Fluid catalytically cracked residual oil, catalytically cracked gas oil, and starting material oil for needle coke

Abstract

The present invention relates to a starting material oil for needle coke, said starting material oil containing a catalytically cracked gas oil and a fluid catalytically cracked residual oil, wherein the starting material oil for needle coke has a density of 0.95-1.40 g / cm3 at 15°C and a dynamic viscosity of 18 mm2 / s or less at 100°C, and contains at most 1.15 mass% sulfur components.

Description

Fluid catalytic cracking residue, catalytic cracking light oil, and feedstock oil for needle coke

[0001] The present invention relates to fluid catalytic cracking residue, catalytic cracking light oil, and feedstock oil for needle coke. This application claims priority based on Japanese Patent Application No. 2024-230095 filed in Japan on December 26, 2024, and incorporates its content herein by reference.

[0002] Due to the decreasing demand for heavy oil, the effective utilization of surplus heavy oil has been under consideration. Examples of heavy oil include atmospheric distillation residue obtained by treating crude oil with an atmospheric distillation unit, vacuum distillation residue obtained by treating the atmospheric distillation residue with a vacuum distillation unit, direct desulfurized residue obtained by directly treating the atmospheric distillation residue with a hydrodesulfurization unit, fluid catalytic cracking residue obtained by a fluid catalytic cracking reaction, ethylene bottom oil by-produced in an ethylene cracker using naphtha as a raw material, catalytic reforming residue by-produced in catalytic reforming using naphtha as a raw material, and the like.

[0003] As part of the effective utilization of heavy oil, the production of carbon materials using heavy oil has been under consideration. Conventionally, mainly coal-based residual oil has been used in the production of carbon materials. Carbon materials have required characteristics depending on their type, and said characteristics are derived from the characteristics of the feedstock oil. For example, when the carbon material is needle coke, a feedstock oil with appropriate ranges of density, kinematic viscosity, and sulfur content is required for product quality and efficient production.

[0004] Patent Document 1 discloses a feedstock oil composition for a negative electrode carbon material of a lithium-ion secondary battery, using the bottom oil of a residual oil fluid catalytic cracking unit and the residue of a vacuum distillation unit, or the bottom oil of a residual oil fluid catalytic cracking unit, the residue of a vacuum distillation unit, and the bottom oil of a fluid catalytic cracking unit as raw materials.

[0005] Patent Document 2 discloses a method for producing petroleum coke, characterized by coking a raw material oil containing a first heavy oil which is vacuum distillation residue with an initial boiling point of 300°C or higher, an asphalt content of 12% by mass or less, a saturation content of 50% by mass or more, and a sulfur content of 0.3% by mass or less, and a second heavy oil which is obtained by fluid catalytic cracking of a raw material oil containing atmospheric distillation residue, vacuum distillation residue, shale oil, tar sand bitumen, Orinoco tar, or heavy oil obtained by hydrorefining these, with an initial boiling point of 200°C or higher, a sulfur content of 0.5% by mass or less, and a nitrogen content of 0.2% by mass or less.

[0006] Patent Document 3 discloses a method for producing petroleum needle coke, which includes a step of coking a raw material oil containing at least a light oil with a final boiling point of 380°C or lower and an asphaltene component of 0% by mass, and a heavy oil with an initial boiling point of 200°C or higher, an aromatic component of 50% by mass or more, a sulfur content of 0.5% by mass or less, and a nitrogen content of 0.2% by mass or less.

[0007] Patent No. 5490636 Patent No. 4809675 Patent No. 6339105

[0008] From the viewpoint of further flexible utilization of heavy oils derived from crude oil, it is necessary to manufacture carbon materials using raw material oils that are combinations of heavy oils other than those disclosed in the above-mentioned Patent Documents 1 to 3. The present invention has been made in view of the above circumstances, and aims to provide fluid catalytic cracking residue and catalytic cracking light oil used as raw material oil for needle coke, which enable the effective utilization of heavy oils. It also aims to provide a raw material oil for needle coke that includes the fluid catalytic cracking residue and the catalytic cracking light oil.

