A method for hydrotreating residual oil

Abstract

The present invention discloses a method for hydrotreating residual oil. The method adopts a fixed-bed hydrogenation process, including: in the presence of hydrogen, a residual oil raw material is contacted with at least one hydroremoval carbon residue catalyst and at least one hydrodenitrogenation catalyst in sequence for hydrogenation reaction to obtain hydrogenated oil; the hydroremoval carbon residue catalyst is a sulfided catalyst, including a carrier and active metals Mo and Ni, further including Se, characterized by TEM-EDS method, and the Se content distributed in the Ni-Mo-S active phase region accounts for 65%-95% of the total Se content; the hydrodenitrogenation catalyst is a sulfided catalyst, including a carrier and active metals Mo and Ni, further including Ga, characterized by TEM-EDS method, and the Ga content distributed in the Ni-Mo-S active phase region accounts for 60%-95% of the total Ga content. The residual oil hydrotreating method of the present invention has the effect of deep carbon removal and denitrification.

Description

Technical Field

[0001] The present invention relates to the field of residual oil hydrogenation, in particular to a residual oil hydrogenation treatment method. Background Art

[0002] Residue hydrotreating technology is a primary means of reducing the weight and cleaning of residue oil. Residue oil has a complex structure, including polycyclic aromatic hydrocarbons, sulfur compounds, and nitrogen compounds. These are all molecules that need to be converted during the hydroconversion process. However, the properties and conversion characteristics of these substances vary significantly. To achieve efficient conversion of these substances, the ideal method is to use a high-performance graded catalyst system. The basic principle of grading is that the catalyst particles, average pore size, and activity are arranged from large to small along the direction of the reacting liquid phase flow.

[0003] In recent years, researchers have continuously developed new hydrodesulfurization catalysts, hydrodecarbonization and hydrodenitrogenation catalysts, or residue hydrotreating catalyst grading methods.

[0004] CN110465305A discloses a method for preparing an acidic supported hydrodesulfurization catalyst. The method comprises: loading a molecular sieve onto the surface of a carbon-based material to produce an acidic carbon-based support material; preparing a precursor solution of the hydrodesulfurization catalyst's active components, impregnating the acidic carbon-based support material into the precursor solution, and then drying and calcining the resulting acidic supported hydrodesulfurization catalyst. This catalyst utilizes the isomerization properties of its acidity to remove substituted sulfides. However, the additional acidity increases the risk of carbon deposition and coking on the catalyst when processing heavy oils, reducing the catalyst's operational stability.

[0005] CN104096584B discloses a method for preparing a transition metal phosphide catalyst that can be used for residual oil hydrodesulfurization and hydrodenitrogenation reactions. This method uses a mixture of alumina and activated carbon as a carrier, with the active components being Ni2P, MoO3, WO3, CoO, and NiO. This method somewhat alleviates the problem of nickel aluminate formation during conventional high-temperature metal ion reduction processes, improving catalyst activity to a certain extent. However, the use of activated carbon as a partial carrier reduces the total acid content and mechanical strength of the carrier, decreases the dispersion of the active metal, and hinders further improvement in the desulfurization and denitrification rates of the catalyst.

[0006] CN106622264A discloses a hydrogenation carbon removal catalyst. The catalyst contains an active metal component and a modified hydrogenation catalyst support. The modified hydrogenation catalyst support includes a support and a metal promoter and an acidic promoter supported on the support. The metal promoter and the acidic promoter are distributed in layers on the support, with the shell layer being the metal promoter and the core layer being the acidic promoter. The metal promoter is a Group IA metal component and / or a Group IIA metal component, and the acidic promoter is selected from at least one component of F, P, and B. The active metal component in the catalyst is still loaded on the catalyst support using a conventional impregnation method, and the carbon removal performance of the catalyst still needs to be further improved.

[0007] CN105567311A discloses a catalyst grading method for residue hydroprocessing. The total acid content of each catalyst gradually increases along the flow direction, the proportion of Lewis acid in the total acid gradually decreases, and the proportion of Bronsted acid in the total acid gradually increases. Although the selectivity of the catalyst can be altered by adjusting the acidity of the support, the dispersion of the active metal on the highly acidic surface is limited, affecting the utilization rate of the active metal in the catalyst.

[0008] CN107880931A discloses a fixed-bed hydrogenation catalyst grading method and a heavy oil hydrotreating method. This method employs a serially connected replaceable zone and a main reaction zone along the flow direction. The replaceable zone is configured with two parallel rotation zones. During normal operation of the device, at least one rotation zone operates simultaneously with the main reaction zone. While this method extends the device's operating time, it does not substantially improve the catalyst's hydrogenation activity or operating time, and maintaining long-term operation still requires the consumption of a large amount of hydrogenation catalyst. Summary of the Invention

[0009] In view of the shortcomings of the prior art, the present invention provides a residual oil hydroprocessing method, which has the effects of deep carbon removal and nitrogen removal.

[0010] The present invention provides a residual oil hydroprocessing method, which adopts a fixed bed hydrogenation process, comprising: in the presence of hydrogen, the residual oil raw material is contacted with at least one hydroremoval carbon residue catalyst and at least one hydrodenitrogenation catalyst in sequence to carry out a hydrogenation reaction to obtain hydrogenated oil;

[0011] The hydroremoval of carbon residue catalyst is a sulfided catalyst, comprising a support and active metals Mo and Ni, and also comprising Se, wherein, as characterized by TEM-EDS, the Se content distributed in the Ni-Mo-S active phase region accounts for 65%-95% of the total Se content, preferably 78%-95%;

[0012] The hydrodenitrogenation catalyst is a sulfided catalyst, including a carrier and active metals Mo and Ni, and also Ga. Characterized by TEM-EDS method, the Ga content distributed in the Ni-Mo-S active phase region accounts for 60%-95% of the total Ga content, preferably 75%-90%.

[0013] Furthermore, the hydroremoval of carbon residue catalyst is characterized by TEM-EDS method, and the sulfur content at the corners of the Ni-Mo-S active phase accounts for less than 6.0% of the total sulfur content in the Ni-Mo-S active phase, and further ranges from 0.5% to 4.0%.

[0014] Furthermore, the hydrodecarbonization catalyst has a molybdenum content of 8%-20%, preferably 12.5%-16.5%, calculated as Mo, and a nickel content of 1.5%-6.5%, preferably 2.0%-5.0%, calculated as Ni, based on the mass of the hydrodecarbonization catalyst.

[0015] Furthermore, the hydrogenation carbon removal catalyst has a sulfur content of 4%-15%, preferably 6%-12%, calculated as S, and a Se content of 0.5%-5.0%, preferably 1.0%-4.0%, calculated as Se, based on the mass of the hydrogenation carbon removal catalyst.

