10.3 MPa and 370° C. for 12 hours. After that, we switched to the raw material oil for activity evaluation.

[Example 1]
(Manufacture of alumina molded body)
After heating 10 kg of a 5% by mass aqueous sodium aluminate solution to 60° C., 2.8 kg of a 25% by mass aluminum sulfate aqueous solution was slowly added, and the pH of the solution was finally adjusted to 7. At this time, the temperature of the solution was maintained at 60°C. The alumina slurry produced by the above operation 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 a 10% by mass ammonia aqueous solution was further added to adjust the aqueous dispersion of the gel to pH 11. Next, the aqueous gel dispersion was heated to 90° C. and aged for 40 hours while stirring and refluxing. Thereafter, 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 obtained aqueous gel dispersion, water was added at room temperature to adjust the water content so that the viscosity 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 with a kneader until uniform. The cake obtained by kneading was put into an extruder to form a four-leaf-shaped extruded product with a major axis of 1.3 mm and a minor axis of 1.1 mm. This molded product was dried at 110° C. for 10 hours, and fired by adjusting the firing temperature and firing time so as to obtain the physical properties of silicon collector A listed in Table 3, to obtain alumina molded product A containing silica. . Note that the amount of silica particles added was adjusted to have the composition shown in Table 3.

(Support of hydrogenation active ingredient)
A molybdenum/nickel aqueous solution was prepared by dissolving ammonium paramolybdate and nickel nitrate in 100 g of ion-exchanged water. Note that the amounts of ammonium paramolybdate and nickel nitrate were set according to the compositions shown in Table 3. An alumina molded body A was impregnated with a molybdenum-nickel aqueous solution in an eggplant-shaped flask to obtain an impregnated body. The impregnated body was dried and then baked at 550° C. for 3 hours in an air atmosphere to obtain a silicon collector A. The content of each element in silicon scavenger A in terms of oxide, and the specific surface area, pore volume, average pore diameter, and average pore diameter ±1.5 nm of the total pore volume of silicon scavenger A. The volume ratio of pores having pore diameters is shown in Table 3 (hereinafter, silicon scavengers B to H are also shown in the same manner). In addition, "pore distribution" in Table 3 means "the ratio of the volume of pores having a pore diameter of the average pore diameter ±1.5 nm to the total pore volume."

Using silicon scavenger A, raw oil was hydrogenated for 1000 days. Thereafter, the silicon scavenger A is extracted from the reactor, the silicon content is measured by the method described above, and the silicon content extracted from the silicon scavenger A is reduced by reducing the silicon content derived from the silica originally contained in the silicon scavenger A. The amount of silicon deposited in the scavenger A (in terms of element) was calculated. The results are shown in Table 3 (hereinafter, the same applies to Examples 2 to 6 and Comparative Examples 1 and 2).

[Example 2]
(Manufacture of alumina molded body)
After heating 10 kg of a 5% by mass aqueous sodium aluminate solution to 60° C., 2.8 kg of a 25% by mass aluminum sulfate aqueous solution was slowly added, and the pH of the solution was finally adjusted to 7. At this time, the temperature of the solution was maintained at 60°C. The alumina slurry produced by the above operation 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 a 10% by mass ammonia aqueous solution was further added to adjust the aqueous dispersion of the gel to pH 11. Next, the aqueous gel dispersion was heated to 90° C. and aged for 40 hours while stirring and refluxing. Thereafter, 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 obtained aqueous gel dispersion, water was added at room temperature to adjust the water content so that the viscosity was easy to mold. 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 with a kneader until uniform. The cake obtained by kneading was put into an extruder to form a four-leaf-shaped extruded product with a major axis of 1.3 mm and a minor axis of 1.1 mm. This molded product was dried at 110°C for 10 hours, and fired by adjusting the firing temperature and firing time so that it had the physical properties of silicon collector B listed in Table 3. An alumina molded body B was obtained. Note that the amounts of silica particles, zinc oxide particles, and phosphoric acid added were set to the compositions shown in Table 3.