[0009] To solve the above problems, the present invention has the following embodiments: [1A] A fluid catalytic cracking residue for producing needle coke raw material oil by mixing with catalytic cracking light oil, wherein the density of the needle coke raw material oil at 15°C is 0.95 to 1.40 g / cm³ ３ The kinematic viscosity at 100°C is 18 mm². ２ [1B] A fluid catalytic cracking residue having a density of 1.00 to 1.30 g / cm³ at 15°C.３ 、 1.05 to 1.30 g / cm ３ 、 0.95 to 1.15 g / cm ３ 、 1.00 to 1.15 g / cm ３ 、 or 1.05 to 1.15 g / cm ３ and having a kinematic viscosity at 100 °C of 15 mm ２ / s or less, 13 mm ２ / s or less, 1 to 18 mm ２ / s, 1 to 15 mm ２ / s, or 1 to 13 mm ２ / s, and having a sulfur content of 1.1 mass% or less, 1.08 mass% or less, 0.10 to 1.15 mass%, 0.10 to 1.1 mass%, or 0.10 to 1.08 mass%, the fluid catalytic cracking residual oil according to [1A]. [1C] The asphaltene content of the feedstock oil for needle coke is 5.0 mass% or less, 4.0 mass% or less, 3.0 mass% or less, 0.1 to 5.0 mass%, 0.1 to 4.0 mass%, or 0.1 to 3.0 mass%, the fluid catalytic cracking residual oil according to [1A] or [1B]. [1D] The nitrogen content of the feedstock oil for needle coke is 0.2 mass% or less, 0.15 mass% or less, 0.12 mass% or less, 0.01 to 0.2 mass%, 0.01 to 0.15 mass%, or 0.01 to 0.12 mass%, the fluid catalytic cracking residual oil according to any one of [1A] to [1C]. [1E] The ash content of the feedstock oil for needle coke is 0.1 mass% or less, 0.05 mass% or less, 0.045 mass% or less, 0.01 to 0.1 mass%, 0.01 to 0.05 mass%, or 0.01 to 0.045 mass%, the fluid catalytic cracking residual oil according to any one of [1A] to [1D]. [1F] The density of the fluid catalytic cracking residual oil at 15 °C is 0.96 to 1.40 g / cm ３ 、 1.00 to 1.40 g / cm ３ 、 or 1.07 to 1.40 g / cm ３ and having a kinematic viscosity at 100 °C of 50 mm ２ / s or less, 40 mm[[ID={28}]] ２ / s or less, 30 mm ２ / s or less, 19 to 50 mm ２ / s, 19 to 40 mm ２ / s, or 19 to 30 mm ２The fluid catalytic cracking residue according to any one of [1A] to [1E], wherein the sulfur content is 1.40% by mass or less, 1.35% by mass or less, 1.20% by mass or less, 0.1 to 1.40% by mass, 0.1 to 1.35% by mass, 0.1 to 1.20% by mass, greater than 1.15% by mass and 1.40% by mass or less, greater than 1.15% by mass and 1.35% by mass or less, or greater than 1.15% by mass and 1.20% by mass or less. [1G] The fluid catalytic cracking residue according to any one of [1A] to [1F], wherein the asphaltene content of the fluid catalytic cracking residue is 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 0.1 to 5.0% by mass, 0.1 to 4.0% by mass, or 0.1 to 3.0% by mass. [1H] The fluid catalytic cracking residue according to any one of [1A] to [1G], wherein the nitrogen content of the fluid catalytic cracking residue is 0.30% by mass or less, 0.25% by mass or less, 0.15% by mass or less, 0.01 to 0.30% by mass, 0.01 to 0.25% by mass, or 0.01 to 0.15% by mass. [1I] The fluid catalytic cracking residue according to any one of [1A] to [1H], wherein the ash content of the fluid catalytic cracking residue is 0.5% by mass or less, 0.4% by mass or less, 0.1% by mass or less, 0.001 to 0.5% by mass, 0.001 to 0.4% by mass, or 0.001 to 0.1% by mass. [2A] Catalytic cracking light oil for producing needle coke raw material oil by mixing with fluid catalytic cracking residue, wherein the density of the needle coke raw material oil at 15°C is 0.95 to 1.40 g / cm³. ３ The kinematic viscosity at 100°C is 18 mm². ２ Catalytic cracking light oil having a density of 1.15% by mass or less and a sulfur content of 1.15% by mass or less. [2B] The density of the needle coke raw material oil at 15°C is 1.00 to 1.30 g / cm³. ３ , 1.05-1.30g / cm ３ , 0.95-1.15g / cm ３ , 1.00-1.15g / cm ３ , or 1.05 to 1.15 g / cm³ ３ The kinematic viscosity at 100°C is 15 mm². ２ / s or less, 13mm ２ / s or less, 1-18mm ２ / s, 1-15mm ２ / s, or 1-13 mm ２[2A] Catalytic cracking light oil according to [2A], wherein the sulfur content is 1.1% by mass or less, 1.08% by mass or less, 0.10 to 1.15% by mass, 0.10 to 1.1% by mass, or 0.10 to 1.08% by mass. [2C] Catalytic cracking light oil according to [2A] or [2B], wherein the asphaltene content of the needle coke feedstock is 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 0.1 to 5.0% by mass, 0.1 to 4.0% by