A method and system for producing both lubricating base oil and industrial white oil

Abstract

The present disclosure relates to a method and system for producing lubricating base oil and industrial white oil. The method comprises: feeding residual oil into a solvent deasphalting unit for solvent deasphalting refining treatment to obtain deasphalted oil; feeding hydrogen, vacuum gas oil and the deasphalted oil into a hydrocracking unit to contact with a first hydrogenation catalyst for first hydrogenation reaction to obtain hydrogenated oil; feeding the hydrogenated oil into a first separation unit for first separation treatment to obtain naphtha, aviation kerosene, diesel, light tail oil component and heavy tail oil component; feeding the light tail oil component into a first catalytic dewaxing reaction unit to contact with a second hydrogenation catalyst for second hydrogenation reaction to obtain first hydrogenation dewaxed oil; feeding the heavy tail oil component into a second catalytic dewaxing reaction unit to contact with a third hydrogenation catalyst for third hydrogenation reaction to obtain second hydrogenation dewaxed oil; and feeding the first hydrogenation dewaxed oil and the second hydrogenation dewaxed oil into a second separation unit for second separation treatment. The quality of the oil product is significantly improved.

Description

Technical Field

[0001] The disclosure relates to the production of base oils and industrial white oils, specifically to a method and system for producing both lubricating oil base oils and industrial white oils. Background Technology

[0002] Existing methods for producing Group III lubricating oil base oils with a viscosity index >120 generally use paraffinic crude oil, hydrocracking tail oil, etc., as feedstocks combined with hydrotreating. However, when using this method to process intermediate feedstocks to produce lubricating oil base oils with a viscosity index >120, deep conversion of the feedstock oil is generally required. Therefore, the following problems exist:

[0003] When it is necessary to produce heavy base oils, the feedstock oil has a wide distillation range. During the isomerization process, it is not possible to produce both light and heavy base oils simultaneously, resulting in low lubricant yield and significant viscosity loss. Furthermore, due to the harsh reaction conditions, the product viscosity loss is large, the oil color deteriorates, and the stability is poor, leading to poor quality of high-viscosity oils. Summary of the Invention

[0004] The purpose of this disclosure is to provide a method and system for producing both lubricating oil base oil and industrial white oil, which can achieve narrow fraction feeding, produce high viscosity index base oil and high viscosity industrial white oil, and improve oil quality.

[0005] To achieve the above objectives, the first aspect of this disclosure provides a method for producing both lubricating oil base oil and industrial white oil, comprising the following steps:

[0006] S1. The residual oil is fed into the solvent deasphalting unit for solvent deasphalting and refining treatment to obtain deasphalted oil;

[0007] S2. Hydrogen, vacuum wax oil and the deasphalted oil are introduced into the hydrocracking unit and contacted with the first hydrocracking catalyst to carry out the first hydrocracking reaction and obtain hydrocracking product oil. The first hydrocracking catalyst includes a hydrotreatment catalyst, a hydrocracking catalyst and a hydrorefining catalyst.

[0008] S3. The hydrotreated oil is fed into the first separation unit for the first separation process to obtain naphtha, jet fuel, diesel, light tail oil components and heavy tail oil components; wherein the distillation cut-off points of the light tail oil components and heavy tail oil components are any values ​​within the range of 450 to 500°C.

[0009] S4. The light tail oil component is introduced into the first catalytic dewaxing reaction unit and contacted with the second hydrogenation catalyst to carry out the second hydrogenation reaction, thereby obtaining the first hydrogenated dewaxed oil; the heavy tail oil component is introduced into the second catalytic dewaxing reaction unit and contacted with the third hydrogenation catalyst to carry out the third hydrogenation reaction, thereby obtaining the second hydrogenated dewaxed oil; the second hydrogenation catalyst and the third hydrogenation catalyst each independently include a hydrogenation isomerization catalyst and a post-hydrogenation refining catalyst;

[0010] S5. The first hydrodewaxed oil and the second hydrodewaxed oil are fed into the second separation unit for a second separation process to obtain lubricating oil base oil and industrial white oil.

[0011] Optionally, in step S1, the conditions for the solvent deasphalting and refining treatment include:

[0012] In the extraction tower, the volume ratio of solvent to residue oil is (2-10):1, the top temperature of the extraction tower is 20-150℃, and the pressure is 2-6MPa; preferably, the volume ratio of solvent to residue oil is (3-8):1, and the top temperature of the extraction tower is 30-120℃, and the pressure is 3-5MPa.

[0013] Optionally, the solvent is selected from one or more of hydrocarbons with 3 to 7 carbon atoms, condensate oil, light naphtha, and gasoline; preferably, the solvent includes propane, or the solvent includes propane and one or more of ethane, propylene, butane, and pentane; more preferably, the content of propane in the solvent is 80 to 100% by weight, preferably 90 to 100% by weight, and even more preferably 95 to 100% by weight.

[0014] Preferably, the solvent deasphalting and refining treatment results in the deasphalted oil having a carbon residue value of 10% by weight or less, more preferably 6% by weight or less;

[0015] Optionally, the residue oil is selected from one or more of vacuum residue oil and atmospheric residue oil.

[0016] Optionally, the hydrotreatment catalyst, hydrocracking catalyst, and hydrorefining catalyst are arranged sequentially along the flow direction of the mixed feedstock in the hydrocracking unit; step S2 includes:

[0017] The vacuum wax oil and the deasphalted oil are mixed and then introduced into the hydrocracking unit. The mixed feedstock is first contacted with the hydrotreating catalyst for a hydrotreating reaction; then it is contacted with the hydrocracking catalyst for a hydrocracking reaction; and finally it is contacted with the hydrorefining catalyst for a hydrorefining reaction to obtain the hydrotreated oil.

[0018] Preferably, a hydrotreating protectant is further disposed upstream of the hydrotreating catalyst along the flow direction of the mixed feedstock in the hydrocracking unit; the volume ratio of the hydrotreating protectant: hydrotreating catalyst: hydrocracking catalyst: hydrorefining catalyst is (5-35):100:(70-250):(20-180); preferably (10-30):100:(80-220):(40-150);

[0019] Optionally, the volume ratio of the depressurized wax oil to the deasphalted oil is (2-30):1, preferably (5-20):1;

[0020] Preferably, the residual carbon value of the mixture of the vacuum wax oil and the deasphalted oil is not greater than 2% by weight; more preferably, it is not greater than 1% by weight.

[0021] Optionally, in step S2, the processing conditions of the hydrocracking unit include:

[0022] The hydrogenation reaction was carried out at a temperature of 330–430 °C, a hydrogen partial pressure of 10–20 MPa, and a volume hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600–2000):1; preferably, the hydrogenation reaction temperature is 350–390°C, the hydrogen partial pressure is 12–18 MPa, and the volume hourly space velocity is 0.6–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800-1500):1;

[0023] The hydrocracking reaction is carried out at a temperature of 350–450 °C, a hydrogen partial pressure of 10–20 MPa, and a volume hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600–2000):1; preferably, the hydrocracking reaction temperature is 370–410°C, the hydrogen partial pressure is 12–18 MPa, and the volume hourly space velocity is 0.6–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800-1500):1;

[0024] The hydrogenation purification reaction is carried out at temperatures of 280–420 °C, hydrogen partial pressures of 10–20 MPa, and volume hourly space velocities of 0.5–5.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600–2000):1; preferably, the hydrogenation refining reaction temperature is 300–380°C, the hydrogen partial pressure is 12–18 MPa, and the volume hourly space velocity is 0.6–2.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800-1500):1.

[0025] Optionally, in step S2, the hydrogenation catalyst includes a first support, an active metal component, an optional first auxiliary agent, and an optional organic additive.

[0026] The first carrier is selected from one or more of alumina, silicon dioxide, titanium dioxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide, natural zeolite, and clay; preferably, it is selected from one or more of alumina and silicon dioxide-alumina; the active metal component includes a first active metal component and a second active metal component; the first active metal component is selected from one or more of nickel and cobalt; the second active metal component is selected from one or more of molybdenum and tungsten; the first auxiliary agent is selected from one or more of fluorine, boron, and phosphorus; the organic additive is selected from one or more of oxygen-containing organic compounds and nitrogen-containing organic compounds; preferably, the oxygen-containing organic compound is selected from one or more of organic alcohols and organic acids; preferably, the nitrogen-containing organic compound is selected from one or more of organic amines; more preferably, the oxygen-containing organic compound is selected from one or more of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, and malic acid; the nitrogen-containing organic compound is selected from one or more of ethylenediamine, EDTA, and their ammonium salts.

[0027] Preferably, based on the total weight of the hydrogenation catalyst, the content of the first active metal component (calculated as oxide) is 1-5% by weight, the content of the second active metal component (calculated as oxide) is 12-35% by weight, the content of the first auxiliary agent (calculated as element) is 0-9% by weight, and the molar ratio of the organic additive to all active metal components (calculated as oxide) is 0-2:1.

[0028] More preferably, the first carrier comprises γ-alumina; the active metal component comprises tungsten oxide and nickel oxide; the first additive comprises fluorine; and more preferably, based on the total weight of the hydrogenation catalyst, the nickel oxide content is 1-5% by weight, the tungsten oxide content is 12-35% by weight, the fluorine content is 1-9% by weight, and the balance is γ-alumina.

[0029] Optionally, in step S2, the hydrocracking catalyst includes a second support and one or more of group VIII metals and group VIB metals supported on the second support.

[0030] Preferably, the second support comprises a Y-type molecular sieve and an amorphous composite oxide; the amorphous composite oxide is selected from one or more of silicon oxide, aluminum oxide, titanium oxide, and zirconium oxide;

[0031] More preferably, based on the total weight of the hydrocracking catalyst, the content of the group VIII metals is 2-8% by weight, the content of the group VIB metals is 12-33% by weight, the content of the Y-type molecular sieve is 1-30% by weight, and the content of the amorphous composite oxide is 50-80% by weight, wherein the group VIII metals and group VIB metals are in oxide form.

[0032] Optionally, in step S2, the hydrorefining catalyst includes a third support and a third active metal component supported on the third support;

[0033] Optionally, the third carrier is selected from one or more of alumina and silicon oxide; the third active metal component is selected from one or more of nickel, molybdenum and magnesium.

[0034] Preferably, based on the total weight of the hydrorefining catalyst, the third active metal, in oxide form, contains 0.5–2.6 wt% magnesium oxide, 1.5–5.5 wt% molybdenum oxide, 20–28 wt% nickel oxide, and 64–78 wt% of the third support.

[0035] Optionally, the saturated hydrocarbon content in the hydrogenated oil obtained in step S2 is greater than 80% by weight; preferably greater than 85% by weight; and more preferably greater than 90% by weight.

[0036] Optionally, the sulfur content of the tail oil obtained in step S3 is less than 50 μg / g, and the nitrogen content is less than 10 μg / g; the distillation range of the light tail oil component is 350℃~500℃; the distillation range of the heavy tail oil component is above 500℃, and the color of the heavy tail oil is greater than 0 seppudé.