[0016] Furthermore, the content of the carrier in the hydroremoval of carbon residue catalyst is 55%-80%, preferably 55%-70%, based on the mass of the hydroremoval of carbon residue catalyst.

[0017] Furthermore, in the hydrogenation carbon removal catalyst, the carrier is at least one of alumina, silicon oxide, amorphous silica-alumina, etc. The specific surface area of ​​the carrier is 150-350m 2 / g, preferably 200-300m 2 / g, and the pore volume of the carrier is 0.5-1.2cm 3 / g, preferably 0.7-1.0cm 3 / g.

[0018] Furthermore, the hydrodenitrogenation catalyst is characterized by TEM-EDS method, and the sulfur content at the corners of the Ni-Mo-S active phase accounts for less than 4.0% of the total sulfur content in the Ni-Mo-S active phase, and further ranges from 0.5% to 3.0%.

[0019] Furthermore, the hydrodenitrogenation catalyst has a molybdenum content of 10%-20%, preferably 13%-18%, calculated as Mo, and a nickel content of 1.5%-6.5%, preferably 2.0%-6%, calculated as Ni, based on the mass of the hydrodenitrogenation catalyst.

[0020] Furthermore, the hydrodenitrogenation catalyst has a Ga content of 0.4% to 4.0%, preferably 0.8% to 3.0%, based on the mass of the hydrodenitrogenation catalyst.

[0021] Furthermore, the hydrodenitrogenation catalyst has a sulfur content in the form of S of 8% to 15%, preferably 9% to 14%, based on the mass of the hydrodenitrogenation catalyst.

[0022] Furthermore, the hydrodenitrogenation catalyst has a carrier content of 55%-75%, preferably 55%-70%, based on the mass of the hydrodenitrogenation catalyst.

[0023] Furthermore, in the hydrodenitrogenation catalyst, the carrier can be an inorganic refractory oxide, such as at least one of alumina, silicon oxide, amorphous silicon aluminum, etc. The specific surface area of ​​the carrier is 200-500m 2 / g, preferably 250-400m 2 / g, pore volume of 0.4-1.0cm 3 / g, preferably 0.6-0.8cm 3 / g. The carrier may also be doped with one or more of the modifying elements such as phosphorus, silicon, boron, fluorine, sodium, etc. The amount of the modifying element added is a conventional amount, preferably accounting for 0.5%-6.0% of the carrier mass.

[0024] Furthermore, the preparation method of the hydrogenation carbon residue removal catalyst comprises:

[0025] (1) performing a sulfurization treatment on the oxidized hydrogenation catalyst to obtain a sulfurized hydrogenation catalyst;

[0026] (2) subjecting the sulfided hydrogenation catalyst obtained in step (1) to a desulfurization treatment;

[0027] (3) reacting the catalyst treated in step (2) with a mixed gas of hydrogen selenide and hydrogen to obtain a hydrogenation carbon removal catalyst.

[0028] Furthermore, the preparation method of the hydrodenitrogenation catalyst comprises:

[0029] (1) performing a primary sulfurization on an oxidized hydrogenation catalyst to obtain a sulfurized hydrogenation catalyst;

[0030] (II) subjecting the sulfided hydrogenation catalyst obtained in step (I) to a desulfurization treatment;

[0031] (III) contacting the catalyst treated in step (II) with an organic solution containing Ga element and a stabilizer to react and obtain a hydrodenitrogenation catalyst.

[0032] The present invention also provides a residual oil hydroprocessing method, which adopts a fixed bed hydrogenation process, comprising: in the presence of hydrogen, the residual oil feedstock is contacted with at least one hydroremoval of carbon residue catalyst and at least one hydrodenitrogenation catalyst in sequence to carry out a hydrogenation reaction to obtain hydrogenated oil;

[0033] The hydrogenation carbon residue removal catalyst is prepared by the following method, which comprises:

[0034] (1) performing a sulfurization treatment on the oxidized hydrogenation catalyst to obtain a sulfurized hydrogenation catalyst;

[0035] (2) subjecting the sulfided hydrogenation catalyst obtained in step (1) to a desulfurization treatment;

[0036] (3) reacting the catalyst treated in step (2) with a mixed gas of hydrogen selenide and hydrogen to obtain a hydrogenation carbon removal catalyst;

[0037] The hydrodenitrogenation catalyst is prepared by the following method, which comprises:

[0038] (1) performing a primary sulfurization on an oxidized hydrogenation catalyst to obtain a sulfurized hydrogenation catalyst;

[0039] (II) subjecting the sulfided hydrogenation catalyst obtained in step (I) to a desulfurization treatment;

[0040] (III) contacting the catalyst treated in step (II) with an organic solution containing Ga element and a stabilizer to react and obtain a hydrodenitrogenation catalyst.

[0041] Furthermore, in step (1), the oxidized hydrogenation catalyst comprises: a support, and active metal components of molybdenum and nickel. Based on the mass of the catalyst, the support content is 50%-80%, the molybdenum content as oxide is 12%-30%, and the nickel content as oxide is 2%-8%.

[0042] Furthermore, in step (1), the carrier of the oxidized hydrogenation catalyst is at least one of aluminum oxide, silicon oxide, amorphous silicon aluminum, etc. The specific surface area of ​​the carrier is 150-350m 2 / g, preferably 200-300m 2 / g, and the pore volume of the carrier is 0.5-1.2cm 3 / g, preferably 0.7-1.0cm 3 / g.

[0043] Furthermore, in step (1), the oxidized hydrogenation catalyst is a catalyst having a heavy oil hydrogenation function, which can be prepared by conventional methods in the art or purchased as a commercial catalyst.

[0044] Furthermore, in step (1), the sulfurization treatment is a full sulfurization treatment, i.e., the active metals in the oxidized hydrogenation catalyst are completely sulfurized. A known sulfurization method can be used. For example, the conditions for the initial sulfurization are as follows: a temperature of 240-400°C, preferably 280-380°C, a sulfurization time of 3-8 hours, a hydrogen pressure of 2.0-12.0 MPa, preferably 3.0-10.0 MPa, and a hydrogen flow rate of 2.0-15.0 mL·min -1 ·g -1 Oxidized hydrogenation catalyst, preferably 3.0-10.0 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

[0045] Furthermore, in step (1), the sulfiding liquid used in the sulfiding treatment comprises a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-phenyl polysulfide, and dimethyl sulfoxide, and the organic solvent is at least one of cyclohexane, n-heptane, aviation kerosene, and diesel. The mass fraction of the sulfur-containing compound in the sulfiding liquid is 2%-6%, preferably 4%-6%. The flow rate of the sulfiding liquid is 0.5-4.0 mL·h -1 ·g -1 Oxidized hydrogenation catalyst, preferably 1.0-4.0 mL·h -1 ·g -1 Oxidative hydrogenation catalyst.