mass, or 0.1 to 3.0% by mass. [2D] Catalytic cracking light oil according to any one of [2A] to [2C], wherein the nitrogen content of the needle coke feedstock is 0.2% by mass or less, 0.15% by mass or less, 0.12% by mass or less, 0.01 to 0.2% by mass, 0.01 to 0.15% by mass, or 0.01 to 0.12% by mass. [2E] The catalytic cracking light oil according to any one of [2A] to [2D], wherein the ash content of the needle coke raw material oil is 0.1% by mass or less, 0.05% by mass or less, 0.045% by mass or less, 0.01 to 0.1% by mass, 0.01 to 0.05% by mass, or 0.01 to 0.045% by mass. [2F] The catalytic cracking light oil has a density of 0.75 to 0.94 g / cm³ at 15°C. ３ , 0.80-0.93g / cm ３ , or 0.85-0.92 g / cm³ ３ The kinematic viscosity at 100°C is 10 mm ２ / s or less, 5mm ２ / s or less, 3mm ２ / s or less, 0.5-10mm ２ / s, 0.5-5mm ２ / s, or 0.5-3 mm ２[2G] Catalytic cracking diesel fuel according to any one of [2A] to [2E], wherein the sulfur content is 0.5% by mass or less, 0.3% by mass or less, 0.2% by mass or less, 0.01 to 0.5% by mass, 0.01 to 0.3% by mass, or 0.01 to 0.2% by mass. [2G] Catalytic cracking diesel fuel according to any one of [2A] to [2F], wherein the asphaltene content of the catalytic cracking diesel fuel is 1% by mass or less, 0.1% by mass or less, 0.01% by mass or less, 0.001 to 1% by mass, 0.001 to 0.1% by mass, or 0.001 to 0.01% by mass. [2H] Catalytic cracking light oil according to any one of [2A] to [2G], wherein the nitrogen content of the catalytic cracking light oil is 0.2% by mass or less, 0.15% by mass or less, 0.1% by mass or less, 0.01 to 0.2% by mass, 0.01 to 0.15% by mass, or 0.01 to 0.1% by mass. [2I] Catalytic cracking light oil according to any one of [2A] to [2H], wherein the ash content of the catalytic cracking light oil is 0.1% by mass or less, 0.01% by mass or less, 0.005% by mass or less, 0.0001 to 0.1% by mass, 0.0001 to 0.01% by mass, or 0.0001 to 0.005% by mass. [3A] A raw material oil for needle coke comprising catalytic cracking light oil and fluid catalytic cracking residue, wherein the density of the raw material oil for needle coke at 15°C is 0.95 to 1.40 g / cm³. ３ The kinematic viscosity at 100°C is 18 mm². ２ [3B] Needle coke raw material oil having a density of 1.00 to 1.30 g / cm³ at 15°C. ３ , 1.05-1.30g / cm ３ , 0.95-1.15g / cm ３ , 1.00-1.15g / cm ３ , or 1.05 to 1.15 g / cm³ ３ The kinematic viscosity at 100°C is 15 mm². ２ / s or less, 13mm ２ / s or less, 1-18mm ２ / s, 1-15mm ２ / s, or 1-13 mm ２The needle coke raw material oil according to [3A], wherein the ratio is / s and the sulfur content is 1.1% by mass or less, 1.08% by mass or less, 0.10 to 1.15% by mass, 0.10 to 1.1% by mass, or 0.10 to 1.08% by mass. [3C] The needle coke raw material oil according to [3A] or [3B], wherein the asphaltene content of the needle coke raw material oil is 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 0.1 to 5.0% by mass, 0.1 to 4.0% by mass, or 0.1 to 3.0% by mass. [3D] Needle coke raw material oil according to any one of [3A] to [3C], wherein the nitrogen content of the needle coke raw material oil is 0.2% by mass or less, 0.15% by mass or less, 0.12% by mass or less, 0.01 to 0.2% by mass, 0.01 to 0.15% by mass, or 0.01 to 0.12% by mass. [3E] Needle coke raw material oil according to any one of [3A] to [3D], wherein the ash content of the needle coke raw material oil is 0.1% by mass or less, 0.05% by mass or less, 0.045% by mass or less, 0.01 to 0.1% by mass, 0.01 to 0.05% by mass, or 0.01 to 0.045% by mass. [3F] Needle coke raw material oil according to any one of [3A] to [3E], wherein the total content of catalytic cracking light oil and fluid catalytic cracking residue relative to the total volume of the needle coke raw material oil is 80% by volume or more. [3G] Needle coke raw material oil according to any one of [3A] to [3F], wherein the total content of catalytic cracking light oil and fluid catalytic cracking residue with respect to the total volume of the needle coke raw material oil is 90% by volume or more, 95% by volume or more, or 100% by volume. [3H] Needle coke raw material oil according to any one of [3A] to [3G], wherein the volume ratio of the content of catalytic cracking light oil to the content of fluid catalytic cracking residue is 0.05 to 2.5, 0.05 to 2.0, 0.05 to 1.0, or 0.1 to 0.5.