[0037] Preferably, the sulfur content of the tail oil is below 20 μg / g, and the nitrogen content is below 5 μg / g; the distillation range of the light tail oil component is between 380℃ and 490℃; the distillation range of the heavy tail oil component is above 490℃, and the color of the heavy tail oil fraction is greater than 6 seppudé.

[0038] More preferably, the sulfur content of the tail oil is less than 10 μg / g, and the nitrogen content is less than 2 μg / g; the distillation range of the light tail oil component is 390℃~470℃; the distillation range of the heavy tail oil component is above 470℃, and the color of the heavy tail oil fraction is greater than 8 Cépôt de Cépôt.

[0039] Optionally, in step S4, the first hydroisomerization catalyst and the first post-hydrogenation refining catalyst are sequentially arranged along the material flow direction in the first catalytic dewaxing reaction unit, so that after the light tail oil component enters the first catalytic dewaxing reaction unit, it first contacts the first hydroisomerization catalyst to carry out the first hydroisomerization catalytic reaction; then it contacts the first post-hydrogenation refining catalyst to carry out the first post-hydrogenation refining reaction, thereby obtaining the first hydrodewaxed oil;

[0040] In the second catalytic dewaxing reaction unit, the second hydroisomerization catalyst and the second post-hydrogenation refining catalyst are sequentially arranged along the material flow direction, so that after the heavy tail oil component enters the second catalytic dewaxing reaction unit, it first contacts the second hydroisomerization catalyst to carry out the second hydroisomerization catalytic reaction; then it contacts the second post-hydrogenation refining catalyst to carry out the second post-hydrogenation refining reaction, thereby obtaining the second hydrodewaxed oil.

[0041] Preferably, the content of the first hydrogenation purification catalyst is 50-200% by volume, based on the first hydroisomerization catalyst, and preferably 80-150% by volume.

[0042] Based on the second hydroisomerization catalyst, the content of the second hydrorefining catalyst is 50-200% by volume, preferably 80-150% by volume.

[0043] Optionally, in step S4, the reaction conditions in the first catalytic dewaxing reaction unit include:

[0044] The first hydroisomerization catalytic reaction is carried out at a temperature of 280–400 °C, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.4–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300–1200):1; preferably, the temperature of the first hydroisomerization catalytic reaction is 300–360°C, the pressure is 8–18 MPa, and the liquid hourly space velocity is 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400-1000):1;

[0045] The purification reaction after hydrogenation is carried out at a temperature of 150–300℃, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.4–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300–1200):1; preferably, the refining reaction temperature after hydrogenation is 180–280°C, the pressure is 8–18 MPa, and the liquid hourly space velocity is 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400-1000):1;

[0046] The reaction conditions in the second catalytic dewaxing reaction unit include:

[0047] The second hydroisomerization catalytic reaction is carried out at a temperature of 300–420 °C, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.3–1.8 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300–1200):1; preferably, the second hydroisomerization catalytic reaction temperature is 320–380°C, the pressure is 8–18 MPa, and the liquid hourly space velocity is 0.4–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400-1000):1;

[0048] The purification reaction after the second hydrogenation is carried out at a temperature of 150–300℃, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.3–1.8 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300–1200):1; preferably, the refining reaction temperature after hydrogenation is 180–260°C, the pressure is 8–18 MPa, and the liquid hourly space velocity is 0.4–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400-1000):1.

[0049] Optionally, in step S4, the first hydroisomerization catalyst and the second hydroisomerization catalyst each independently include a mesoporous molecular sieve, an inorganic oxide, and a fourth active metal component.

[0050] Optionally, the mesoporous molecular sieve is a type with a short axis of Major axis is The molecular sieve has a one-dimensional elliptical pore structure; preferably, the mesoporous molecular sieve is selected from one or more of ZSM-22, Nu-10, Theta-1, ISI-1, ZSM-23, SAPO-11, SAPO-31, and SAPO-41 molecular sieves; more preferably, the mesoporous molecular sieve is ZSM-22 molecular sieve.

[0051] Optionally, the fourth active metal component is selected from one or more of cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum, and tungsten; preferably platinum;

[0052] Optionally, the inorganic oxide is selected from one or more of alumina and silicon oxide;

[0053] More preferably, based on the total weight of the hydroisomerization catalyst, the content of the mesoporous molecular sieve is 30-70% by weight, the content of the inorganic oxide is 30-70% by weight, and the content of the fourth active metal component in reduced state is 0.2-1% by weight.

[0054] Optionally, the first and second hydrogenation refining catalysts each independently comprise a silica-alumina support and a fifth active metal component supported on the silica-alumina support.

[0055] Preferably, based on the weight of the silicon-aluminum support, the silicon-aluminum support comprises 16-20% by weight of silicon (calculated as oxide) and 78-82% by weight of aluminum (calculated as oxide); optionally, the ratio of pyridine infrared β-acid to L-acid measured at 200°C on the silicon-aluminum support is 0.06-0.085.

[0056] Optionally, the fifth active metal component is selected from one or more of platinum and palladium;

[0057] Preferably, when the fifth active metal component is platinum and palladium, the content of reduced palladium is 0.1-5% by weight, more preferably 0.2-2% by weight, based on the total weight of the fifth active metal component calculated as oxides; and the content of reduced platinum is 0.1-5% by weight, more preferably 0.2-2% by weight.

[0058] The second aspect of this disclosure provides a system for producing both lubricating oil base oil and industrial white oil. The system includes a solvent deasphalting unit, a hydrocracking unit, a first separation unit, a first catalytic dewaxing reaction unit, a second catalytic dewaxing reaction unit, and a separation unit.

[0059] The deasphalting unit is configured to perform solvent deasphalting and refining treatment on the residual oil to obtain deasphalted oil.

[0060] The hydrocracking unit includes a first hydrocracking catalyst, and the hydrocracking unit is configured to contact hydrogen, vacuum wax oil and deasphalted oil from the deasphalting unit with the first hydrocracking catalyst to carry out a first hydrocracking reaction to obtain hydrocracking product oil; wherein the first hydrocracking catalyst includes a hydrotreating catalyst, a hydrocracking catalyst and a hydrorefining catalyst.

[0061] The first separation unit is configured to perform a first separation process on the hydrocracking product oil from the hydrocracking unit to obtain naphtha, jet fuel, diesel, light tail oil components and heavy tail oil components;

[0062] The first catalytic dewaxing reaction unit includes a second catalyst. The first catalytic dewaxing reaction unit is configured to contact the light tail oil component with the second hydrogenation catalyst to carry out a second hydrogenation reaction and obtain a first hydrogenated dewaxing oil.

[0063] The second catalytic dewaxing reaction unit includes a third catalyst. The second catalytic dewaxing reaction unit is configured to contact the heavy tail oil component with the third hydrotreating catalyst to carry out a third hydrotreating reaction and obtain a second hydrotreated dewaxed oil. The second and third hydrotreating catalysts each independently include a hydroisomerization catalyst and a post-hydrotreating refining catalyst.

[0064] The second separation unit is configured to perform a second separation process on the first hydrodewaxed oil from the first catalytic dewaxing reaction unit and the second hydrodewaxed oil from the second catalytic dewaxing reaction unit to obtain lubricating oil base oil and industrial white oil.

[0065] Through the above technical solution, this disclosure provides a method and system for producing both lubricating oil base oil and industrial white oil. This disclosure introduces deasphalted oil obtained from deasphalting residual oil and vacuum wax oil into a hydrocracking unit for reaction, achieving the goal of producing lubricating oil base oil and industrial white oil while improving resource utilization. Furthermore, the hydrocracking unit is equipped with a hydrorefining catalyst to enhance its aromatic saturation function, increasing the aromatic content of the hydrocracking product oil, which is beneficial for subsequent catalytic dewaxing. In the first separation unit, the tail oil in the hydrocracking product oil is further separated into light and heavy tail oil components. These components are then introduced separately into the catalytic dewaxing reaction unit for reaction. Narrow-fraction feed improves reaction selectivity, facilitating the production of high viscosity index base oil and high viscosity industrial white oil, thereby improving oil quality.

[0066] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0067] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings:

[0068] Figure 1 This is an exemplary flowchart of a method and system for producing both lubricating oil base oil and industrial white oil, as provided in this disclosure. Detailed Implementation

[0069] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit this disclosure.

[0070] The first aspect of this disclosure provides a method for producing both lubricating oil base oil and industrial white oil, such as... Figure 1 As shown, it includes the following steps:

[0071] S1. The residual oil is fed into the solvent deasphalting unit for solvent deasphalting and refining treatment to obtain deasphalted oil;

[0072] S2. Hydrogen, vacuum wax oil and the deasphalted oil are introduced into the hydrocracking unit and contacted with the first hydrocracking catalyst to carry out the first hydrocracking reaction and obtain hydrocracking product oil. The first hydrocracking catalyst includes a hydrotreatment catalyst, a hydrocracking catalyst and a hydrorefining catalyst.

[0073] S3. The hydrotreated oil is fed into the first separation unit for the first separation process to obtain naphtha, jet fuel, diesel, light tail oil components and heavy tail oil components; wherein the distillation cut-off points of the light tail oil components and heavy tail oil components are any values ​​within the range of 450 to 500°C.

[0074] S4. The light tail oil component is introduced into the first catalytic dewaxing reaction unit and contacted with the second hydrogenation catalyst to carry out the second hydrogenation reaction, thereby obtaining the first hydrogenated dewaxed oil; the heavy tail oil component is introduced into the second catalytic dewaxing reaction unit and contacted with the third hydrogenation catalyst to carry out the third hydrogenation reaction, thereby obtaining the second hydrogenated dewaxed oil; the second hydrogenation catalyst and the third hydrogenation catalyst each independently include a hydrogenation isomerization catalyst and a post-hydrogenation refining catalyst;

[0075] S5. The first hydrodewaxed oil and the second hydrodewaxed oil are fed into the second separation unit for a second separation process to obtain lubricating oil base oil and industrial white oil.

[0076] This disclosure provides a method for producing both lubricating oil base oil and industrial white oil. The method involves introducing deasphalted oil obtained from deasphalting residual oil and vacuum wax oil into a hydrocracking unit for reaction. This achieves the goal of producing lubricating oil base oil and industrial white oil while improving resource utilization. Furthermore, the hydrocracking unit utilizes a hydrorefining catalyst to enhance its aromatic saturation function, increasing the aromatic content of the hydrocracking product and facilitating subsequent catalytic dewaxing. In a first separation unit, the tail oil from the hydrocracking product is further separated into light and heavy tail oil components. These components are then introduced separately into a catalytic dewaxing unit for individual reaction. Narrow-fraction feed improves reaction selectivity, facilitating the production of high viscosity index base oil and high viscosity industrial white oil, thereby improving oil quality.

[0077] In one specific embodiment, the residue oil is selected from one or more of vacuum residue oil and atmospheric residue oil; preferably, it is vacuum residue oil.

[0078] In this disclosure, the method and conditions for solvent deasphalting and refining can be conventional methods and conditions, and can include three steps: mixing, extraction and sedimentation separation. For example, it can be carried out in an extraction and sedimentation system consisting of an extraction tower and a sedimentation tower: first, the residual oil is mixed with the solvent and then sent to the extraction tower for full extraction, and then sedimentation separation is carried out in the sedimentation tower to complete the solvent deasphalting process.