[0046] Furthermore, in step (2), the desulfurization treatment is a mild desulfurization treatment, which is performed in at least one of the following ways:

[0047] (a) desulfurizing the sulfided hydrogenation catalyst obtained in step (1) using hydrogen containing hydrogen sulfide;

[0048] (b) desulfurizing the sulfided hydrogenation catalyst obtained in step (1) using a sulfiding liquid in the presence of hydrogen.

[0049] Furthermore, in step (2), the desulfurization treatment temperature is 180-370° C., preferably 200-300° C., the treatment time is 4-24 hours, preferably 6-16 hours, and the total pressure is 2.0-18.0 MPa, preferably 4.0-15.0 MPa.

[0050] Furthermore, the temperature of the desulfurization treatment in step (2) is 50 to 100° C. lower than the temperature of the sulfurization treatment in step (1).

[0051] Furthermore, in method (a), the volume ratio of hydrogen sulfide to hydrogen is 200:1 to 800:1, preferably 300:1-600:1, and the total gas flow rate is 5-30 mL·min -1 ·g -1 Oxidized hydrogenation catalyst, preferably 10-20 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

[0052] Furthermore, in method (b), the sulfiding liquid comprises a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-phenyl polysulfide, and dimethyl sulfoxide; and the organic solvent is at least one of cyclohexane, n-heptane, aviation kerosene, and diesel. The mass fraction of the sulfur-containing compound in the sulfiding liquid is 0.1%-0.6%. During the desulfurization process, the flow rate of the sulfiding liquid is 0.2-2.0 mL·h -1 ·g -1 Oxidized hydrogenation catalyst, preferably 0.4-1.5 mL·h -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate is 5-30mL·min -1 ·g -1 Oxidized hydrogenation catalyst, preferably 10-20 mL·min -1 ·g -1 Oxidative hydrogenation catalyst

[0053] Furthermore, in step (3), the reaction conditions are as follows: reaction temperature is 120-250°C, preferably 150-220°C, reaction time is 1-8 hours, preferably 2-6 hours; reaction pressure is 2.0-12.0 MPa, preferably 4.0-8.0 MPa, the volume fraction of hydrogen selenide in the mixed gas is 1%-20%, preferably 3%-15%, the volume fraction of hydrogen is 80%-99%, preferably 85%-97%. The flow rate of the mixed gas is 5-40 mL·min -1 ·g -1 Oxidized hydrogenation catalyst, preferably 10-30 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

[0054] The preparation method of the hydrodenitrogenation catalyst provided by the present invention comprises:

[0055] (1) performing a primary sulfurization on an oxidized hydrogenation catalyst to obtain a sulfurized hydrogenation catalyst;

[0056] (II) subjecting the sulfided hydrogenation catalyst obtained in step (I) to a desulfurization treatment;

[0057] (III) mixing the catalyst treated in step (II) with an organic solution containing Ga element and a stabilizer, and reacting the mixture to obtain a hydrodenitrogenation catalyst.

[0058] Furthermore, in step (I), the oxidized hydrogenation catalyst comprises: a support, and active metal components of molybdenum and nickel. Based on the mass of the catalyst, the support comprises 50% to 75%, the molybdenum comprises 15% to 40% as an oxide, and the nickel comprises 15% to 23% as an oxide.

[0059] Furthermore, in step (I), the carrier of the oxidized hydrogenation catalyst is at least one of aluminum oxide, silicon oxide, amorphous silicon aluminum, etc. The specific surface area of ​​the carrier is 200-500m 2 / g, preferably 250-400m 2 / g. The pore volume of the carrier is 0.4-1.0cm 3 / g, preferably 0.6-0.8cm 3 The carrier may be doped with one or more of the modifying elements such as phosphorus, silicon, boron, fluorine, sodium, etc. The amount of the modifying element added is a conventional amount, preferably accounting for 0.5% to 6.0% of the carrier mass.

[0060] Furthermore, in step (I), the oxidized hydrogenation catalyst is a catalyst having a heavy oil hydrogenation function, which can be prepared by conventional methods in the art or purchased as a commercial catalyst, such as a residue hydrodenitrogenation catalyst.

[0061] Furthermore, in step (I), the primary sulfidation is full sulfidation, i.e., the active metals in the oxidized hydrogenation catalyst are fully sulfided. A known sulfidation method can be used. For example, the primary sulfidation conditions are as follows: a temperature of 240-400°C, preferably 280-380°C, a sulfidation time of 3-8 hours, a hydrogen pressure of 2.0-12.0 MPa, preferably 3.0-10.0 MPa, and a hydrogen flow rate of 2.0-15.0 mL·min -1 ·g -1 Oxidized hydrogenation catalyst, preferably 3.0-10.0 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

[0062] Furthermore, in step (I), the sulfiding liquid used in the sulfidation treatment comprises a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-phenyl polysulfide, and dimethyl sulfoxide, and the organic solvent is at least one of cyclohexane, n-heptane, aviation kerosene, and diesel. The mass fraction of the sulfur-containing compound in the sulfiding liquid is 2%-6%, preferably 4%-6%. The flow rate of the sulfiding liquid is 0.5-4.0 mL·h -1 ·g -1 Oxidized hydrogenation catalyst, preferably 1.0-4.0 mL·h -1 ·g -1 Oxidative hydrogenation catalyst.

[0063] Furthermore, in step (II), the desulfurization treatment is a mild desulfurization treatment, which is carried out in at least one of the following ways:

[0064] (i) desulfurizing the sulfided hydrogenation catalyst obtained in step (I) using hydrogen containing hydrogen sulfide;

[0065] (ii) desulfurizing the sulfided hydrogenation catalyst obtained in step (I) using a sulfiding liquid in the presence of hydrogen.

[0066] Furthermore, in step (II), the desulfurization treatment temperature is 180-370° C., preferably 200-300° C., the treatment time is 4-24 hours, preferably 6-16 hours, and the total pressure is 2.0-18.0 MPa, preferably 4.0-15.0 MPa.

[0067] Furthermore, the temperature of the desulfurization treatment in step (II) is 50 to 100° C. lower than the temperature of the sulfurization treatment in step (I).