(Support of hydrogenation active ingredient)
Hydrogenation active component in the same manner as in Example 1, except that alumina molded body B was used instead of alumina molded body A, and the amounts of ammonium paramolybdate and nickel nitrate were adjusted so that the composition was as shown in Table 3. was supported to obtain silicon collector B.

Using silicon scavenger B, raw oil was hydrogenated for 1000 days. Thereafter, the silicon scavenger B was extracted from the reactor, the silicon content was measured by the method described above, and the silicon content extracted from the silicon scavenger B was reduced by reducing the silicon content derived from the silica originally contained in the silicon scavenger B. The amount of silicon deposited in the scavenger B (in terms of element) was calculated.

[Example 3]
(Manufacture of alumina molded body)
An alumina molded article was produced 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 have the composition shown in Table 3, and the firing temperature and firing time of the alumina molded article were changed. I got a C.

(Support of hydrogenation active ingredient)
Hydrogenation active component in the same manner as in Example 1, except that alumina molded body C was used instead of alumina molded body A, and the amounts of ammonium paramolybdate and nickel nitrate were adjusted so that the composition was as shown in Table 3. was supported to obtain a silicon collector C.

Using silicon scavenger C, the raw oil was hydrogenated for 1000 days. After that, the silicon scavenger C was extracted from the reactor, the silicon content was measured by the method described above, and the silicon content extracted from the silicon scavenger C was reduced by reducing the silicon content derived from the silica originally contained in the silicon scavenger C. The amount of silicon deposited in the scavenger C (in terms of element) was calculated.

[Example 4]
(Manufacture of alumina molded body)
An alumina molded article was produced 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 have the composition shown in Table 3, and the firing temperature and firing time of the alumina molded article were changed. I got a D.

(Support of hydrogenation active ingredient)
Hydrogenation active component in the same manner as in Example 1, except that alumina molded body D was used instead of alumina molded body A, and the amounts of ammonium paramolybdate and nickel nitrate were adjusted so that the composition was as shown in Table 3. was supported to obtain silicon collector D.

Using silicon scavenger D, raw oil was hydrogenated for 1000 days. Thereafter, the silicon scavenger D was extracted from the reactor, the silicon content was measured by the method described above, and the silicon content extracted from the silica originally contained in the silicon scavenger D was reduced. The amount of silicon deposited in the scavenger D (in terms of element) was calculated.

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

(Support of hydrogenation active ingredient)
Hydrogenation active component in the same manner as in Example 1, except that alumina molded body E was used instead of alumina molded body A, and the amounts of ammonium paramolybdate and nickel nitrate were adjusted so that the composition was as shown in Table 3. was supported to obtain silicon collector E.

Using silicon scavenger E, raw oil was hydrogenated for 1000 days. Thereafter, the silicon scavenger E was extracted from the reactor, the silicon content was measured by the method described above, and the silicon content extracted from the silicon scavenger E was reduced by reducing the silicon content derived from the silica originally contained in the silicon scavenger E. The amount of silicon deposited in the scavenger E (in terms of element) was calculated.

[Example 6]
(Manufacture of alumina molded body)
An 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 have the composition shown in Table 3, and the firing temperature and firing time of the alumina molded product were changed.

(Support of hydrogenation active ingredient)
Hydrogenation active component in the same manner as in Example 1, except that alumina molded body F was used instead of alumina molded body A, and the amounts of ammonium paramolybdate and nickel nitrate were adjusted to have the composition shown in Table 3. was supported to obtain silicon collector F.

Using silicon scavenger F, the raw oil was hydrogenated for 1000 days. Thereafter, the silicon scavenger F is extracted from the reactor, the silicon content is measured by the method described above, and the silicon content extracted from the silica originally contained in the silicon scavenger F is reduced. The amount of silicon deposited in the scavenger F (in terms of element) was calculated.