[0010] According to the present invention, it is possible to provide a fluid catalytic cracking residue and catalytic cracking light oil used as a raw material oil for needle coke, which enable the effective utilization of heavy oil. Furthermore, it is possible to provide a raw material oil for needle coke containing the fluid catalytic cracking residue and the catalytic cracking light oil.

[0011] The embodiments of the present invention will be described in detail below, but the following description is merely one example of an embodiment of the present invention, and the present invention is not limited to these contents and can be modified and implemented within the scope of its gist.

[0012] <Definitions> The definitions of terms used herein are as follows: Fluid catalytic cracking residue is the residue obtained when cracked oil, which is obtained by contacting raw material oil with a fluid catalytic cracking catalyst in a fluid catalytic cracking unit, is distilled. Examples of the raw material oil include atmospheric distillation residue, vacuum distillation residue, and vacuum distilled light oil obtained by treating atmospheric distillation residue with a vacuum distillation unit. That is, the fluid catalytic cracking unit also includes a residue fluid catalytic cracking unit. Catalytic cracking light oil refers to a fraction obtained as an intermediate fraction when raw material oil is subjected to fluid catalytic cracking in a fluid catalytic cracking unit or a residue fluid catalytic cracking unit, with a boiling point range of 170°C to 390°C in atmospheric distillation. The raw material oil is the same as described for fluid catalytic cracking residue. Catalytic cracking light oil is the heaviest fraction of the distillate of cracked oil, and fluid catalytic cracking residue is a fraction heavier than catalytic cracking light oil. There are no particular restrictions on the fluid catalytic cracking unit or residue fluid catalytic cracking unit, and known equipment can be used.

[0013] 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 kinematic viscosity at 100°C can be measured in accordance with JIS K 2283:2000 "Crude oil and petroleum products - Kinematic viscosity test method and viscosity index calculation method". The asphaltene content can be measured in accordance with JPI-5S-22-83 "Compositional analysis of asphalt by column chromatography". 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 2609:2022 "Crude oil and petroleum products - Chemiluminescence method for nitrogen content test". Ash content can be measured in accordance with JIS K2272:1998 "Crude oil and petroleum products - Test methods for ash content and sulfated ash content". In this specification, the lower and upper limits of the oil property parameters can be arbitrarily combined.

[0014] ≪Fluid Catalytic Cracking Residue≫ The fluid catalytic cracking residue in this embodiment is fluid catalytic cracking residue used to produce needle coke raw material oil by mixing it with catalytic cracking light oil. By mixing the fluid catalytic cracking residue with catalytic cracking light oil, the density of the needle coke raw material oil at 15°C is increased to 0.95 to 1.40 g / cm³. ３ The kinematic viscosity at 100°C was 18 mm ２ The sulfur content can be adjusted to 1.15% by mass or less, below / s.

[0015] The density of the residual fluid catalytic cracking oil at 15°C is 0.96–1.40 g / cm³. ３ Preferably, it is 1.00 to 1.40 g / cm³. ３ It is more preferable that the concentration be 1.07 to 1.40 g / cm³. ３ It is even more preferable that the density of the fluid catalytic cracking residue at 15°C is within the aforementioned range, as this makes it easier to adjust the density to that of the needle coke feedstock oil described later.

[0016] The kinematic viscosity of the residual fluid in catalytic cracking at 100°C is 50 mm². ２ Preferably, it should be less than or equal to 40 mm ２ It is more preferable that it be less than or equal to / s, and 30 mm ２ It is even more preferable that the kinematic viscosity is less than or equal to / s. A lower limit of kinematic viscosity is, for example, 19 mm. ２ The values ​​given are / s. The kinematic viscosity is 19-50 mm². ２ It is preferable that it be / s, and 19 to 40 mm ２ It is more preferable that it be / s, and 19-30 mm ２ It is even more preferable that the kinematic viscosity of the fluid catalytic cracking residue at 100°C is below the above upper limit. If the kinematic viscosity of the fluid catalytic cracking residue at 100°C is below the above upper limit, it becomes easier to adjust it to the kinematic viscosity of the needle coke raw material oil described later. Since the kinematic viscosity of the fluid catalytic cracking residue at 100°C is high, it is difficult to use it as is as a needle coke raw material oil. In the present invention, the kinematic viscosity can be adjusted by mixing it with catalytic cracking diesel fuel.

[0017] The asphaltene content of the fluid catalytic cracking residue is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.0% by mass or less. For example, the lower limit of the asphaltene content is 0.1% by mass. The asphaltene content is preferably 0.1 to 5.0% by mass, more preferably 0.1 to 4.0% by mass, and even more preferably 0.1 to 3.0% by mass. If the asphaltene content of the fluid catalytic cracking residue is below the above upper limit, it becomes easier to adjust it to the asphaltene content of the needle coke feedstock oil described later.

[0018] The sulfur content of the fluid catalytic cracking residue is preferably 1.40% by mass or less, more preferably 1.35% by mass or less, and even more preferably 1.20% by mass or less. The lower limit of the sulfur content is not particularly limited, but for example, it can be 0.1% by mass. The sulfur content of the fluid catalytic cracking residue may be high, for example, it may exceed 1.15% by mass. The sulfur content is preferably 0.1 to 1.40% by mass, more preferably 0.1 to 1.35% by mass, and even more preferably 0.1 to 1.20% by mass. The sulfur content is preferably greater than 1.15% by mass and 1.40% by mass or less, more preferably greater than 1.15% by mass and 1.35% by mass or less, and even more preferably greater than 1.15% by mass and 1.20% by mass or less. If the sulfur content of the fluid catalytic cracking residue is below the above upper limit, it becomes easier to adjust it to the sulfur content of the raw material oil for needle coke described later. Because the sulfur content of residual fluid catalytic cracking is high, it is difficult to use it directly as a raw material for needle coke. In this invention, the sulfur content can be adjusted by mixing it with catalytic cracking diesel fuel.