[0068] Furthermore, in mode (i), the volume ratio of hydrogen sulfide to hydrogen is 200:1-800:1, preferably 300:1-600:1, and the total gas flow rate is 5-30 mL·min -1 ·g -1 Oxidized hydrogenation catalyst, preferably 10-20 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

[0069] Furthermore, in method (ii), the sulfiding liquid comprises a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-phenyl polysulfide, and dimethyl sulfoxide; and the organic solvent is at least one of cyclohexane, n-heptane, aviation kerosene, and diesel. The mass fraction of the sulfur-containing compound in the sulfiding liquid is 0.1%-0.6%. During the desulfurization process, the flow rate of the sulfiding liquid is 0.2-2.0 mL·h -1 ·g -1-1 Oxidized hydrogenation catalyst, preferably 0.4-1.5 mL·h -1 ·g -1-1 Oxidized hydrogenation catalyst, hydrogen flow rate is 5-30mL·min -1 ·g -1 Oxidized hydrogenation catalyst, preferably 10-20 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

[0070] Furthermore, in step (III), the organic solution containing the Ga element and the stabilizer comprises one or more of the solvent selected from toluene, cyclohexane, decahydronaphthalene, tetrahydronaphthalene, and n-heptane, the Ga-containing compound selected from one or more of gallium acetylacetonate and triethylgallium, and the stabilizer selected from one or more of triethanolamine, diethanolamine, monoethanolamine, and aniline. The organic solution containing the Ga element and the stabilizer comprises the Ga compound in an amount of 0.5% to 5% by weight, preferably 1.5% to 4% by weight, and the stabilizer in an amount of 2% to 8% by weight, preferably 3% to 6% by weight.

[0071] Furthermore, in step (III), the reaction temperature is 80-200°C, preferably 100-160°C, the pressure is 0.2-4.0 MPa, preferably 0.5-2.0 MPa, the reaction time is 2-12 hours, preferably 4-10 hours. The flow rate of hydrogen is 2-20 mL·min -1 ·g -1 Oxidized hydrogenation catalyst, preferably 5-15 mL·min -1 ·g -1 Oxidized hydrogenation catalyst. The flow rate of the organic solution containing Ga element and stabilizer is 2-10mL·h -1 ·g -1 Oxidized hydrogenation catalyst, preferably 3-8 mL·h -1 ·g -1 Oxidative hydrogenation catalyst.

[0072] Furthermore, the operating conditions of the fixed bed hydrogenation process are as follows: reaction temperature of 300-400°C, reaction pressure of 8.0-25.0 MPa, hydrogen-to-oil volume ratio of 500:1-1500:1, liquid hourly volume space velocity of 0.1-1.0h -1 .

[0073] Furthermore, the hydrodecarbonization catalyst and hydrodenitrogenation catalyst can be loaded in a variety of graded ways, and the gradation principle can adopt the conventional gradation principle, such as gradually decreasing particle size and average pore size and gradually increasing activity along the liquid phase flow direction.

[0074] Furthermore, to extend the service life of the hydrodecarbonization and denitrification catalysts and enhance the effectiveness of their gradation, it is preferred to load a hydrogenation protective agent, a hydrodemetallization catalyst, and a hydrodesulfurization catalyst before the hydrodecarbonization and hydrodenitrification catalysts. The hydrogenation protective agent, hydrodemetallization catalyst, and hydrodesulfurization catalyst can be catalysts commonly used in the art.

[0075] Furthermore, the total loading volume of the hydroremoval of carbon residue catalyst and the hydrodenitrogenation catalyst accounts for more than 50% of the total catalyst loading volume, preferably 60%-85%.

[0076] Furthermore, the loading volume ratio of the hydroremoval of carbon residue catalyst to the hydrodenitrogenation catalyst is 1:3-3:1.

[0077] Furthermore, the nitrogen content of the residual oil feedstock is above 2000 μg / g, further 2500-4500 μg / g, the carbon residue value is above 10 wt%, further 15 wt%-20 wt%.The residual oil feedstock includes at least one of atmospheric residue, vacuum residue, and deasphalted oil.

[0078] Furthermore, the obtained hydrogenated oil can be used as feed for a catalytic cracking unit, or as feed for a hydrocracking unit, or as feed for a heavy oil deep catalytic cracking unit (DCC).

[0079] Compared with the prior art, the present invention has the following advantages:

[0080] 1. The fixed-bed residue oil hydrotreating method of the present invention adopts a specific hydrodecarbonization catalyst and a hydrodenitrogenation catalyst for graded loading, has ultra-deep carbon removal activity, high denitrification activity, and good catalyst stability.

[0081] 2. The preparation method of the hydrodenitrogenation catalyst of the present invention is to first perform initial sulfurization and desulfurization on the oxidized hydrogenation catalyst, so that the metal active phase to be modified is in a specific desulfurized high-activity state, the outer layer of the active phase edge is exposed active metal, and at the same time, the internal tricoordinate sulfur atoms and the stable Ni-Mo-S crystal structure of the hydrogenation active phase can be effectively retained. The modified Ga element can more effectively contact the outer metal phase of the active phase, so that in the obtained hydrodenitrogenation catalyst, Ga, Ni, Mo and S form a Ga-Ni-Mo-S combined mixed active phase, thereby achieving the purpose of modification.

[0082] 3. The preparation method of the hydrogenation carbon removal catalyst of the present invention places the metal active phase to be modified in a highly active state with slight sulfur loss, and the outer layer of the active phase edge is exposed active metal. At the same time, the internal three-coordinate sulfur atoms and the stable MoS2 crystal structure of the hydrogenation active phase can be effectively retained, so that the modified Se additive can more effectively contact the outer metal layer of the active phase, so that Se, Ni, Mo and S form a Se-Ni-Mo-S combined mixed active phase, thereby achieving the purpose of modification. DETAILED DESCRIPTION

[0083] The present invention will be further described below with reference to the examples, but it should be understood that the scope of the present invention is not limited by the examples. In the present invention, unless otherwise explicitly stated, percentages and percentage contents are all based on mass.

[0084] In the present invention, the hydrogenation carbon removal catalyst is characterized by TEM-EDS (transmission electron microscopy-energy dispersive X-ray spectroscopy), and the instrument model used is JY / T 011-1996, JEM-1400Flash. The measurement process is as follows: the catalyst particles are ground, and the sample is prepared by a suspension method. 0.1g of the catalyst sample is placed in a 2mL container, ultrasonically dispersed with anhydrous ethanol, and the supernatant is taken. Two to three drops are taken with a dropper and dropped onto a sample net with a diameter of 3mm. The sample is dried to obtain a sample to be tested, and then the sample to be tested is observed and analyzed by TEM. The Se content distribution is statistically analyzed in combination with EDS, and the ratio of the Se content distributed in the Ni-Mo-S active phase region to the total Se content (using Se-Ni-Mo-S / Se) is obtained based on the corresponding peak area of ​​Se. 总 The present invention selects 20 TEM images and combines them with the average value obtained by EDS analysis.