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

(Support of hydrogenation active ingredient)
Hydrogenation active component in the same manner as in Example 1, except that alumina molded body G was used instead of alumina molded body A, and the amounts of ammonium paramolybdate and nickel nitrate were adjusted so that the composition was as shown in Table 3. was supported to obtain silicon collector G.

Using silicon scavenger G, the raw oil was hydrogenated for 1000 days. Thereafter, the silicon scavenger G is extracted from the reactor, the silicon content is measured by the method described above, and the silicon content extracted from the silica originally contained in the silicon scavenger G is reduced. The amount of silicon deposited in the scavenger G (in terms of element) was calculated.

[Comparative example 2]
(Manufacture of alumina molded body)
An 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 have 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 a silicon collector H.

Using silicon scavenger H, the raw oil was hydrogenated for 1000 days. After that, the silicon scavenger H was extracted from the reactor, the silicon content was measured by the method described above, and the silicon content extracted from the silicon scavenger H was reduced by reducing the silicon content derived from the silica originally contained in the silicon scavenger H. The amount of silicon deposited in the scavenger H (in terms of element) was calculated.

The silicon scavengers of Examples 1 to 6 of the present invention have an average pore diameter of less than 7 nm and a pore volume of less than 0.55 mL/g, and the silicon scavengers of Comparative Example 1 that have an average pore diameter of less than 7 nm. It was found that compared to the silicon scavenger of Example 2, the silicon scavenger had a larger amount of silicon deposited and was superior in silicon scavenging ability.

FIG. 1 shows the relationship between the average pore diameter of the silicon scavengers of Examples 1 to 6 and Comparative Examples 1 and 2 and the amount of silicon deposited in the silicon scavengers. As shown in FIG. 1, it was found that there is a correlation between the average pore diameter and the amount of silicon deposited. It was found that the silicon trapping agents of Examples 1 and 2, each having an average pore diameter of around 10 nm, were particularly excellent in silicon trapping ability. In addition, the silicon scavengers of Examples 1 to 6 and Comparative Example 1 contain a hydrogenation active component, and the silicon scavenger of Comparative Example 2 does not contain a hydrogenation active component. All the silicon scavengers of Examples 1 to 6 and Comparative Examples 1 and 2 have a correlation between the average pore diameter and the amount of silicon deposited. That is, the silicon-trapping ability was not affected (or hardly affected) by the presence or absence of the hydrogenation active component, and it was thought that the pore structure of the silicon-trapping agent was important.

The silicon scavenger according to the present invention is useful in a method for hydrotreating heavy hydrocarbon oil because it has excellent silicon scavenging ability for feedstock oil containing heavy coker cracked hydrocarbon oil.

Claims (4)

A silicone scavenger for feedstock oil containing heavy coker cracked hydrocarbon oil,
The silicon scavenger includes alumina,
The content of alumina with respect to the total mass of the silicon scavenger is 50% by mass or more,
The silicon scavenger is a raw material oil containing heavy coker cracked hydrocarbon oil, characterized in that it has pores with an average pore diameter of 7 to 13 nm and a pore volume of 0.55 to 0.75 mL/g. silicone scavenger. The silicon collector according to claim 1, further comprising a hydrogenation active component, and the hydrogenation active component is supported on the alumina. Raw material oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 mass ppm was heated 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. Feedstock oil containing heavy coker cracked hydrocarbon oil, characterized in that it is brought into sequential contact with the silicon scavenger and the hydrotreating catalyst according to claim 1 or 2 at a space velocity of 0.1 to 2.0 h ^-1 . How to collect silicon. Raw material oil containing heavy coker cracked hydrocarbon oil with a silicon concentration of 0.1 to 15.0 mass ppm was heated 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. Feedstock oil containing heavy coker cracked hydrocarbon oil, characterized in that it is brought into sequential contact with the silicon scavenger and the hydrotreating catalyst according to claim 1 or 2 at a space velocity of 0.1 to 2.0 h ^-1 . Hydrotreating method.

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