[0079] In one embodiment, the conditions for the solvent deasphalting and refining treatment in step S1 include:

[0080] In the extraction tower, the volume ratio of solvent to residue oil is (2-10):1, the top temperature of the extraction tower is 20-150℃, and the pressure is 2-6MPa; preferably, the volume ratio of solvent to residue oil is (3-8):1, the top temperature of the extraction tower is 30-120℃, and the pressure is 3-5MPa.

[0081] In one embodiment, the solvent is selected from one or more of hydrocarbons with 3 to 7 carbon atoms, condensate oil, light naphtha, and gasoline; preferably, the solvent includes propane, or the solvent includes propane and one or more of ethane, propylene, butane, and pentane; more preferably, the content of propane in the solvent is 80 to 100% by weight, preferably 90 to 100% by weight, more preferably 95 to 100% by weight; more preferably 98 to 100% by weight.

[0082] In one specific embodiment, the solvent deasphalting and refining treatment results in the deasphalted oil having a residual carbon value of less than 10% by weight, preferably less than 6% by weight; a color value of no greater than 8; a content of n-heptane-insoluble matter of no greater than 200 ppm; and a drying point of the light deasphalted oil of no greater than 700°C. In this disclosure, color refers to the color value measured using GB / T 6540.

[0083] In one embodiment, the hydrotreatment catalyst, hydrocracking catalyst, and hydrorefining catalyst are sequentially arranged along the flow direction of the mixed feedstock in the hydrocracking unit; step S2 includes:

[0084] The vacuum wax oil and the deasphalted oil are mixed and then introduced into the hydrocracking unit. The mixed feedstock is first contacted with the hydrotreatment catalyst for a hydrotreatment reaction; then it is contacted with the hydrocracking catalyst for a hydrocracking reaction; and finally it is contacted with the hydrorefining catalyst for a hydrorefining reaction to obtain the hydrotreated oil.

[0085] In a preferred embodiment, the hydrocracking unit is further provided with a hydroprotective agent; along the material flow direction in the hydrocracking unit, the hydroprotective agent is positioned upstream of the hydrotreatment catalyst, so that the vacuum wax oil and the deasphalted oil mixture first come into contact with the hydroprotective agent in the hydrocracking unit for a hydroprotective reaction, and then sequentially come into contact with the hydrotreatment catalyst, the hydrocracking catalyst, and the hydrorefining catalyst for a reaction.

[0086] In one embodiment, the volume ratio of the hydrogenation protectant: hydrogenation treatment catalyst: hydrocracking catalyst: hydrorefining catalyst is (5-35):100:(70-250):(20-180).

[0087] In a preferred embodiment, the volume ratio of the hydrotreating protectant: hydrotreatment catalyst: hydrocracking catalyst: hydrorefining catalyst is (10-30):100:(80-220):(40-150). Using the above four catalysts according to this embodiment can achieve better hydrocracking results in the hydrocracking unit.

[0088] In one embodiment, the volume ratio of the depressurized wax oil to the deasphalted oil is (20-30):1, preferably (5-20):1;

[0089] Preferably, the residual carbon value of the mixture of the vacuum wax oil and the deasphalted oil is not greater than 2% by weight; more preferably, it is not greater than 1% by weight.

[0090] In this disclosure, the hydrocracking unit reaction in step S2 is primarily used to remove gum, sulfur, and nitrogen compounds from the feedstock, as well as the aromatic saturation and ring-opening reactions, so that they are converted into useful lubricating oil components. Therefore, provided that this objective is sufficient, the method and conditions can be conventional methods and conditions.

[0091] In a preferred embodiment, the saturated hydrocarbon content in the hydrogenated oil obtained in step S2 is greater than 80% by weight; preferably greater than 85% by weight; and more preferably greater than 90% by weight.

[0092] In one specific embodiment, the processing conditions of the hydrocracking unit in step S2 include:

[0093] The hydrogenation reaction was carried out at a temperature of 330–430 °C, a hydrogen partial pressure of 10–20 MPa, and a volume hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600-2000):1;

[0094] The hydrocracking reaction is carried out at a temperature of 350–450 °C, a hydrogen partial pressure of 10–20 MPa, and a volume hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600-2000):1;

[0095] The hydrogenation purification reaction is carried out at temperatures of 280–420 °C, hydrogen partial pressures of 10–20 MPa, and volume hourly space velocities of 0.5–5.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600-1000):1;

[0096] Optionally, the hydrogenation protection reaction is carried out at a temperature of 330–430 °C, a hydrogen partial pressure of 10–20 MPa, and a volume hourly space velocity of 1.5–30 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600-2000):1.

[0097] This disclosure adds a hydrorefining reaction after the hydrotreatment and hydrocracking reactions, which can further improve the degree of hydrosaturation and increase the viscosity and quality of the final lubricating oil base oil and industrial white oil. In this disclosure, the reaction temperature refers to the average reaction temperature in each catalytic reaction.

[0098] In a preferred embodiment, the hydrogenation reaction is carried out at a temperature of 350–390°C, a hydrogen partial pressure of 12–18 MPa, and a volume hourly space velocity of 0.6–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800-1500):1;

[0099] The hydrocracking reaction is carried out at 370–410 °C, with a hydrogen partial pressure of 12–18 MPa and a volume hourly space velocity of 0.6–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800-1500):1;

[0100] Preferably, the hydrogenation refining reaction is carried out at a temperature of 300–380°C, a hydrogen partial pressure of 12–18 MPa, and a volume hourly space velocity of 0.6–2.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800-1500):1;

[0101] Optionally, the hydrogenation protection reaction is carried out at a temperature of 350–390 °C, a hydrogen partial pressure of 12–18 MPa, and a volume hourly space velocity of 1.8–12 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800-1500):1. Performing the hydrotreating process in step S2 according to this embodiment can further improve the hydrotreating effect and obtain oil of better quality.

[0102] In one embodiment, the hydrotreating catalyst comprises a first support, an active metal component, an optional first auxiliary agent, and an optional organic additive.

[0103] The first carrier comprises a heat-resistant inorganic oxide carrier, and the first carrier is selected from one or more of alumina, silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide, natural zeolite, and clay; for example, the first carrier may be selected from one or more of alumina, silicon oxide, titanium oxide, magnesium oxide, silicon oxide-alumina, alumina-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium oxide, silicon oxide-thorium oxide, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium oxide, titanium oxide-zirconium oxide, silicon oxide-alumina-thorium oxide, silicon oxide-alumina-titanium oxide, silicon oxide-alumina-magnesium oxide, silicon oxide-alumina-zirconium oxide, natural zeolite, and clay; preferably, it is selected from one or more of alumina and silicon oxide-alumina (composite carrier);

[0104] The active metal component includes a first active metal component and a second active metal component; the first active metal component is selected from one or more of nickel and cobalt; the second active metal component is selected from one or more of molybdenum and tungsten.

[0105] The first auxiliary agent is selected from one or more of fluorine, boron and phosphorus;

[0106] The organic additive is selected from one or more of oxygen-containing organic compounds and nitrogen-containing organic compounds; preferably, the oxygen-containing organic compound is selected from one or more of organic alcohols and organic acids; preferably, the nitrogen-containing organic compound is selected from one or more of organic amines; more preferably, the oxygen-containing organic compound is selected from one or more of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, and malic acid; the nitrogen-containing organic compound is selected from one or more of ethylenediamine, EDTA (ethylenediaminetetraacetic acid), and their ammonium salts.

[0107] In a preferred embodiment, based on the total weight of the hydrotreating catalyst, the content of the first active metal, calculated as oxide, is 1-5% by weight; the content of the second active metal, calculated as oxide, is 12-35% by weight; and the content of the first auxiliary agent, calculated as element, is 0-9% by weight. Optionally, the molar ratio of the organic matter to all active metal components, calculated as oxide, is 0-2:1.

[0108] In one specific embodiment, the first carrier comprises γ-alumina, the active metal component comprises tungsten oxide and nickel oxide, and the first additive comprises fluorine; preferably, based on the total weight of the hydrogenation catalyst, the nickel oxide content is 1-5% by weight, the tungsten oxide content is 12-35% by weight, the fluorine content is 1-9% by weight, and the balance is γ-alumina.

[0109] The catalysts used in this disclosure may be selected from one or more of the prior art catalysts capable of achieving this function. They may be commercially available or prepared using any existing method.

[0110] In one embodiment, in step S2, the hydrocracking catalyst includes a second support and one or more of group VIII metals and group VIB metals supported on the second support.

[0111] Preferably, the second carrier comprises a Y-type molecular sieve and an amorphous composite oxide; more preferably, the amorphous composite oxide is selected from one or more of silicon oxide, aluminum oxide, titanium oxide and zirconium oxide.

[0112] In a preferred embodiment, based on the total weight of the hydrocracking catalyst, the content of Group VIII metals is 2-8% by weight, the content of Group VIB metals is 12-33% by weight, the content of Y-type molecular sieve is 1-30% by weight, and the content of amorphous composite oxides is 50-80% by weight, wherein the Group VIII metals and Group VIB metals are in oxide form.

[0113] The hydrocracking catalyst II used in this disclosure can be selected from one or more of the prior art catalysts capable of performing this function. They can be commercially available or prepared using any existing method.

[0114] In one specific embodiment, the most probable pore size of the second support in the hydrocracking catalyst described in step S2 is 3–20 nm, and the pore size concentration of the second support is 15–42. The most probable pore size is determined using the BET method. The pore size concentration refers to the ratio of the peak height to the full width at half maximum (FWHM) of the peak in the dV / dr distribution curve as a function of pore size, determined by the BET method. dV / dr represents the derivative of the specific pore volume with respect to the pore size. Preferably, the most probable pore size of the second support is 5–15 nm, and the pore size concentration of the support is 18–40.

[0115] In one specific embodiment, the Y-type molecular sieve in the hydrocracking catalyst is obtained through modification treatment. The modification treatment may specifically include rare earth exchange treatment, dealumination treatment, etc. The dealumination treatment includes thermal or hydrothermal dealumination, chemical dealumination, or a combination of both. The conditions for hydrothermal dealumination include calcining the NHY molecular sieve in the presence of steam, thereby extracting framework aluminum into non-framework aluminum, increasing the framework silicon-to-aluminum ratio, and decreasing the cell constant and ion exchange capacity. Changing the treatment temperature, time, and steam partial pressure can adjust the degree of dealumination and the size of the cell constant. The chemical dealumination methods include: EDTA complexation dealumination, SiCl gas-phase isomorphic substitution dealumination, (NH)SiF liquid-phase isomorphic substitution dealumination, and oxalic acid liquid-phase complexation dealumination. One method combines hydrothermal and chemical dealuminization. Specific conditions include: first, hydrothermal dealuminization, followed by chemical treatment to remove non-framework aluminum; acid, alkali solutions, salts (such as KF), complexing agents (such as EDTA) can be used. While using weak acid for dealuminization, the remaining Na in the molecular sieve system is also removed.