[0085] In the present invention, the sulfur content of the corners of the Ni-Mo-S active phase accounts for the total sulfur content in the Ni-Mo-S active phase, and the TEM-EDS method is used to characterize the sulfur content of the corners of the Ni-Mo-S active phase. The instrument model used is JY / T 011-1996, JEM-1400Flash. The determination process is as follows: the catalyst particles are ground, and the sample is prepared by a suspension method. 0.1g of the catalyst sample is placed in a 2mL container, ultrasonically dispersed with anhydrous ethanol, the supernatant is taken, two or three drops are taken with a dropper, and dropped on a sample net with a diameter of 3mm. After drying, the sample to be tested is obtained, and then TEM is used to observe and analyze the sample to be tested. Any active phase observed under a TEM electron microscope is selected, and then the sulfur content of the active phase less than 1nm away from the edge endpoint (which can be considered as the corner position of the active phase) and the sulfur content in the active phase are statistically analyzed in combination with EDS. The sulfur content of the corners of the Ni-Mo-S active phase accounts for the total sulfur content in the Ni-Mo-S active phase, measured by the corresponding peak area of ​​sulfur (measured by S 边角位 / S 总 The present invention selects 20 TEM images and combines them with the average value obtained by EDS analysis.

[0086] In the present invention, the TEM-EDS characterization method for the hydrodenitrogenation catalyst is the same as that for the hydrodecarbonization catalyst, and the ratio of the Ga content distributed in the Ni-Mo-S active phase region to the total Ga content (Ga-Ni-Mo-S / Ga 总 The sulfur content at the corners of the Ni-Mo-S active phase accounts for the total sulfur content in the Ni-Mo-S active phase (expressed by S 边角位 / S 总 express).

[0087] Example 1

[0088] Weigh 1000.0g of alumina dry powder, add 20.0g of citric acid and 20.0g of sesbania powder, mix well, add 1000.0g of aqueous solution containing 1.0% nitric acid, roll for 20.0min, and squeeze into strips using a 1.8mm diameter clover plate. Dry at 120℃ for 6.0h and then calcine at 700℃ for 6.0h. The calcined carrier is designated as S-1 (Analysis shows that the pore properties of the carrier are as follows: the specific surface area of ​​the carrier is 270m 2 / g, the pore volume of the carrier is 0.9cm 3 74.2 g of ammonium heptamolybdate tetrahydrate, 47.3 g of nickel nitrate hexahydrate, and 150.0 g of deionized water were weighed and stirred at 60° C. for 20 min. The mixture was cooled to room temperature and then diluted to 200.0 mL with deionized water. The resulting solution was designated Q-1.

[0089] Take 200 g of carrier S-1, use Q-1 to impregnate it, dry it naturally for 24 hours, then dry it at 120°C for 4 hours, and then calcine it at 450°C for 5.0 hours. The resulting oxidized catalyst is recorded as CT-1 (based on the weight of the catalyst, the carrier content is 73.3%, the molybdenum content as oxide is 22.2%, and the nickel content as oxide is 4.5%).

[0090] Take 1000g of cyclohexane and 50.0g of dimethyl disulfide, and the prepared sulfiding liquid is recorded as SQ-1.

[0091] Take 1000g of cyclohexane and 2.0g of dimethyl disulfide, and the prepared sulfide liquid is recorded as TQ-1.

[0092] 20.0 g of CT-1 was placed in a reaction tube and subjected to sulfidation treatment using SQ-1. During the sulfidation process, the hydrogen pressure was 6.0 MPa, the hydrogen flow rate was 300.0 mL / min, the flow rate of the sulfiding liquid SQ-1 was 40.0 mL / h, the sulfidation temperature was 350°C, and the sulfidation time was 6 hours. The obtained sulfided hydrogenation catalyst was recorded as SCT-1.

[0093] The reaction tube temperature was lowered to 260°C, the hydrogen pressure was adjusted to 5.0 MPa, the hydrogen flow rate was 200.0 mL / min, and TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h. The treatment time was 9 hours. The resulting catalyst was designated TCT-1.

[0094] The temperature of the reaction tube was lowered to 160°C and the pressure was adjusted to 5.0 MPa. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube. The volume fraction of hydrogen in the mixture was 95% and the volume fraction of hydrogen selenide was 5%. The flow rate of the mixture was 300.0 mL / min, and the treatment time was 3.0 hours. The resulting catalyst was designated ECT-1.

[0095] Example 2

[0096] The preparation process of the sulfided hydrogenation catalyst, denoted as SCT-1, was the same as that in Example 1.

[0097] Take 1000g of cyclohexane and 3.0g of carbon disulfide, and the prepared sulfide liquid is recorded as TQ-2.

[0098] The temperature of the reaction tube containing the sulfided hydrogenation catalyst SCT-1 was lowered to 280°C, and the hydrogen pressure was adjusted to 6.0 MPa at a hydrogen flow rate of 300.0 mL / min. TQ-2 was introduced into the reaction tube at a flow rate of 40.0 mL / h. The treatment time was 12 hours. The resulting catalyst was designated TCT-2.

[0099] The reaction tube temperature was lowered to 180°C and the pressure was adjusted to 8.0 MPa. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube at a volume fraction of 93% hydrogen and 7% hydrogen selenide at a flow rate of 400.0 mL / min. The treatment time was 4.0 hours. The resulting catalyst was designated ECT-2.

[0100] Example 3

[0101] The preparation process of the sulfided hydrogenation catalyst SCT-1 is the same as that in Example 1.

[0102] Take 1000g of cyclohexane and 4.0g of dimethyl sulfoxide to prepare a sulfide solution, which is recorded as TQ-3.

[0103] The temperature of the reaction tube containing the sulfurized hydrogenation catalyst SCT-1 was lowered to 300°C, the hydrogen pressure was adjusted to 10.0 MPa, and the hydrogen flow rate was 400.0 mL / min. TQ-3 was introduced into the reaction tube at a flow rate of 40.0 mL / h. The treatment time was 12 hours. The resulting catalyst was designated TCT-3.

[0104] The reaction tube temperature was lowered to 200°C and the pressure was adjusted to 7.0 MPa. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube at a volume fraction of 90% hydrogen and 10% hydrogen selenide at a flow rate of 500.0 mL / min. The treatment time was 5.0 hours. The resulting catalyst was designated ECT-3.

[0105] Example 4

[0106] The preparation process of the sulfided hydrogenation catalyst SCT-1 is the same as that in Example 1.