[0019] The nitrogen content of the fluid catalytic cracking residue is preferably 0.30% by mass or less, more preferably 0.25% by mass or less, and even more preferably 0.15% by mass or less. The lower limit of the nitrogen content is not particularly limited, but for example, it is 0.01% by mass. The nitrogen content is preferably 0.01 to 0.30% by mass, more preferably 0.01 to 0.25% by mass, and even more preferably 0.01 to 0.15% by mass. If the nitrogen content of the fluid catalytic cracking residue is below the above upper limit, it becomes easier to adjust it to the nitrogen content of the needle coke feedstock oil described later.

[0020] The ash content of the fluid catalytic cracking residue is preferably 0.5% by mass or less, more preferably 0.4% by mass or less, and even more preferably 0.1% by mass or less. The lower limit of the ash content is not particularly limited, but for example, it is 0.001% by mass. The ash content is preferably 0.001 to 0.5% by mass, more preferably 0.001 to 0.4% by mass, and even more preferably 0.001 to 0.1% by mass. If the ash content of the fluid catalytic cracking residue is below the above upper limit, it becomes easier to adjust it to the ash content of the raw material oil for needle coke described later.

[0021] ≪Catalytic Cracking Light Oil≫ The catalytic cracking light oil of this embodiment is catalytic cracking light oil for producing needle coke raw material oil by mixing it with fluid catalytic cracking residue. By mixing catalytic cracking light oil with fluid catalytic cracking residue, the density of the needle coke raw material oil at 15°C is increased to 0.95 to 1.40 g / cm³. ３ The kinematic viscosity at 100°C was 18 mm ２ The sulfur content can be adjusted to 1.15% by mass or less, below / s.

[0022] The density of catalytic cracking diesel fuel at 15°C is 0.75–0.94 g / cm³. ３ Preferably, it is 0.80 to 0.93 g / cm³. ３ It is more preferable that the concentration be 0.85 to 0.92 g / cm³. ３It is even more preferable that the density of catalytic cracking diesel fuel at 15°C is within the above range. If the density of catalytic cracking diesel fuel at 15°C is within the above range, it becomes easier to adjust it to the density of the needle coke raw material oil described later. Since the density of catalytic cracking diesel fuel at 15°C is low, it is difficult to use it as is as a needle coke raw material oil. In the present invention, the density at 15°C can be adjusted by mixing it with the residual fluid catalytic cracking oil.

[0023] The kinematic viscosity of catalytic cracking diesel fuel at 100°C is 10 mm². ２ It is preferable that it be less than or equal to 5 mm ２ It is more preferable that it be less than or equal to / s, and 3 mm ２ It is even more preferable that the kinematic viscosity is less than or equal to / s. A lower limit of kinematic viscosity is, for example, 0.5 mm. ２ The values ​​given are / s. The kinematic viscosity is 0.5 to 10 mm². ２ It is preferable that the value be / s, and the value is 0.5 to 5 mm. ２ It is more preferable that the value be / s, and the value is 0.5 to 3 mm. ２ It is even more preferable that the kinematic viscosity of catalytic cracking diesel fuel at 100°C is below the above upper limit.

[0024] The asphaltene content of catalytic cracking diesel fuel is preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less. For example, the lower limit of the asphaltene content is 0.001% by mass. The asphaltene content is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.1% by mass, and even more preferably 0.001 to 0.01% by mass. If the asphaltene content of catalytic cracking diesel fuel is below the above upper limit, it becomes easier to adjust it to the asphaltene content of the needle coke feedstock oil described later.

[0025] The sulfur content of catalytic cracking diesel fuel is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and even more preferably 0.2% by mass or less. The lower limit of the sulfur content is not particularly limited, but for example, it is 0.01% by mass. The sulfur content is preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.3% by mass, and even more preferably 0.01 to 0.2% by mass. If the sulfur content of catalytic cracking diesel fuel is below the above upper limit, it becomes easier to adjust it to the sulfur content of the needle coke feedstock oil described later.

[0026] The nitrogen content of catalytic cracking diesel fuel is preferably 0.2% by mass or less, more preferably 0.15% by mass or less, and even more preferably 0.1% by mass or less. The lower limit of the nitrogen content is not particularly limited, but for example, it is 0.01% by mass. The nitrogen content is preferably 0.01 to 0.2% by mass, preferably 0.01 to 0.15% by mass, and even more preferably 0.01 to 0.1% by mass. If the nitrogen content of catalytic cracking diesel fuel is below the above upper limit, it becomes easier to adjust it to the nitrogen content of the needle coke feedstock oil described later.