[0116] In one specific embodiment, the second support for the hydrocracking catalyst is prepared by the following method: mixing an amorphous composite oxide precursor, a Y-type molecular sieve, a peptide, and water to obtain a raw material mixture; feeding the raw material mixture into an extruder, and extruding it after kneading to obtain a molded body; calcining the molded body to obtain the second support, wherein the temperature of the molded body at the outlet of the extruder is 40–150°C. The amount of raw materials added during the preparation of the second support can be adjusted according to the target composition of the second support; the preparation process conditions can also adopt conventional process conditions in the art.

[0117] In a preferred embodiment, in step S2, the hydrorefining catalyst includes a third support and a third active metal component supported on the third support; the third support is selected from one or more of alumina and silica; the third active metal component is selected from one or more of nickel, molybdenum, and magnesium. In this disclosure, the introduction of three active metal components—nickel, molybdenum, and magnesium—into the hydrorefining catalyst, especially the introduction of magnesium, is beneficial in preventing cracking reactions under the high-temperature conditions of post-refining treatment, thereby improving the quality of the tail oil.

[0118] In a preferred embodiment, based on the total weight of the hydrorefining catalyst, the third active metal, in oxide form, comprises 0.5–2.6 wt% magnesium oxide, 1.5–5.5 wt% molybdenum oxide, 20–28 wt% nickel oxide, and 64–78 wt% third support.

[0119] In this disclosure, the hydrorefining catalyst is referred to as III. The hydrorefining catalyst III can be selected from one or more catalysts in the prior art that can achieve this function. They can be commercially available products or prepared using any existing method.

[0120] In this disclosure, the method and conditions for step S3, which involves entering the first separation unit for the first separation process, are conventional methods and conditions. For example, separation is performed using distillation, a method known in the art, which typically includes one or more flash distillation, atmospheric distillation, and vacuum distillation units to achieve the desired separation. The apparatus used for the first separation process also has a conventional structure in the art.

[0121] In one specific embodiment, the sulfur content of the tail oil obtained in step S3 is less than 50 μg / g, and the nitrogen content is less than 10 μg / g; the distillation range of the light tail oil component is 350℃~500℃; the distillation range of the heavy tail oil component is above 500℃, and the color of the heavy tail oil is greater than 0 seppudé.

[0122] In a preferred embodiment, the sulfur content of the separated tail oil is less than 20 μg / g, and the nitrogen content is less than 5 μg / g; the distillation range of the light tail oil component is 380℃ to 490℃; the distillation range of the heavy tail oil component is above 490℃, and the color of the heavy tail oil fraction is greater than 6 seppudé.

[0123] In a more preferred embodiment, the sulfur content of the separated tail oil is less than 10 μg / g, and the nitrogen content is less than 2 μg / g; the distillation range of the light tail oil component is 390℃ to 470℃; the distillation range of the heavy tail oil component is above 470℃, and the color of the heavy tail oil fraction is greater than 8 Cépôt color. In this disclosure, the color of the tail oil is determined by the GB / 3555 Cépôt color method.

[0124] In this disclosure, the first and second catalytic dewaxing reaction units in step S4 are for the purpose of hydrogenation conversion of large linear hydrocarbon molecules. The catalysts used are selected from one or more of the catalytic dewaxing catalysts and isomerization dewaxing catalysts well-known in the art. More specifically, the first and second catalytic dewaxing reaction units in this disclosure can be the same reaction apparatus or different reaction apparatuses. When the same reaction apparatus is used, the light and heavy tail oil components can be introduced stepwise, for example, the light tail oil component can be introduced first, and after the reaction is completed, the heavy tail oil component can be introduced for further reaction.

[0125] In one specific embodiment, in step S4, a first hydroisomerization catalyst and a first post-hydrogenation refining catalyst are sequentially arranged along the material flow direction in the first catalytic dewaxing reaction unit, so that after the light tail oil component enters the first catalytic dewaxing reaction unit, it first contacts the first hydroisomerization catalyst to carry out the first hydroisomerization catalytic reaction; then it contacts the first post-hydrogenation refining catalyst to carry out the first post-hydrogenation refining reaction, thereby obtaining the first hydrodewaxed oil;

[0126] In the second catalytic dewaxing reaction unit, the second hydroisomerization catalyst and the second post-hydrogenation refining catalyst are sequentially arranged along the material flow direction, so that after the heavy tail oil component enters the second catalytic dewaxing reaction unit, it first contacts the second hydroisomerization catalyst to carry out the second hydroisomerization catalytic reaction; then it contacts the second post-hydrogenation refining catalyst to carry out the second post-hydrogenation refining reaction, thereby obtaining the second hydrodewaxed oil.

[0127] In a preferred embodiment, the content of the first hydrogenation purification catalyst is 50-200% by volume, preferably 80-150% by volume, based on the first hydroisomerization catalyst.

[0128] Based on the second hydroisomerization catalyst, the content of the second hydrorefining catalyst is 50-200% by volume, preferably 80-150% by volume.

[0129] In one embodiment, in step S4, the reaction conditions in the first catalytic dewaxing reaction unit include: a first hydroisomerization catalytic reaction temperature of 280–400°C, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.4–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300–1200):1; the refining reaction temperature after the first hydrogenation is 150–300℃, the pressure is 3–20 MPa, and the liquid hourly space velocity is 0.4–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300-1200):1;

[0130] The reaction conditions in the second catalytic dewaxing reaction unit include: a second hydroisomerization catalytic reaction temperature of 300–420 °C, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.3–1.8 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300–1200):1; the second hydrogenation refining reaction temperature is 150–300℃, the pressure is 30–20 MPa, and the liquid hourly space velocity is 0.3–1.8 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300-1200):1.

[0131] In a preferred embodiment, in step S4, the reaction conditions in the first catalytic dewaxing reaction unit include: a first hydroisomerization catalytic reaction temperature of 300–360°C, a pressure of 8–18 MPa, and a liquid hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400–1000):1; the refining reaction temperature after the first hydrogenation is 180–280℃, the pressure is 8–18 MPa, and the liquid hourly space velocity is 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400-1000):1;

[0132] The reaction conditions in the second catalytic dewaxing reaction unit include: a second hydroisomerization catalytic reaction temperature of 320–380 °C, a pressure of 8–18 MPa, and a liquid hourly space velocity of 0.4–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400–1000):1; the refining reaction temperature after the second hydrogenation is 180–260℃, the pressure is 8–18 MPa, and the liquid hourly space velocity is 0.4–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400-1000):1. Processing under the conditions of this embodiment can further improve oil quality.

[0133] In one specific embodiment, the first hydroisomerization catalyst and the second hydroisomerization catalyst each independently comprise a mesoporous molecular sieve, an inorganic oxide, and a fourth active metal component.

[0134] Optionally, the mesoporous molecular sieve is a type with a short axis of Major axis is The molecular sieve has a one-dimensional elliptical pore structure; preferably, the mesoporous molecular sieve is selected from one or more of ZSM-22, Nu-10, Theta-1, ISI-1, ZSM-23, SAPO-11, SAPO-31, and SAPO-41 molecular sieves; more preferably, the mesoporous molecular sieve is ZSM-22 molecular sieve.

[0135] Optionally, the fourth active metal component is selected from one or more of cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum, and tungsten; preferably platinum;

[0136] Optionally, the inorganic oxide is selected from one or more of alumina and silicon oxide;

[0137] More preferably, based on the total weight of the hydroisomerization catalyst, the content of the mesoporous molecular sieve is 30-70% by weight, the content of the inorganic oxide is 30-70% by weight, and the content of the fourth active metal component in reduced state is 0.2-1% by weight.

[0138] The hydroisomerization catalysts described in this disclosure can be selected from one or more of the prior art catalysts capable of performing this function. They can be commercially available or prepared using any existing method.

[0139] In step S4 of this disclosure, the first and second post-hydrogenation refining catalysts are used for the purpose of saturating aromatic hydrocarbons with hydrogen. The catalysts used are selected from one or more of the hydrorefining catalysts well known in the art.

[0140] In one embodiment, the first and second hydrogenation refining catalysts each independently comprise a silicon-aluminum support and a fifth active metal component supported on the silicon-aluminum support.

[0141] Preferably, based on the weight of the silicon-aluminum support, the silicon-aluminum support comprises 16-20% by weight of silicon (calculated as oxide) and 78-82% by weight of aluminum (calculated as oxide); optionally, the ratio of pyridine infrared β-acid to L-acid measured at 200°C on the silicon-aluminum support is 0.06-0.085.

[0142] Optionally, the fifth active metal component is selected from one or more of platinum and palladium;

[0143] Preferably, when the fifth active metal component is platinum and palladium, the content of reduced palladium is 0.1-5% by weight, more preferably 0.2-2% by weight, based on the total weight of the fifth active metal component calculated as oxides; and the content of reduced platinum is 0.1-5% by weight, more preferably 0.2-2% by weight.

[0144] In one embodiment, in step S5, the method and conditions for the first hydrodewaxed oil and the second hydrotreated wax oil to enter the second separation unit for the second separation process are conventional methods and conditions. For example, a distillation method is used for separation, which is well known in the art and typically includes one or more flash distillation, atmospheric distillation, and vacuum distillation operation units to achieve the desired separation. The apparatus used for the separation process also has a conventional structure in the art.

[0145] The second aspect of this disclosure provides a system for producing lubricating oil base oil and industrial white oil, the system comprising a solvent deasphalting unit, a hydrocracking unit, a first separation unit, a first catalytic dewaxing reaction unit, a second catalytic dewaxing reaction unit, and a separation unit;

[0146] The deasphalting unit is configured to perform solvent deasphalting and refining treatment on the residual oil to obtain deasphalted oil.

[0147] The hydrocracking unit includes a first hydrocracking catalyst, and the hydrocracking unit is configured to contact hydrogen, vacuum wax oil and deasphalted oil from the deasphalting unit with the first hydrocracking catalyst to carry out a first hydrocracking reaction to obtain hydrocracking product oil; wherein the first hydrocracking catalyst includes a hydrotreating catalyst, a hydrocracking catalyst and a hydrorefining catalyst.

[0148] The first separation unit is configured to perform a first separation process on the hydrocracking product oil from the hydrocracking unit to obtain naphtha, jet fuel, diesel, light tail oil components and heavy tail oil components;

[0149] The first catalytic dewaxing reaction unit includes a second catalyst. The first catalytic dewaxing reaction unit is configured to contact the light tail oil component with the second hydrogenation catalyst to carry out a second hydrogenation reaction and obtain a first hydrogenated dewaxing oil.

[0150] The second catalytic dewaxing reaction unit includes a third catalyst. The second catalytic dewaxing reaction unit is configured to contact the heavy tail oil component with the third hydrotreating catalyst to carry out a third hydrotreating reaction and obtain a second hydrotreated dewaxed oil. The second and third hydrotreating catalysts each independently include a hydroisomerization catalyst and a post-hydrotreating refining catalyst.