[0107] The temperature of the reaction tube containing the sulfided hydrogenation catalyst SCT-1 was lowered to 270°C, and the reaction pressure was adjusted to 6.0 MPa. A mixture of hydrogen and hydrogen sulfide was introduced simultaneously, with a hydrogen:hydrogen sulfide partial pressure ratio of 400:1 and a mixed gas flow rate of 400.0 mL / min. The treatment time was 12 hours. The resulting catalyst was designated TCT-4.

[0108] The reaction tube temperature was lowered to 180°C and the pressure was adjusted to 8.0 MPa. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube at a volume fraction of 93% hydrogen and 7% hydrogen selenide at a flow rate of 500.0 mL / min. The treatment time was 4.0 hours. The resulting catalyst was designated ECT-4.

[0109] Example 5

[0110] The preparation process of the sulfided hydrogenation catalyst SCT-1 is the same as that in Example 1.

[0111] The reaction tube temperature was lowered to 250°C, and the reaction pressure was adjusted to 6.0 MPa. A mixture of hydrogen and hydrogen sulfide was introduced simultaneously, with a hydrogen to hydrogen sulfide partial pressure ratio of 400:1 and a mixed gas flow rate of 400.0 mL / min. The treatment time was 12 hours. The resulting catalyst was designated TCT-5.

[0112] The temperature of the reaction tube was lowered to 210°C, and the pressure was adjusted to 7.0 MPa. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube, with a hydrogen volume fraction of 88% and a hydrogen selenide volume fraction of 12% at a flow rate of 300.0 mL / min. The treatment time was 5.0 hours. The resulting catalyst was designated ECT-5.

[0113] Example 6

[0114] Weigh 1000.0g of alumina dry powder, add 30.0g of citric acid and 10.0g of sesbania powder, mix well, add 900.0g of aqueous solution containing 2.0% nitric acid, roll for 30.0min, and squeeze into strips using a 1.6mm diameter clover plate. Dry at 120℃ for 6.0h and then calcine at 600℃ for 6.0h. The calcined carrier is designated as S-2 (the carrier has a specific surface area of ​​304m 2 / g, pore volume is 0.75cm 3 Weigh 120.0 g of ammonium heptamolybdate tetrahydrate, 80.0 g of nickel nitrate hexahydrate, and 120.0 g of deionized water. Stir thoroughly at 80° C. for 30 min, cool to room temperature, and then dilute to 180.0 mL with deionized water. The resulting solution is designated Q-2.

[0115] Take 200 g of carrier S-2, impregnate it with Q-2, dry it naturally for 24 hours, then dry it at 120°C for 4 hours, and then calcine it at 420°C for 4.0 hours. The resulting oxidized catalyst is recorded as CT-2 (based on the weight of the catalyst, the carrier content is 68.4%, the molybdenum content as oxide is 26.5%, and the nickel content as oxide is 6.1%).

[0116] Take 1000g of cyclohexane and 60.0g of dimethyl disulfide, and the prepared sulfiding liquid is recorded as SQ-2.

[0117] Take 1000g of cyclohexane and 2.0g of dimethyl disulfide, and the prepared sulfide liquid is recorded as TQ-6.

[0118] 1000 g of toluene, 25.0 g of gallium acetylacetonate, and 40.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, which was designated as GQ-6.

[0119] 20.0 g of CT-2 was loaded into a reaction tube and sulfided using SQ-2. During the sulfidation process, the hydrogen pressure was 6.0 MPa, the hydrogen flow rate was 300.0 mL / min, the flow rate of the sulfiding liquid SQ-2 was 40.0 mL / h, the sulfidation temperature was 350°C, and the sulfidation time was 6 hours. The obtained sulfided hydrogenation catalyst was recorded as SCT-2.

[0120] The reaction tube temperature was lowered to 260°C, the hydrogen pressure was adjusted to 5.0 MPa, the hydrogen flow rate was 200.0 mL / min, and TQ-6 was introduced into the reaction tube at a flow rate of 30.0 mL / h. The treatment time was 9 hours. The resulting catalyst was designated TCT-6.

[0121] The reaction tube temperature was lowered to 110°C, the hydrogen pressure was adjusted to 0.8 MPa, the hydrogen flow rate was 120.0 mL / min, and GQ-6 was introduced into the reaction tube at a flow rate of 120.0 mL / h. The treatment time was 8.0 hours. The resulting catalyst was designated ECT-6.

[0122] Example 7

[0123] The preparation process of the sulfided hydrogenation catalyst SCT-2 is the same as that in Example 6.

[0124] Take 1000g of cyclohexane and 3.0g of dimethyl disulfide, and the prepared sulfide liquid is recorded as TQ-7.

[0125] 1000 g of toluene, 15.0 g of triethylgallium, and 50.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, which was designated as GQ-7.

[0126] The temperature of the reaction tube containing the sulfurized hydrogenation catalyst SCT-2 was lowered to 280°C, the hydrogen pressure was adjusted to 6.0 MPa, and the hydrogen flow rate was 300.0 mL / min. TQ-7 was introduced into the reaction tube at a flow rate of 40.0 mL / h. The treatment time was 12 hours. The resulting catalyst was designated TCT-7.

[0127] The reaction tube temperature was lowered to 130°C, the pressure was adjusted to 1.2 MPa, the hydrogen flow rate was 150.0 mL / min, and GQ-7 was introduced into the reaction tube at a flow rate of 120.0 mL / h. The treatment time was 8.0 hours. The resulting catalyst was designated ECT-7.

[0128] Example 8

[0129] The preparation process of the sulfided hydrogenation catalyst SCT-2 is the same as that in Example 6.

[0130] Take 1000g of cyclohexane and 4.0g of dimethyl disulfide, and the prepared sulfiding liquid is recorded as TQ-8.

[0131] 1000 g of toluene, 10.0 g of triethylgallium, 20.0 g of gallium acetylacetonate, and 60.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, which was designated as GQ-8.

[0132] The temperature of the reaction tube containing the sulfurized hydrogenation catalyst SCT-2 was lowered to 300°C, the hydrogen pressure was adjusted to 10.0 MPa, and the hydrogen flow rate was 400.0 mL / min. TQ-8 was introduced into the reaction tube at a flow rate of 40.0 mL / h. The treatment time was 12 hours. The resulting catalyst was designated TCT-8.

[0133] The reaction tube temperature was lowered to 150°C, the pressure was adjusted to 1.8 MPa, the hydrogen flow rate was 180.0 mL / min, and GQ-8 was introduced into the reaction tube at a flow rate of 120.0 mL / h. The treatment time was 8.0 hours. The resulting catalyst was designated ECT-8.