[0027] The ash content of catalytic cracking diesel fuel is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and even more preferably 0.005% by mass or less. The lower limit of the ash content is not particularly limited, but for example, it is 0.0001% by mass. The ash content is preferably 0.0001 to 0.1% by mass, more preferably 0.0001 to 0.01% by mass, and even more preferably 0.0001 to 0.005% by mass. If the ash content of catalytic cracking diesel fuel is below the above upper limit, it becomes easier to adjust it to the ash content of the needle coke raw material oil described later.

[0028] ≪Needle Coke Raw Material Oil≫ The needle coke raw material oil of this embodiment (hereinafter also simply referred to as "raw material oil") includes catalytic cracking light oil and fluid catalytic cracking residue. The density of the raw material oil at 15°C is 0.95 to 1.40 g / cm³. ３ The kinematic viscosity at 100°C is 18 mm². ２ The pH is less than or equal to / s, and the sulfur content is 1.15% by mass or less.

[0029] The raw material oil includes catalytically cracked diesel fuel and fluid catalytic cracking residue. The total content of catalytically cracked diesel fuel and fluid catalytic cracking residue relative to the total volume of the raw material oil is preferably 80% by volume or more, more preferably 90% by volume or more, and even more preferably 95% by volume or more. The total content of catalytically cracked diesel fuel and fluid catalytic cracking residue relative to the total volume of the raw material oil may be 100% by volume.

[0030] The raw material oil may include catalytically cracked light oil and fluid catalytic cracking residue, as well as heavy extracts, which are particularly heavy oils among the oils extracted and removed by solvent extraction of lubricating oil base oils, such as atmospheric distillation residue, vacuum distillation residue, cutback residue obtained by mixing vacuum distillation residue with a light base material, direct desulfurization residue, atmospheric distillation light oil, vacuum distillation light oil, hydrodesulfurization light oil, and hydrocracked heavy oil, as well as pyrolysis heavy oil, pyrolysis light oil, tumbled oil, and coal tar residue. When the raw material oil contains vacuum distillation residue, the content of vacuum distillation residue relative to the total volume of the raw material oil is preferably 5% by volume or less, and more preferably 1% by volume or less. In one embodiment, it is preferable that the raw material oil does not contain vacuum distillation residue. The raw material oil may also contain distillates, which are light oils other than catalytically cracked light oil. When the raw material oil contains distillates other than catalytically cracked diesel fuel, the content of the other distillates relative to the total volume of the raw material oil is preferably 5% by volume or less, more preferably less than 5% by volume, and even more preferably 1% by volume or less. In one embodiment, it is preferable that the raw material oil does not contain distillates other than catalytically cracked diesel fuel.

[0031] The volume ratio of catalytic cracking diesel fuel to the content of fluid catalytic cracking residue is preferably 0.05 to 2.5, more preferably 0.05 to 2.0, even more preferably 0.05 to 1.0, and particularly preferably 0.1 to 0.5. When the volume ratio is within the above range, it is easier to satisfy the properties of the raw material oil described later.

[0032] The density of the raw material oil at 15°C is 0.95–1.40 g / cm³. ３ The concentration is 1.00 to 1.30 g / cm³. ３ Preferably, it is 1.05 to 1.30 g / cm³. ３It is more preferable that it is. Further, in one embodiment, the density of the feedstock oil at 15 ° C is 0.95 to 1.15 g / cm ３ It is preferable that it is, and 1.00 to 1.15 g / cm ３ It is more preferable that it is, and 1.05 to 1.15 g / cm ３ It is more preferable that it is. When the density is at least the lower limit value, the yield of needle coke is likely to improve. When the density is at most the upper limit value, when the density is at most the upper limit value, the influence of heavy components is reduced, and the generation and growth of mesophase are likely to proceed.

[0033] The kinematic viscosity of the feedstock oil at 100 ° C is 18 mm ２ / s or less, and it is preferable that it is 15 mm ２ / s or less, and it is more preferable that it is 13 mm ２ / s or less. As the lower limit value of the kinematic viscosity, for example, 1 mm ２ / s can be mentioned. The kinematic viscosity is preferably 1 to 18 mm ２ / s, more preferably 1 to 15 mm ２ / s, and even more preferably 1 to 13 mm ２ / s. When the kinematic viscosity is at most the upper limit value, oil feeding by piping is easy and efficient.

[0034] The asphaltene content of the feedstock oil is preferably 5.0 mass% or less, more preferably 4.0 mass% or less, and even more preferably 3.0 mass% or less. As the lower limit value of the asphaltene content, for example, 0.1 mass% can be mentioned. The asphaltene content is preferably 0.1 to 5.0 mass%, more preferably 0.1 to 4.0 mass%, and even more preferably 0.1 to 3.0 mass%. When the asphaltene content is at most the upper limit value, it becomes difficult to generate needle coke having a complex structure by premature coking.