[0151] The second separation unit is configured to perform a second separation process on the first hydrodewaxed oil from the first catalytic dewaxing reaction unit and the second hydrodewaxed oil from the second catalytic dewaxing reaction unit to obtain lubricating oil base oil and industrial white oil.

[0152] In a preferred embodiment, the hydrotreating catalyst, hydrocracking catalyst, and hydrorefining catalyst are sequentially arranged along the flow direction of the mixed feedstock in the hydrocracking unit. Preferably, a hydroprotective agent is also arranged upstream of the hydrotreating catalyst along the flow direction of the mixed feedstock in the hydrocracking unit. The volume ratio of the hydroprotective agent: hydrotreating catalyst: hydrocracking catalyst: hydrorefining catalyst is (5-35):100:(70-250):(20-180); preferably (10-30):100:(80-220):(40-150).

[0153] In a preferred embodiment, in the first catalytic dewaxing reaction unit, the first hydroisomerization catalyst and the first post-hydrogenation refining catalyst are sequentially arranged along the material flow direction; preferably, the content of the first post-hydrogenation refining catalyst, based on the first hydroisomerization catalyst, is 50-200% by volume, preferably 80-150% by volume; in the second catalytic dewaxing reaction unit, in the second catalytic dewaxing reaction unit, the second hydroisomerization catalyst and the second post-hydrogenation refining catalyst are sequentially arranged along the material flow direction; preferably, the content of the second post-hydrogenation refining catalyst, based on the second hydroisomerization catalyst, is 50-200% by volume, preferably 80-150% by volume.

[0154] In this disclosure, the apparatus used in the systems for producing lubricating base oils and industrial white oils are all conventionally selected structures in the art.

[0155] Process conditions not specifically listed in the embodiments or comparative examples of this application can be selected from conventional process conditions in the art.

[0156] The present disclosure is further described in detail below through examples.

[0157] In the following examples and comparative examples, the catalysts used were sourced from the following sources:

[0158] The commercial brand name of the hydrorefining catalyst I is RN-410, which was purchased from Changling Catalyst Factory. Based on the total weight of the catalyst, its composition includes: molybdenum oxide not less than 26.5% by weight, nickel oxide not less than 4.2% by weight, and the remainder being aluminum oxide.

[0159] The commercial brand name of the hydrocracking catalyst II is RHC-131. It was purchased from Changling Catalyst Factory. Based on the total weight of the catalyst, its composition includes: tungsten oxide not less than 24.5% by weight, nickel oxide not less than 6.5% by weight, and the remainder is mesoporous silica-alumina and molecular sieves, with Y-type molecular sieves accounting for 5-10% by weight.

[0160] The commercial brand name of the hydrogenation protectant IV is RG-1. It was purchased from Changling Catalyst Factory. Based on the total weight of the catalyst, its composition includes: molybdenum oxide not less than 5.5% by weight, nickel oxide not less than 1.0% by weight, and the remainder being aluminum oxide.

[0161] Both the first and second hydroisomerization catalysts are catalyst V, with the commercial brand name RIW-2, purchased from Changling Catalyst Factory. Based on the total weight of the catalyst, their composition includes: platinum not less than 0.3% by weight, the remainder being molecular sieves and alumina, with the molecular sieve content being 40% by weight based on the total weight of the catalyst.

[0162] Both the first and second post-hydrogenation refining catalysts are catalyst VI, with the commercial brand name RLF-20, purchased from Changling Catalyst Factory. Based on the total weight of the catalyst, its composition includes: platinum not less than 0.1 wt%, palladium not less than 0.2 wt%, and the remainder being amorphous silicon and aluminum.

[0163] The hydrorefining catalyst III in the comparative example is commercially available as RN-410, purchased from Changling Catalyst Factory. Based on the total weight of the catalyst, its composition includes: molybdenum oxide not less than 26.5% by weight, nickel oxide not less than 4.2% by weight, and the remainder being aluminum oxide.

[0164] In this disclosure, the elemental content of the catalyst was determined using X-ray fluorescence method.

[0165] Preparation Example 1

[0166] The hydrorefining catalyst III used in the examples was prepared by the following method:

[0167] Weigh 1600g of aluminum hydroxide powder (product of Changling Catalyst Factory) and 400g of boehmite (product of Shandong Aluminum Factory) and extrude them on an extruder into clover-shaped strips with an outer circle diameter of 1.5 mm. Dry the wet strips at 120℃ for 4 hours and calcine them at 600℃ for 3 hours under air circulation to obtain the carrier.

[0168] Weigh 100g of the above-mentioned carrier, soak it in 100ml of an aqueous solution containing 19.9g of magnesium nitrate for 2h, dry it at 120℃ for 5h, and then calcine it at 400℃ for 4h under air circulation to obtain a magnesium-containing carrier.

[0169] Weigh 224.6g of basic nickel carbonate, 170.0g of ammonium carbonate, and 17.0g of molybdenum trioxide, place them in a beaker, add 280g of concentrated ammonia, stir and dissolve, and dilute with deionized water to 538.8ml to obtain a co-impregnation solution containing nickel and molybdenum.

[0170] The magnesium-containing support was impregnated with the above co-impregnation solution for 1.5 h at a liquid-to-solid volume ratio of 3:1. After filtration, the wet strip was dried at 110 °C for 5 h and calcined at 220 °C for 3 h. 90 mL of the co-impregnation solution was added to the filtrate, followed by a second impregnation. After 2 h, the solution was filtered, dried at 100 °C for 8 h, and calcined at 240 °C for 6 h to obtain hydrorefining catalyst III. Its weight composition was: magnesium oxide 2.0 wt%, molybdenum oxide 3.1 wt%, nickel oxide 26.6 wt%, and the balance being γ-Al₂O₃.

[0171] Preparation Example 2

[0172] Hydrogen refining catalyst was prepared according to Preparation Example 1. The difference between this comparative example and Preparation Example 1 is that magnesium is not introduced, and the support is directly immersed in a co-impregnation solution containing nickel and molybdenum for impregnation; thus, hydrogen refining catalyst D-III was prepared.

[0173] Its weight composition is: 3.1% molybdenum oxide, 26.6% nickel oxide, and the balance is γ-Al2O3.

[0174] Example 1

[0175] according to Figure 1 The process shown takes into account both the production of lubricating oil base oil and industrial white oil. The residue oil is a type of vacuum distillation bottom oil, and its properties are listed in Table 1. The properties of the vacuum wax oil are listed in Table 3.

[0176] (1) In the solvent deasphalting unit:

[0177] The residue from the extraction tower with a distillation range >520℃ and C3 alkane (propane) were introduced from the top and bottom of the extraction tower, respectively, and subjected to countercurrent contact within the tower for solvent deasphalting and refining of the residue. Operating conditions included: top temperature of the extraction tower 40℃, pressure 4.0 MPa, and solvent ratio 6.0 (v / v). The yield and properties of the deasphalted oil obtained after extraction are listed in Table 2.

[0178] (2) In the hydrocracking unit:

[0179] The catalyst is a graded combination of catalyst IV (hydrogenation protectant), I (hydrogenation treatment catalyst), II (hydrocracking catalyst), and III (hydrorefining catalyst). The hydrocracking reaction unit can be selected from three reactors in series, two reactors in series, or a single reactor. In this embodiment, it is a two reactors in series.

[0180] The catalyst ratio is IV:I:II:III = 25:100:120:80 (volume ratio).

[0181] The properties of the hydrocracking feedstock, reaction conditions, and product yields (based on the hydrocracking feedstock oil) of the hydrocracking unit are listed in Tables 3 and 4. In Table 4, the distillation range of the light tail oil component obtained by separation is 390℃ to 470℃, and the distillation range of the heavy tail oil component is above 470℃.

[0182] (3) In the first catalytic dewaxing reaction unit and the second catalytic dewaxing reaction unit:

[0183] The first catalytic dewaxing reaction unit and the second catalytic dewaxing reaction unit use the same reaction device, including: the isomer catalyst V and the post-refining catalyst VI adopt a two-reaction-one-stage series mode, wherein the catalyst V (hydroisomerization catalyst): VI (hydrorefining catalyst) = 1:0.8 (volume ratio). The light tail oil component is introduced first for reaction and after the reaction is completed, the heavy tail oil component is introduced for reaction.

[0184] The reaction conditions and product properties of the light and heavy tail oil components are listed in Tables 5 to 7.

[0185] According to the analysis data, the method provided in this disclosure can produce lubricating oil base oil with a viscosity index greater than 120 (HVI III) and a pour point less than -24°C, which can also be used as No. 32 Group II industrial white oil product; at the same time, it can produce No. 100 Group II industrial white oil product with a viscosity index of 127, which can be used as HVI III 12cst base oil product.

[0186] Table 1 Properties of vacuum residue

[0187]

[0188]

[0189] Table 2 Properties of Deasphalted Oil

[0190] Brand Deasphalted oil Yield / weight % 28.00 <![CDATA[Density (20 °C) / g·cm -3 > 0.9456 <![CDATA[Kinematic viscosity / mm 2 ·s -1 > 100℃ 36.28 Color / Number 8.00 Pour point / °C 54.00 Residual char / % by weight 5.20 Sulfur content / weight % 2.80 Nitrogen content / weight % 0.14 <![CDATA[Acid value / mgKOH·g -1 > 0.40 Yield / weight % 28.00

[0191] Table 3 Properties of Hydrocracking Feed

[0192] Brand Stress-relieving wax oil Deasphalted oil Mixed feed Mixing ratio / weight% 82.00 18.00 100.00 <![CDATA[Density (20 °C) / g·cm -3 > 0.9225 0.9476 0.9268 <![CDATA[Kinematic viscosity / mm 2 ·s -1 > 100℃ 9.45 36.28 14.25 Color / Number 4.00 8.00 6.20 Pour point / °C 34.00 54.00 36.00 Residual char / % by weight 0.02 5.20 0.96 Sulfur content / weight % 1.80 2.80 1.98 Nitrogen content / weight % 0.12 0.14 0124 <![CDATA[Acid value / mgKOH·g -1 > 0.10 0.40 0.18

[0193] Table 4 Results of hydrocracking unit reaction

[0194]

[0195]

[0196] Table 5. Isomerization and dewaxing reaction of hydrotreated tail oil (light tail oil component) at 390℃~470℃

[0197] Reaction conditions Hydrogen partial pressure / MPa 15.0 <![CDATA[Hydroisomerization / Post-refining space velocity per hour -1 > 1.0 / 0.8 Average reaction temperature at ℃ for hydroisomerization / post-purification 320 / 210 Hydrogen-to-oil volume ratio 500 reaction results Naphtha yield / weight % 8.34 Diesel yield / weight % 12.23 2cst base oil yield / weight % 2.30 3cst base oil yield / weight % 5.46 6cst base oil yield / weight % 70.52

[0198] Table 6. Isomerization and Dewaxing Reaction of Hydrogenated Tail Oil (Heavy Tail Oil Component) at >470℃

[0199]

[0200]

[0201] Table 7 Properties of Base Oil Products

[0202] project 6CST base oil 1 6cst base oil 2 12cst base oil 2 <![CDATA[Viscosity at 40℃ / (mm 2 / s)]]> 29.74 29.52 95.38 <![CDATA[Viscosity at 100℃ / (mm 2 / s)]]> 5.626 5.500 12.64 Viscosity Index 131 125 128 Pour point / ℃ -18 -24 -18 Flash point / °C >220 >220 >220 Aromatic content / weight % <0.1 <0.1 <0.5 Color / Seybert +30 +30 +30

[0203] In this disclosure, "6cst base oil 1" refers to 6cst base oil generated by the reaction of light tail oil components; "6cst base oil 2" and "12cst base oil 2" refer to 6cst base oil and 12cst base oil generated by the reaction of heavy tail oil components, respectively.