[0134] Example 9

[0135] The preparation process of the sulfurized catalyst SCT-2 is the same as that of Example 6.

[0136] The temperature of the reaction tube containing the sulfided hydrogenation catalyst SCT-2 was lowered to 280°C, the reaction pressure was adjusted to 6.0 MPa, and a mixture of hydrogen and hydrogen sulfide was introduced into the reaction tube at a volume ratio of 400:1 and a total flow rate of 400 mL / min. The treatment time was 12 hours. The resulting catalyst was designated TCT-9.

[0137] 1000 g of toluene, 15.0 g of triethylgallium, 15.0 g of gallium acetylacetonate, and 60.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, which was designated as GQ-9.

[0138] The reaction tube temperature was lowered to 150°C, the pressure was adjusted to 0.6 MPa, the hydrogen flow rate was 150.0 mL / min, and GQ-9 was introduced into the reaction tube at a flow rate of 120.0 mL / h. The treatment time was 8.0 hours. The resulting catalyst was designated ECT-9.

[0139] Example 10

[0140] The preparation process of the sulfurized catalyst SCT-2 is the same as that of Example 6.

[0141] The temperature of the reaction tube containing the sulfided hydrogenation catalyst SCT-2 was lowered to 280°C, the reaction pressure was adjusted to 6.0 MPa, and a mixture of hydrogen and hydrogen sulfide was introduced into the reaction tube at a volume ratio of 500:1 and a total flow rate of 500 mL / min. The treatment time was 12 hours. The resulting catalyst was designated TCT-10.

[0142] 1000 g of toluene, 10.0 g of triethylgallium, 20.0 g of gallium acetylacetonate, and 60.0 g of triethanolamine were prepared to prepare an organic solution containing gallium, which was designated as GQ-10.

[0143] The reaction tube temperature was lowered to 150°C, the pressure was adjusted to 0.6 MPa, the hydrogen flow rate was 150.0 mL / min, and GQ-10 was introduced into the reaction tube at a flow rate of 120.0 mL / h. The treatment time was 8.0 hours. The resulting catalyst was designated ECT-10.

[0144] Comparative Example 1

[0145] 20.0 g of CT-1 was placed in a reaction tube and sulfurized using SQ-1. During the sulfurization process, the hydrogen pressure was 6.0 MPa, the hydrogen flow rate was 300.0 mL / min, the flow rate of the sulfurizing liquid SQ-1 was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6.0 hours. The catalyst after sulfurization was recorded as DCT-1.

[0146] Comparative Example 2

[0147] The preparation process of catalyst DCT-1 is the same as that of Comparative Example 1.

[0148] The reaction tube containing DCT-1 was cooled to 260°C. The hydrogen pressure was adjusted to 5.0 MPa at a hydrogen flow rate of 200.0 mL / min. TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h. The treatment time was 9 hours. The resulting catalyst was designated DCT-2.

[0149] Comparative Example 3

[0150] The preparation process of the sulfided hydrogenation catalyst SCT-1 is the same as that in Example 1.

[0151] The reaction tube containing SCT-1 was cooled to 180°C and the hydrogen pressure was adjusted to 8.0 MPa. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube at a volume fraction of 93% hydrogen and 7% hydrogen selenide at a flow rate of 400.0 mL / min for 4.0 hours. The resulting catalyst was designated DCT-3.

[0152] Comparative Example 4

[0153] The preparation process of catalyst DCT-1 is the same as that of Comparative Example 1.

[0154] The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen pressure was adjusted to 5.0 MPa, the hydrogen flow rate was 200.0 mL / min, and the treatment time was 9 hours. The resulting catalyst was designated DTCT-4.

[0155] The temperature of the reaction tube was lowered to 160°C, and the pressure was adjusted to 5.0 MPa. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube. The volume fraction of hydrogen was 95%, and the volume fraction of hydrogen selenide was 5%. The flow rate of the mixed gas was 300.0 mL / min, and the treatment time was 3.0 hours. The resulting catalyst was designated DCT-4.

[0156] Comparative Example 5

[0157] 20.0 g of CT-1 was placed in a reaction tube. A mixture of hydrogen and hydrogen selenide (90% by volume hydrogen and 10% by volume hydrogen selenide) was introduced into the tube. The reaction temperature was 200°C, the pressure was 7.0 MPa, the flow rate of the mixed gas was 500.0 mL / min, and the reaction time was 5.0 hours. The resulting catalyst was designated DCT-5.

[0158] Comparative Example 6

[0159] 20.0 g of CT-2 was placed in a reaction tube and sulfurized using SQ-2. During the sulfurization process, the hydrogen pressure was 6.0 MPa, the hydrogen flow rate was 300.0 mL / min, the flow rate of the sulfurizing liquid SQ-2 was 40.0 mL / h, the sulfurization temperature was 350°C, and the sulfurization time was 6 hours. The catalyst after sulfurization was recorded as DCT-6.

[0160] Comparative Example 7

[0161] The preparation process of catalyst DCT-6 is the same as that of Comparative Example 6.

[0162] The reaction tube containing DCT-6 was cooled to 260°C. The hydrogen pressure was adjusted to 5.0 MPa at a hydrogen flow rate of 200.0 mL / min. TQ-6 was introduced into the reaction tube at a flow rate of 30.0 mL / h. The treatment time was 9 hours. The resulting catalyst was designated DCT-7.

[0163] Comparative Example 8

[0164] The preparation process of the sulfided hydrogenation catalyst SCT-2 is the same as that in Example 6.

[0165] The reaction tube containing SCT-2 was cooled to 110°C and the pressure was adjusted to 0.8 MPa. Hydrogen was introduced at a rate of 120 mL / min. GQ-6 was introduced into the reaction tube at a rate of 120 mL / h for 8 hours. The resulting catalyst was designated DCT-8.

[0166] Comparative Example 9

[0167] The preparation process of the sulfided hydrogenation catalyst SCT-2 is the same as that in Example 6.

[0168] The reaction tube containing SCT-2 was cooled to 260°C, the hydrogen pressure was adjusted to 5.0 MPa, the hydrogen flow rate was 240.0 mL / min, and the treatment time was 9 hours. The resulting catalyst was designated DTCT-9.

[0169] The reaction tube temperature was lowered to 110°C, the pressure was adjusted to 0.8 MPa, the gas flow rate was 120.0 mL / min, and GQ-6 was introduced into the reaction tube at a flow rate of 120 L / h. The treatment time was 8.0 hours. The resulting catalyst was designated DCT-9.

[0170] Comparative Example 10

[0171] The preparation process of carrier S-2 is the same as that of Example 6.