[0035] The sulfur content of the raw material oil is 1.15% by mass or less, preferably 1.1% by mass or less, and more preferably 1.08% by mass or less. The lower limit of the sulfur content is not particularly limited, but for example, it can be 0.10% by mass. The sulfur content is preferably 0.10 to 1.15% by mass, more preferably 0.10 to 1.1% by mass, and even more preferably 0.10 to 1.08% by mass. When the sulfur content is below the above upper limit, the puffing of the resulting needle coke can be sufficiently suppressed, and the coefficient of thermal expansion tends to be low.

[0036] The nitrogen content of the raw material oil is preferably 0.2% by mass or less, more preferably 0.15% by mass or less, and even more preferably 0.12% by mass or less. The lower limit of the nitrogen content is not particularly limited, but for example, it is 0.01% by mass. The nitrogen content is preferably 0.01 to 0.2% by mass, more preferably 0.01 to 0.15% by mass, and even more preferably 0.01 to 0.12% by mass. When the nitrogen content is below the above upper limit, puffing of the resulting needle coke can be sufficiently suppressed, and the coefficient of thermal expansion tends to be low.

[0037] The ash content of the raw material oil is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.045% by mass or less. The lower limit of the ash content is not particularly limited, but for example, it is 0.01% by mass. The ash content is preferably 0.01 to 0.1% by mass, more preferably 0.01 to 0.05% by mass, and even more preferably 0.01 to 0.045% by mass. When the ash content is below the above upper limit, the generation and growth of the mesophase proceeds more easily.

[0038] <Method for Manufacturing Raw Material Oil> The mixing of fluid catalytic cracking residue and catalytic cracking diesel fuel may be carried out by tank blending or line blending. Tank blending is a mixing method in which the fluid catalytic cracking residue and catalytic cracking diesel fuel, which are raw material oils, in a tank (storage tank) are mixed for several hours, for example, using an agitator such as a jet mixer or propeller mixer, to adjust the various properties of the resulting mixed oil. Line blending is a mixing method in which the fluid catalytic cracking residue and catalytic cracking diesel fuel, which are multiple types of raw material oils, are mixed in a turbulent flow within a line (transport pipe) to adjust the various properties of the resulting mixed oil. Tank blending or line blending may be carried out, for example, at a crude oil storage base or refinery. Note that the mixing method used in the method for manufacturing raw material oil in this embodiment is not limited to tank blending or line blending. Furthermore, tank blending may also be carried out by ship's hold blending. Ship hold blending is a type of tank blending described above, and refers to the blending of raw material oils, including fluid catalytic cracking residue and catalytic cracking diesel fuel, within the ship's hold (tank) during transport. Ship hold blending eliminates the need to own separate tanks for blending and allows for efficient mixing.

[0039] <Method for manufacturing needle coke> Needle coke can be manufactured by a process of coking the above raw material oil and a process of calcining the coke produced by coking.

[0040] Examples of caulking methods include delayed caulking, screw breaking, flexi-caulking, the Yurika process, and H-Oil. In delayed caulking, the raw material oil is rapidly passed through a heating tube while being heated before being introduced into a coke drum where caulking proceeds. The conditions for caulking are not particularly limited. The heating temperature for caulking may be, for example, 400-600°C or 450-550°C. The heating time may be, for example, 24-72 hours or 36-60 hours.

[0041] Coke can be calcined using calcination equipment such as a rotary kiln or a shaft furnace. The calcination temperature may be, for example, 1000 to 1500°C. The calcination time may be, for example, 2 to 6 hours.

[0042] Needle coke can be used as aggregate for graphite electrodes in electric steelmaking and as carbon material for lithium-ion secondary batteries.

[0043] <Mechanism of Action> As shown in the comparative examples described later, when only fluid catalytic cracking residue is used as a raw material, there are problems with high kinematic viscosity and sulfur content. When only catalytic cracking diesel is used as a raw material, there is a problem with low density. Therefore, it is difficult to use fluid catalytic cracking residue or catalytic cracking diesel alone as raw material for needle coke. On the other hand, the inventors of this application have found that by using a mixture of fluid catalytic cracking residue and catalytic cracking diesel, the shortcomings of each (the problems mentioned above) can be compensated for. It should be noted that while sulfur content, nitrogen content, etc., are weighted averages in the mixed oil, kinematic viscosity, asphaltene content, etc., are properties that do not necessarily become weighted averages, making it difficult to predict that the mixed oil will have the desired properties. Furthermore, in this invention, two or more types of heavy oil are always used, which contributes to the effective utilization of heavy oil.

[0044] 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.

[0045] <Analysis of Properties> (Density) The density at 15°C was measured in accordance with JIS K 2249-1:2011 "Crude oil and petroleum products - Method for determining density - Part 1: Vibration method".

[0046] (Kinematic viscosity) The kinematic viscosity at 100°C was measured in accordance with JIS K 2283:2000 "Crude oil and petroleum products - Test method for kinematic viscosity and method for calculating viscosity index".

[0047] (Asphaltene content) The asphaltene content was measured in accordance with JPI-5S-22-83 "Compositional analysis of asphalt by column chromatography".