[0204] Comparative Example 1

[0205] Referring to the process flow of Example 1, the difference between this comparative example and Example 1 is that: no hydrorefining catalyst is added to the hydrocracking unit; the commercial brand name of hydroprotectant IV is RG-1; the commercial brand name of hydrorefining catalyst I is RN-410; and the commercial brand name of hydrocracking catalyst II is RHC-131. The ratio of catalyst IV:I:II is 25:100:120 (volume ratio). The remaining reaction units and reaction processes are the same as in Example 1.

[0206] The properties of the feedstock are the same as in Table 3. The operations of the hydrocracking reaction unit and the catalytic dewaxing unit are listed in Tables 8-10, and the properties of the products are listed in Table 11. In this comparative example, the heavy tail oil components are darker in color because there is no hydrorefining catalyst in the hydrocracking section.

[0207] Table 8 Results of Hydrocracking Unit Reactions

[0208] Reaction conditions Hydrogen partial pressure / MPa 15.0 <![CDATA[Hydrotreating / Cracking Volumetric Space Velocity / h -1 > 0.7 / 0.58 Average reaction temperature of hydrotreating / cracking / °C 377 / 382 Hydrogen-to-oil volume ratio 1000 reaction results Naphtha yield / weight / % 23.2 Jet fuel yield / weight % 16.7 Diesel yield / weight % 31.2 Residual oil yield / weight % 29.8 Aromatic content (by weight) of hydrogenated oil 8.0 Hydrogenation produced oil saturated hydrocarbon content / wt% 92 Properties of hydrotreated tail oil at 390℃~470℃ <![CDATA[Density (20 °C) / g·cm -3 > 0.856 <![CDATA[100℃ kinematic viscosity / mm 2 ·s -1 > 6.12 Sulfur content / μg / g 11 Nitrogen content / μg / g 1.0 Saipo Special 0 Hydrogenated tail oil properties at >470℃ <![CDATA[Density (20 °C) / g·cm -3 > 0.874 <![CDATA[100℃ kinematic viscosity / mm 2 ·s -1 > 10.44 Sulfur content / μg / g 18 Nitrogen content / μg / g 2 Saipo Special <-16

[0209] Table 9. Isomerization and dewaxing reaction conditions of hydrotreated tail oil at 390℃~470℃

[0210]

[0211]

[0212] Table 10 >470℃ Hydrogenated Tail Oil Isomerization Dewaxing Reaction Conditions

[0213] Reaction conditions Hydrogen partial pressure / MPa 15.0 <![CDATA[Hydroisomerization / Post-refining space velocity per hour -1 > 0.8 / 0.67 Average reaction temperature at ℃ for hydroisomerization / post-purification 335 / 220 Hydrogen-to-oil volume ratio 600 reaction results Naphtha yield / weight % 8.04 Diesel yield / weight % 12.73 2cst base oil yield / weight % 2.55 4cst base oil yield / weight % 3.24 6cst base oil yield / weight % 5.76 12cst base oil yield / weight % 66.25

[0214] Table 11 Properties of Base Oil Products

[0215] project 6CST base oil 1 6cst base oil 2 12cst base oil 2 <![CDATA[Viscosity at 40°C / (mm 2 / s)]]> 30.22 30.64 98.68 <![CDATA[Viscosity at 100℃ / (mm 2 / s)]]> 5.66 5.58 12.84 Viscosity Index 129 122 126 Pour point / ℃ -18 -24 -18 Flash point / °C >220 >220 >220 Aromatic content / weight % <0.8 <1.0 <1.5 Color / Seybert +30 +22 +6

[0216] Comparing Comparative Example 1 with Example 1, it can be seen that Example 1, which uses the method provided in this disclosure, employs a hydrorefining catalyst in the hydrocracking unit. The hydrocracking product obtained from the hydrocracking unit of Example 1 has a lower aromatic content and a higher saturated hydrocarbon content, resulting in a better quality base oil product (e.g., the oil obtained from Example 1 has a higher viscosity index, lower aromatic content, and a higher Seybert number).

[0217] Comparative Example 2

[0218] Referring to the process of Example 1, the difference between this comparative example and Example 1 is that: no residual oil is introduced, and no solvent deasphalting refining treatment is performed; only vacuum wax oil is introduced as a raw material into the hydrocracking unit; the rest of the process and conditions are the same as in Example 1.

[0219] The properties of the raw materials are the same as in Table 3. The operations of the hydrocracking reaction unit and the catalytic dewaxing unit are listed in Tables 12 to 14. The properties of the products are listed in Table 15.

[0220] Table 12 Results of Hydrocracking Unit Reactions

[0221]

[0222]

[0223] Table 13 Isomerization and Dewaxing Reactions of Hydrogenated Tail Oil (Light Tail Oil Components) at 390℃~470℃

[0224] Reaction conditions Hydrogen partial pressure / MPa 15.0 <![CDATA[Hydroisomerization / Post-refining space velocity / h -1 > 1.0 / 0.8 Average reaction temperature at ℃ for hydroisomerization / post-purification 320 / 210 Hydrogen-to-oil volume ratio 500 reaction results Naphtha yield / weight % 7.39 Diesel yield / weight % 13.55 2cst base oil yield / weight % 2.73 3cst base oil yield / weight % 5.86 6cst base oil yield / weight % 67.14

[0225] Table 14 Isomerization and Dewaxing Reactions of Hydrogenated Tail Oil (Heavy Tail Oil Component) at >470℃

[0226] Reaction conditions Hydrogen partial pressure / MPa 15.0 <![CDATA[Hydroisomerization / Post-refining space velocity per hour -1 > 0.8 / 0.67 Average reaction temperature at ℃ for hydroisomerization / post-purification 335 / 220 Hydrogen-to-oil volume ratio 600 reaction results Naphtha yield / weight % 7.14 Diesel yield / weight % 10.73 2cst base oil yield / weight % 3.58 4cst base oil yield / weight % 7.25 8cst base oil yield / weight % 68.76 12cst base oil yield / weight % /

[0227] Table 15 Properties of Base Oil Products

[0228]

[0229]

[0230] Comparing Comparative Example 2 with Example 1, it can be seen that Example 1, which adopts the method provided in this disclosure, introduces residual oil into the process and performs solvent deasphalting and refining treatment. Example 1 can simultaneously produce high viscosity index base oil and high viscosity industrial white oil, thereby improving the quality of oil products.

[0231] Example 2

[0232] The process is the same as in Example 1. The difference between this example and Example 1 is that the hydrorefining catalyst III is replaced with a commercially available hydrorefining catalyst, RN-410.

[0233] The commercial brand names of hydrotreating protectant IV are RG-1, hydrorefining catalyst I are RN-410, hydrocracking catalyst II are RHC-131, and hydrorefining catalyst III are RN-410, with a volume ratio of IV:I:II:III = 25:100:120:80. The first and second catalytic dewaxing reaction units utilize the same reaction apparatus, including: hydrotreating catalytic dewaxing catalyst V (commercial brand name RIW-2) and post-hydrotreating refining catalyst (commercial brand name RLF-20), with a catalyst volume ratio of V:VI = 1:0.8.

[0234] The properties of the feedstock are the same as in Table 3. The operations of the hydrocracking reaction unit and the catalytic dewaxing unit are listed in Tables 16-18, and the properties of the products are listed in Table 19. In this example, RN-410 was used as the hydrorefining catalyst, and the resulting heavy tail oil component had a darker color.

[0235] Table 16 Results of Hydrocracking Unit Reactions

[0236]

[0237]

[0238] Table 17 Isomerization and Dewaxing Reactions of Hydrogenated Tail Oil at 390℃~470℃

[0239] Reaction conditions Hydrogen partial pressure / MPa 15.0 <![CDATA[Hydroisomerization / Post-refining space velocity per hour -1 > 1.0 / 0.8 Average reaction temperature at ℃ for hydroisomerization / post-purification 320 / 210 Hydrogen-to-oil volume ratio 500 reaction results Naphtha yield / weight % 8.66 Diesel yield / weight % 12.11 2cst base oil yield / weight % 2.43 3cst base oil yield / weight % 5.62 6cst base oil yield / weight % 70.44

[0240] Table 18 >470℃ Hydrogenated Tail Oil Isomerization Dewaxing Reaction Conditions

[0241] Reaction conditions Hydrogen partial pressure / MPa 15.0 <![CDATA[Hydroisomerization / Post-refining Space Velocity per Hour -1 > 0.8 / 0.67 Average reaction temperature at ℃ for hydroisomerization / post-purification 335 / 220 Hydrogen-to-oil volume ratio 500 reaction results Naphtha yield / weight % 8.24 Diesel yield / weight % 12.88 2cst base oil yield / weight % 2.65 4cst base oil yield / weight % 3.18 6cst base oil yield / weight % 4.39 12cst base oil yield / weight % 66.55

[0242] Table 19 Properties of Base Oil Products

[0243] project 6cst base oil 1 6cst base oil 2 12cst base oil 2 <![CDATA[Viscosity at 40°C / (mm 2 / s)]]> 29.49 29.52 92.42 <![CDATA[Viscosity at 100℃ / (mm 2 / s)]]> 5.59 5.530 12.33 Viscosity Index 131 125 127 Pour point / ℃ -18 -24 -18 Flash point / °C >220 >220 >220 Aromatic content / weight % <0.5 <0.5 <1.0 Color / Seybert +30 +24 +10

[0244] Comparing Example 2 with Example 1, it can be seen that the hydrorefining catalyst used in Example 1 contains three active metal elements: nickel, molybdenum, and magnesium. The hydrocracking unit of Example 1 produces hydro-oil with lower aromatic content and higher saturated hydrocarbon content (over 98% by weight), resulting in better quality base oil products (e.g., lower aromatic content and higher Seybert number).

[0245] Example 3

[0246] Referring to the process of Example 1, the difference between this comparative example and Example 1 is that the hydrorefining catalyst III is replaced with the hydrorefining catalyst D-III (without magnesium) obtained in Example 2; the rest of the process and conditions are the same as in Example 1.

[0247] The properties of the raw materials are the same as in Table 3. The operations of the hydrocracking reaction unit and the catalytic dewaxing unit are listed in Tables 20-22. The properties of the products are listed in Table 23.

[0248] Table 20 Results of Hydrocracking Unit Reactions

[0249] Reaction conditions Hydrogen partial pressure / MPa 16.0 <![CDATA[Hydrotreating / Cracking / Hydrofining Space Velocity / h -1 > 0.7 / 0.58 / 0.88 Average reaction temperature in hydrotreating / cracking / hydrorefining / °C 377 / 382 / 375 Hydrogen-to-oil volume ratio 1000 reaction results Naphtha yield / weight % 23.2 Jet fuel yield / weight % 17.5 Diesel yield / weight % 30.6 Residual oil yield / weight % 29.4 Aromatic content (by weight) of hydrogenated oil 3.2 Hydrogenation produced oil saturated hydrocarbon content / wt% 96.8 Properties of hydrotreated tail oil at 390℃~470℃ <![CDATA[Density (20 °C) / g·cm -3 > 0.852 <![CDATA[100℃ kinematic viscosity / mm 2 ·s -1 > 6.23 Sulfur content / μg / g 8 Nitrogen content / μg / g 1 Saipo Special 16 Hydrogenated tail oil properties at >470℃ <![CDATA[Density (20 °C) / g·cm -3 > 0.876 <![CDATA[100℃ kinematic viscosity / mm 2 ·s -1 > 10.35 Sulfur content / μg / g 12 Nitrogen content / μg / g 1 Saipo Special 10

[0250] Table 21 Isomerization and Dewaxing Reactions of Hydrogenated Tail Oil (Light Tail Oil Component) at 390℃~470℃

[0251]

[0252]

[0253] Table 22 Isomerization and Dewaxing Reaction of Hydrogenated Tail Oil (Heavy Tail Oil Component) at >470℃

[0254] Reaction conditions Hydrogen partial pressure / MPa 15.0 <![CDATA[Hydroisomerization / Post-refining Space Velocity per Hour -1 > 0.8 / 0.67 Average reaction temperature at ℃ for hydroisomerization / post-purification 335 / 220 Hydrogen-to-oil volume ratio 600 reaction results Naphtha yield / weight % 8.24 Diesel yield / weight % 12.43 2cst base oil yield / weight % 2.62 4cst base oil yield / weight % 3.39 6cst base oil yield / weight % 5.44 12cst base oil yield / weight % 66.85

[0255] Table 23 Properties of Base Oil Products

[0256] project 6cst base oil 1 6cst base oil 2 12cst base oil 2 <![CDATA[Viscosity at 40°C / (mm 2 / s)]]> 29.83 29.76 94.89 <![CDATA[Viscosity at 100℃ / (mm 2 / s)]]> 5.643 5.53 12.55 Viscosity Index 131 125 127 Pour point / ℃ -18 -24 -18 Flash point / °C >220 >220 >220 Aromatic content / weight % <0.2 <0.2 <0.8 Color / Seybert +30 +30 +28

[0257] Comparing Example 3 with Example 1, it can be seen that the hydrorefining catalyst used in Example 1 contains three active metal elements: nickel, molybdenum, and magnesium. The hydrocracking unit of Example 1 produces hydro-oil with lower aromatic content and higher saturated hydrocarbon content (above 98% by weight), resulting in better quality base oil products (e.g., lower aromatic content and higher Seybert number).

[0258] Examples 4-6

[0259] The process is the same as in Example 1, except that the hydrocracking unit reaction conditions are listed in Table 24 and the hydroisomerization dewaxing reaction conditions are listed in Tables 25 and 26. The properties of the raw materials are the same as in Table 3, and the properties of the products are listed in Tables 25 and 26.

[0260] Table 24 Results of Hydrocracking Unit Reactions

[0261]

[0262]

[0263] Table 25 Isomerization and Dewaxing Reactions of Hydrogenated Tail Oil (Light Tail Oil Component) at 390℃~470℃

[0264]

[0265] Table 26 Isomerization and Dewaxing Reactions of Hydrogenated Tail Oil (Heavy Tail Oil Component) at >470℃

[0266]

[0267]

[0268] As can be seen from Tables 24-26 above:

[0269] Comparing Example 4 with Example 1, Example 1 was carried out in the production process according to the catalyst loading volume ratio in the preferred embodiment of this disclosure. The hydrogenated oil obtained in Example 1 had a lower aromatic content and a higher saturated hydrocarbon content, and the quality of the final base oil product was better (for example, the oil obtained in Example 1 had a lower aromatic content and a higher Seybert number).

[0270] Comparing Example 5 with Example 1, in Example 1 the hydrocracking unit was processed according to the process conditions of the preferred embodiment of this disclosure during the production process. The hydrocracking product oil obtained in Example 1 has a lower content of aromatics and a higher content of saturated hydrocarbons, and the quality of the final base oil product is better.

[0271] Comparing Example 6 with Example 1, in Example 1 the base oil product was finally obtained with better quality because the production process was carried out in the first catalytic dewaxing unit and the second catalytic dewaxing unit according to the preferred embodiment of this disclosure.

[0272] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0273] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0274] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A method for producing both lubricating oil base oil and industrial white oil, characterized in that, Includes the following steps: S1. The residual oil is fed into the solvent deasphalting unit for solvent deasphalting and refining treatment to obtain deasphalted oil; S2. Hydrogen, vacuum wax oil, and the deasphalted oil are introduced into a hydrocracking unit and contacted with a first hydrocracking catalyst to carry out a first hydrocracking reaction, yielding hydrotreated oil. The first hydrocracking catalyst includes a hydrotreatment catalyst, a hydrocracking catalyst, and a hydrorefining catalyst. The hydrorefining catalyst includes a third support and a third active metal component supported on the third support. The third support is selected from alumina and / or silica. The third active metal component is nickel, molybdenum, and magnesium. S3. The hydrogenated oil is fed into the first separation unit for the first separation process to obtain naphtha, jet fuel, diesel, light tail oil components and heavy tail oil components. The distillation cut-off points of the light tail oil component and the heavy tail oil component are any values ​​within the range of 450~500℃. S4. The light tail oil component is introduced into the first catalytic dewaxing reaction unit and contacted with the second hydrogenation catalyst to carry out the second hydrogenation reaction, thereby obtaining the first hydrogenated dewaxing oil. The heavy tail oil component is introduced into the second catalytic dewaxing reaction unit and contacted with the third hydrogenation catalyst to carry out the third hydrogenation reaction, thereby obtaining the second hydrogenated dewaxing oil; the second hydrogenation catalyst and the third hydrogenation catalyst each independently include a hydroisomerization catalyst and a post-hydrogenation refining catalyst; S5. The first hydrodewaxed oil and the second hydrodewaxed oil are fed into the second separation unit for a second separation process to obtain lubricating oil base oil and industrial white oil. Along the flow direction of the mixed feedstock in the hydrocracking unit, the hydrotreatment catalyst, the hydrocracking catalyst, and the hydrorefining catalyst are arranged sequentially; step S2 includes: The vacuum wax oil and the deasphalted oil are mixed and then introduced into the hydrocracking unit, and the mixed feedstock is first contacted with the hydrocracking catalyst to carry out a hydrocracking reaction. Then, it is contacted with the hydrocracking catalyst to carry out a hydrocracking reaction; then, it is contacted with the hydrorefining catalyst to carry out a hydrorefining reaction to obtain the hydrotreated oil; along the flow direction of the mixed feedstock in the hydrocracking unit, a hydrotreating protectant is also provided upstream of the hydrotreating catalyst; the volume ratio of the hydrotreating protectant: hydrotreating catalyst: hydrocracking catalyst: hydrorefining catalyst is (5~35):100:(70~250):(20~180); In step S2, based on the total weight of the hydrorefining catalyst, the content of the third active metal in the form of oxides is 0.5-2.6 wt% for magnesium oxide, 1.5-5.5 wt% for molybdenum oxide, 20-28 wt% for nickel oxide, and 64-78 wt% for the third support.

2. The method according to claim 1, characterized in that, In step S1, the conditions for the solvent deasphalting and refining treatment include: In the extraction tower, the volume ratio of solvent to residual oil is (2~10):1, the temperature at the top of the extraction tower is 20~150℃, and the pressure is 2~6MPa.

3. The method according to claim 2, characterized in that, In step S1, the conditions for the solvent deasphalting and refining treatment include: The volume ratio of solvent to residual oil is (3~8):1, the temperature at the top of the extraction tower is 30~120℃, and the pressure is 3~5MPa.

4. The method according to claim 2, characterized in that, The solvent is selected from one or more of hydrocarbons with 3 to 7 carbon atoms, condensate oil, light naphtha, and gasoline.

5. The method according to claim 4, characterized in that, The solvent includes propane.

6. The method according to claim 4, characterized in that, The solvent includes propane and one or more selected from ethane, propylene, butane and pentane.

7. The method according to claim 5 or 6, characterized in that, The solvent contains 80-100% propane by weight.

8. The method according to claim 7, characterized in that, The solvent contains 90-100% propane by weight.

9. The method according to claim 8, characterized in that, The solvent contains 95-100% propane by weight.

10. The method according to claim 2, characterized in that, The solvent deasphalting and refining process results in the deasphalted oil having a carbon residue value of less than 10% by weight.

11. The method according to claim 10, characterized in that, The solvent deasphalting and refining process results in the deasphalted oil having a carbon residue value of less than 6% by weight.

12. The method according to claim 1, characterized in that, In step S1, the residue oil is selected from vacuum residue oil and / or atmospheric residue oil.

13. The method according to claim 1, characterized in that, In step S2, a hydrogenation protectant is also provided upstream of the hydrocracking catalyst along the flow direction of the mixed feedstock in the hydrocracking unit; the volume ratio of the hydrogenation protectant: hydrocracking catalyst: hydrocracking catalyst: hydrorefining catalyst is (10~30):100:(80~220):(40~150).

14. The method according to claim 1, characterized in that, In step S2, the volume ratio of the depressurized wax oil to the deasphalted oil is (2~30):

1.

15. The method according to claim 14, characterized in that, In step S2, the volume ratio of the depressurized wax oil to the deasphalted oil is (5~20):

1.

16. The method according to claim 1, characterized in that, In step S2, the carbon residue of the mixture of the vacuum wax oil and the deasphalted oil is no more than 2% by weight.

17. The method according to claim 16, characterized in that, In step S2, the carbon residue of the mixture of the depressurized wax oil and the deasphalted oil is not greater than 1% by weight.

18. The method according to claim 1, characterized in that, In step S2, the processing conditions of the hydrocracking unit include: The hydrogenation reaction was carried out at a temperature of 330–430 °C, a hydrogen partial pressure of 10–20 MPa, and a volume hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600~2000):1; The hydrocracking reaction is carried out at a temperature of 350–450 °C, a hydrogen partial pressure of 10–20 MPa, and a volume hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600~2000):1; The hydrogenation purification reaction is carried out at temperatures ranging from 280 to 420°C, with hydrogen partial pressures of 10 to 20 MPa and volume hourly space velocities of 0.5 to 5.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (600~2000):

1.

19. The method according to claim 18, characterized in that, In step S2, the processing conditions of the hydrocracking unit include: The hydrogenation reaction was carried out at a temperature of 350–390 °C, a hydrogen partial pressure of 12–18 MPa, and a volume hourly space velocity of 0.6–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800~1500):1; The hydrocracking reaction is carried out at temperatures of 370–410 °C, hydrogen partial pressures of 12–18 MPa, and volume hourly space velocities of 0.6–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800~1500):1; The hydrogenation purification reaction is carried out at a temperature of 300–380 °C, a hydrogen partial pressure of 12–18 MPa, and a volume hourly space velocity of 0.6–2.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (800~1500):

1.