[0048] (Sulfur content) The sulfur content was measured in accordance with JIS K 2541-4:2003 "Crude oil and petroleum products - Test methods for sulfur content, Part 4: Radiation excitation method".

[0049] (Nitrogen content) The nitrogen content was measured in accordance with JIS K 2609:2022 "Crude oil and petroleum products - Chemiluminescence method for testing nitrogen content".

[0050] (Ash content) The ash content was measured in accordance with JIS K2272:1998 "Crude oil and petroleum products - Test methods for ash content and sulfated ash content".

[0051] <Raw Materials> The following materials were used: liquid catalytic cracking residue and catalytic cracking diesel fuel with the properties described in Table 1.

[0052]

[0053] [Example 1] A feedstock oil was prepared by mixing fluid catalytic cracking residue and catalytic cracking diesel fuel. The fluid catalytic cracking residue was 95% by volume and the catalytic cracking diesel fuel was 5% by volume. The density at 15°C, kinematic viscosity at 100°C, asphaltene content, sulfur content, nitrogen content, and ash content of the obtained feedstock oil were measured by the method described above. The results are shown in Table 2.

[0054] [Examples 2-6] Raw material oil was prepared in the same manner as in Example 1, except that the residual fluid catalytic cracking oil and catalytic cracking light oil were mixed in the proportions shown in Table 2. The density at 15°C, kinematic viscosity at 100°C, asphaltene content, sulfur content, nitrogen content, and ash content of the obtained raw material oil were measured using the method described above. The results are shown in Table 2.

[0055] [Comparative Example 1] Only the residue from fluid catalytic cracking was used as the raw material. The density at 15°C, the kinematic viscosity at 100°C, the asphaltene content, sulfur content, nitrogen content, and ash content of the raw material were measured using the method described above. The results are shown in Table 2.

[0056] [Comparative Example 2] Catalytic cracked diesel fuel was used as the raw material. The density at 15°C, kinematic viscosity at 100°C, asphaltene content, sulfur content, nitrogen content, and ash content of the raw material were measured using the method described above. The results are shown in Table 2.

[0057] [Comparative Example 3] A raw material oil was prepared in the same manner as in Example 1, except that the residual fluid catalytic cracking oil and catalytic cracking light oil were mixed in the proportions shown in Table 2. The density at 15°C, kinematic viscosity at 100°C, asphaltene content, sulfur content, nitrogen content, and ash content of the obtained raw material oil were measured using the method described above. The results are shown in Table 2.

[0058]

[0059] In Comparative Example 1, which used only fluid catalytic cracking residue as a raw material, the kinematic viscosity was high, making it difficult to transport the oil through piping and resulting in poor needle coke production efficiency. Furthermore, the high sulfur content prevented puffing of the resulting needle coke, and the thermal expansion coefficient also tended to be high. In Comparative Example 2, which used only catalytic cracking fuel as a raw material, the density was low, resulting in a low needle coke yield. On the other hand, in Examples 1 to 6, which included both fluid catalytic cracking residue and catalytic cracking fuel (volume ratio of fluid catalytic cracking residue to catalytic cracking fuel = 50:50 to 95:5), the density, kinematic viscosity, and sulfur content were within appropriate ranges. It was found that the catalytic cracking fuel compensated for the high kinematic viscosity and sulfur content of the fluid catalytic cracking residue, and the fluid catalytic cracking residue compensated for the low density of the catalytic cracking fuel. In Comparative Example 3, where fluid catalytic cracking residue and catalytic cracking fuel were mixed in a volume ratio of 25:75, the density was low.

[0060] The needle coke raw material oil of the present invention is useful because it uses surplus heavy oils such as residual fluid catalytic cracking oil and catalytic cracking light oil.

Claims

1. A needle coke raw material comprising catalytic cracking diesel fuel and fluid catalytic cracking residue, wherein the density of the needle coke raw material at 15°C is 0.95 to 1.40 g / cm³. ３ The kinematic viscosity at 100°C is 18 mm². ２ Needle coke feedstock oil having a pH of 0.5 / s or less and a sulfur content of 1.15% by mass or less.

2. The needle coke raw material oil according to claim 1, wherein the total content of catalytic cracking light oil and fluid catalytic cracking residue relative to the total volume of the needle coke raw material oil is 80% by volume or more.

3. A fluid catalytic cracking residue for mixing with catalytic cracking diesel oil to produce raw material oil for needle coke, wherein the density of the raw material oil for needle coke at 15°C is 0.95 to 1.40 g / cm³. ３ The kinematic viscosity at 100°C is 18 mm². ２ Fluid catalytic cracking residue with a coefficient of 1.15% by mass or less and a sulfur content of 1.15% by mass or less.

4. Catalytic cracking light oil for producing needle coke raw material oil by mixing with fluid catalytic cracking residue, wherein the density of the needle coke raw material oil at 15°C is 0.95 to 1.40 g / cm³. ３ The kinematic viscosity at 100°C is 18 mm². ２ Catalytic cracking diesel fuel with a viscosity of 1.15% by mass or less and a sulfur content of 1.15% by mass or less.

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