20. The method according to claim 1, characterized in that, In step S2, the hydrogenation catalyst includes a first support, an active metal component, an optional first auxiliary agent, and an optional organic additive. The first carrier is selected from one or more of alumina, silicon dioxide, titanium dioxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide, natural zeolite, and clay; the active metal component includes a first active metal component and a second active metal component; the first active metal component is selected from nickel and / or cobalt; the second active metal component is selected from molybdenum and / or tungsten; the first auxiliary agent is selected from one or more of fluorine, boron, and phosphorus; and the organic additive is selected from oxygen-containing organic compounds and / or nitrogen-containing organic compounds.

21. The method according to claim 20, characterized in that, The first carrier is selected from alumina and / or silicon oxide-alumina.

22. The method according to claim 20, characterized in that, The oxygen-containing organic compound is selected from organic alcohols and / or organic acids; the nitrogen-containing organic compound is selected from one or more organic amines.

23. The method according to claim 22, characterized in that, The oxygen-containing organic compound is selected from one or more of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, and malic acid; the nitrogen-containing organic compound is selected from one or more of ethylenediamine, EDTA, and their ammonium salts.

24. The method according to claim 20, characterized in that, Based on the total weight of the hydrogenation catalyst, the content of the first active metal component (calculated as oxide) is 1-5% by weight, the content of the second active metal component (calculated as oxide) is 12-35% by weight, the content of the first auxiliary agent (calculated as element) is 0-9% by weight, and the molar ratio of the organic additive to all active metal components (calculated as oxide) is 0-2:

1.

25. The method according to claim 24, characterized in that, The first carrier is γ-alumina; the active metal component is tungsten oxide and nickel oxide; and the first additive is fluorine.

26. The method according to claim 25, characterized in that, Based on the total weight of the hydrotreating catalyst, the nickel oxide content is 1-5% by weight, the tungsten oxide content is 12-35% by weight, the fluorine content is 1-9% by weight, and the balance is γ-alumina.

27. The method according to claim 1, characterized in that, In step S2, the hydrocracking catalyst includes a second support and one or more of group VIII and group VIB metals supported on the second support.

28. The method according to claim 27, characterized in that, The second carrier comprises a Y-type molecular sieve and an amorphous composite oxide; the amorphous composite oxide is selected from at least two of silicon oxide, aluminum oxide, titanium oxide and zirconium oxide.

29. The method according to claim 28, characterized in that, Based on the total weight of the hydrocracking catalyst, the content of group VIII metals is 2-8% by weight, the content of group VIB metals is 12-33% by weight, the content of Y-type molecular sieve is 1-30% by weight, and the content of amorphous composite oxides is 50-80% by weight, wherein the group VIII metals and group VIB metals are in oxide form.

30. The method according to claim 1, characterized in that, The hydrogenated oil obtained in step S2 contains more than 80% saturated hydrocarbons by weight.

31. The method according to claim 30, characterized in that, The hydrogenated oil obtained in step S2 contains more than 85% saturated hydrocarbons by weight.

32. The method according to claim 31, characterized in that, The hydrogenated oil obtained in step S2 contains more than 90% saturated hydrocarbons by weight.

33. The method according to claim 1, characterized in that, In step S4, the first hydroisomerization catalyst and the first post-hydrogenation refining catalyst are sequentially arranged along the material flow direction in the first catalytic dewaxing reaction unit, so that after the light tail oil component enters the first catalytic dewaxing reaction unit, it first contacts the first hydroisomerization catalyst to carry out the first hydroisomerization catalytic reaction; then it contacts the first post-hydrogenation refining catalyst to carry out the first post-hydrogenation refining reaction, thereby obtaining the first hydrodewaxed oil. In the second catalytic dewaxing reaction unit, the second hydroisomerization catalyst and the second post-hydrogenation refining catalyst are sequentially arranged along the material flow direction, so that after the heavy tail oil component enters the second catalytic dewaxing reaction unit, it first contacts the second hydroisomerization catalyst to carry out the second hydroisomerization catalytic reaction; then it contacts the second post-hydrogenation refining catalyst to carry out the second post-hydrogenation refining reaction, thereby obtaining the second hydrodewaxed oil.

34. The method according to claim 33, characterized in that, Based on the first hydroisomerization catalyst, the content of the first hydrorefining catalyst is 50-200% by volume. The content of the second hydrogenation purification catalyst is 50-200% by volume, based on the second hydrogenation isomerization catalyst.

35. The method according to claim 34, characterized in that, Based on the first hydroisomerization catalyst, the content of the first hydrorefining catalyst after hydrogenation is 80-150% by volume; The content of the second hydrogenation purification catalyst is 80-150% by volume, based on the second hydrogenation isomerization catalyst.

36. The method according to claim 34, characterized in that, In step S4, the reaction conditions in the first catalytic dewaxing reaction unit include: The first hydroisomerization catalytic reaction is carried out at a temperature of 280–400 °C, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.4–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300~1200):1; The purification reaction after the first hydrogenation is carried out at a temperature of 150–300 °C, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.4–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300~1200):1; The reaction conditions in the second catalytic dewaxing reaction unit include: The second hydroisomerization catalytic reaction is carried out at a temperature of 300–420 °C, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.3–1.8 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300~1200):1; The purification reaction after the second hydrogenation is carried out at a temperature of 150–300 °C, a pressure of 3–20 MPa, and a liquid hourly space velocity of 0.3–1.8 h⁻¹. -1 The hydrogen-to-oil volume ratio is (300~1200):

1.

37. The method according to claim 36, characterized in that, In step S4, the reaction conditions in the first catalytic dewaxing reaction unit include: The first hydroisomerization catalytic reaction is carried out at a temperature of 300–360 °C, a pressure of 8–18 MPa, and a liquid hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400~1000):1; The purification reaction after the first hydrogenation is carried out at a temperature of 180–280 °C, a pressure of 8–18 MPa, and a liquid hourly space velocity of 0.5–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400~1000):1; The reaction conditions in the second catalytic dewaxing reaction unit include: The second hydroisomerization catalytic reaction is carried out at a temperature of 320–380 °C, a pressure of 8–18 MPa, and a liquid hourly space velocity of 0.4–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400~1000):1; The purification reaction after the second hydrogenation is carried out at a temperature of 180–260 °C, a pressure of 8–18 MPa, and a liquid hourly space velocity of 0.4–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is (400~1000):

1.

38. The method according to claim 1, characterized in that, In step S4, the hydroisomerization catalysts of the second and third hydrogenation catalysts each independently include a mesoporous molecular sieve, an inorganic oxide, and a fourth active metal component.

39. The method according to claim 38, characterized in that, The mesoporous molecular sieve is a one-dimensional elliptical pore structure with a short axis of 4.2~4.8 Å and a long axis of 5.4~7.0 Å.

40. The method according to claim 39, characterized in that, The mesoporous molecular sieve is selected from one or more of ZSM-22, Nu-10, Theta-1, ISI-1, ZSM-23, SAPO-11, SAPO-31 and SAPO-41 molecular sieves.

41. The method according to claim 40, characterized in that, The mesoporous molecular sieve is ZSM-22 molecular sieve.

42. The method according to claim 38, characterized in that, The fourth active metal component is selected from one or more of cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum and tungsten.

43. The method according to claim 41, characterized in that, The fourth active metal component is platinum.

44. The method according to claim 38, characterized in that, The inorganic oxide is selected from aluminum oxide and / or silicon oxide.

45. The method according to claim 38, characterized in that, Based on the total weight of the hydroisomerization catalyst, the content of the mesoporous molecular sieve is 30-70% by weight, the content of the inorganic oxide is 30-70% by weight, and the content of the fourth active metal component in reduced state is 0.2-1% by weight.

46. ​​The method according to claim 1, characterized in that, The post-hydrogenation refining catalysts of the second and third hydrogenation catalysts each independently comprise a silicon-aluminum support and a fifth active metal component supported on the silicon-aluminum support.

47. The method according to claim 46, characterized in that, Based on the weight of the silicon-aluminum carrier, the silicon-aluminum carrier comprises 16-20% by weight silicon (calculated as oxide) and 78-82% by weight aluminum (calculated as oxide).

48. The method according to claim 46, characterized in that, The ratio of pyridine β-acid to L-acid measured at 200℃ on the silica-alumina support was 0.06~0.

085.

49. The method according to claim 46, characterized in that, The fifth active metal component is selected from platinum and / or palladium.

50. The method according to claim 49, characterized in that, When the fifth active metal component is platinum and palladium, the content of reduced palladium is 0.1-5% by weight, based on the total weight of the fifth active metal component (calculated as oxides). The content of reduced platinum is 0.1~5% by weight.

51. The method according to claim 50, characterized in that, When the fifth active metal component is platinum and palladium, the content of reduced palladium is 0.2 to 2% by weight, based on the total weight of the fifth active metal component calculated as oxides; and the content of reduced platinum is 0.2 to 2% by weight.

52. A system for the method of producing both lubricating oil base oil and industrial white oil as described in claim 1, characterized in that, The system includes a solvent deasphalting unit, a hydrocracking unit, a first separation unit, a first catalytic dewaxing reaction unit, a second catalytic dewaxing reaction unit, and a separation unit; The deasphalting unit is configured to perform solvent deasphalting and refining treatment on the residual oil to obtain deasphalted oil. The hydrocracking unit includes a first hydrocracking catalyst, and the hydrocracking unit is configured to contact hydrogen, vacuum wax oil and deasphalted oil from the deasphalting unit with the first hydrocracking catalyst to carry out a first hydrocracking reaction to obtain hydrocracking product oil; wherein the first hydrocracking catalyst includes a hydrotreating catalyst, a hydrocracking catalyst and a hydrorefining catalyst. The first separation unit is configured to perform a first separation process on the hydrocracking product oil from the hydrocracking unit to obtain naphtha, jet fuel, diesel, light tail oil components and heavy tail oil components; The first catalytic dewaxing reaction unit includes a second hydrogenation catalyst. The first catalytic dewaxing reaction unit is configured to contact the light tail oil component with the second hydrogenation catalyst to carry out a second hydrogenation reaction and obtain a first hydrogenated dewaxing oil. The second catalytic dewaxing reaction unit includes a third hydrogenation catalyst. The second catalytic dewaxing reaction unit is configured to contact the heavy tail oil component with the third hydrogenation catalyst to carry out a third hydrogenation reaction, thereby obtaining a second hydrogenated dewaxed oil. The second hydrogenation catalyst and the third hydrogenation catalyst each independently include a hydroisomerization catalyst and a post-hydrogenation refining catalyst. The second separation unit is configured to perform a second separation process on the first hydrodewaxed oil from the first catalytic dewaxing reaction unit and the second hydrodewaxed oil from the second catalytic dewaxing reaction unit to obtain lubricating oil base oil and industrial white oil.

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