[0172] Weigh 120.0 g of ammonium heptamolybdate tetrahydrate, 80.0 g of nickel nitrate hexahydrate, 12.0 g of anhydrous gallium nitrate, and 120.0 g of deionized water. Stir thoroughly at 80° C. for 30 min, cool to room temperature, and then dilute to 180.0 mL with deionized water. The resulting solution is recorded as DQ-10.

[0173] 200 g of carrier S-2 was taken and impregnated with DQ-10, dried naturally for 24 hours, dried at 120°C for 4 hours, and calcined at 420°C for 4.0 hours. The obtained oxidized catalyst was recorded as DCT-00.

[0174] 20.0 g of DCT-00 was placed in a reaction tube and sulfurized using SQ-2 (same as in Example 6). During the sulfurization process, the hydrogen pressure was 6.0 MPa, the hydrogen flow rate was 300.0 mL / min, the flow rate of the sulfurizing liquid SQ-2 was 40.0 mL / h, the sulfurization temperature was 350° C., and the sulfurization time was 6 hours. The resulting sulfurized hydrogenation catalyst was designated DCT-10.

[0175] Table 1 Physicochemical composition of the catalysts obtained in each case

[0176]

[0177]

[0178] TEM-EDS characterization of the hydrodecarbonization catalyst and the hydrodenitrogenation catalyst revealed the percentage of Se in the Ni-Mo-S active phase of the hydrodecarbonization catalyst as a percentage of the total Se content, the percentage of Ga in the Ni-Mo-S active phase of the hydrodenitrogenation catalyst as a percentage of the total Ga content, and the percentage of sulfur in the corners of the Ni-Mo-S active phase as a percentage of the total sulfur content in the Ni-Mo-S active phase. See Table 2 for details.

[0179] Table 2 TEM-EDS characterization results of various catalysts

[0180]

[0181] Examples 11-15

[0182] The catalysts obtained in Examples 1-10 were graded and loaded (see Table 4). The properties of the residual oil feedstock used are shown in Table 3. A fixed bed process was used, and a hydrogenation protective agent (FZC-100B), a hydrodemetallization catalyst (FZC-204A), a hydrodesulfurization catalyst (FZC-33B), a hydrodecarbonization catalyst, and a hydrodenitrogenation catalyst were loaded in sequence according to the direction of material flow. The loading volume ratio of the hydrogenation protective agent, the hydrodemetallization catalyst, the hydrodesulfurization catalyst, the hydrodecarbonization catalyst, and the hydrodenitrogenation catalyst was 0.5:1.5:1.5:3.0:3.5. The operating conditions were: reaction temperature 390°C, reaction pressure 20.0 MPa, hydrogen-to-oil volume ratio 1000:1, and liquid hourly space velocity 0.3 h -1 The results of the 2000h evaluation are shown in Table 4.

[0183] Comparative Examples 11-15

[0184] The sulfided catalysts obtained in Comparative Examples 1-10 were graded and loaded (see Table 4). The properties of the residual oil feedstock used are shown in Table 3. A fixed bed process was used, and a hydrogenation protective agent (FZC-100B), a hydrodemetallization catalyst (FZC-204A), a hydrodesulfurization catalyst (FZC-33B), a hydrodecarbonization catalyst, and a hydrodenitrification catalyst were loaded in sequence according to the direction of material flow. The loading volume ratio of the hydrogenation protective agent, hydrodemetallization catalyst, hydrodesulfurization catalyst, hydrodecarbonization catalyst, and hydrodenitrification catalyst was 0.5:1.5:1.5:3.0:3.5. The operating conditions were: reaction temperature 390°C, reaction pressure 20.0 MPa, hydrogen-to-oil volume ratio 1000:1, and liquid hourly space velocity 0.3 h -1 The results of the 2000h evaluation are shown in Table 4.

[0185] Table 3 Properties of residual oil feedstock

[0186] <![CDATA[Density, kg / m 3 > 1002 Vanadium + nickel content, μg / g 99.8 Sulfur content, μg / g 39745 Nitrogen content, μg / g 4153 Saturated fraction, wt% 37.7 Aromatic content, wt% 29.0 Gum, wt% 30.5 Asphaltene, wt% 2.8 Carbon residue value, wt% 19.8

[0187] Table 4 Analysis results of hydrogenation products after 2000h of catalyst evaluation

[0188]

[0189] It can be seen from the evaluation results in Table 4 that the catalyst grading method adopted in the present invention has good hydrogenation carbon removal, hydrogenation saturation ability and good hydrogenation denitrification ability.

Claims

1. A method for hydrotreating residual oil, using a fixed bed hydrogenation process, characterized in that: The method comprises: in the presence of hydrogen, contacting a residual oil raw material with at least one hydroremoval of carbon residue catalyst and at least one hydrodenitrogenation catalyst in sequence to carry out a hydrogenation reaction to obtain hydrogenated oil; The hydroremoval of carbon residue catalyst is a sulfided catalyst, including a carrier and active metals Mo and Ni, and also Se. TEM-EDS characterization shows that the Se content distributed in the Ni-Mo-S active phase region accounts for 65%-95% of the total Se content. The hydrodenitrogenation catalyst is a sulfided catalyst, including a carrier and active metals Mo and Ni, and also Ga. Characterization using the TEM-EDS method shows that the Ga content distributed in the Ni-Mo-S active phase region accounts for 60%-95% of the total Ga content.

2. The method according to claim 1, characterized in that The hydroremoval of carbon residue catalyst was characterized by TEM-EDS method, and the Se content distributed in the Ni-Mo-S active phase region accounted for 78%-95% of the total Se content; The hydrodenitrogenation catalyst is a sulfided catalyst, and is characterized by a TEM-EDS method. The Ga content distributed in the Ni-Mo-S active phase region accounts for 75%-90% of the total Ga content.

3. The method according to claim 1, characterized in that The hydroremoval of carbon residue catalyst is characterized by a TEM-EDS method, and the sulfur content at the corners of the Ni-Mo-S active phase accounts for less than 6.0% of the total sulfur content in the Ni-Mo-S active phase.

4. The method according to claim 3, characterized in that The hydroremoval of carbon residue catalyst is characterized by a TEM-EDS method, and the sulfur content at the corners of the Ni-Mo-S active phase accounts for 0.5%-4.0% of the total sulfur content in the Ni-Mo-S active phase.

5. The method according to claim 1, characterized in that Based on the mass of the hydrodecarbonization catalyst, the content of molybdenum calculated as Mo is 8%-20%, the content of nickel calculated as Ni is 1.5%-6.5%, the content of sulfur element calculated as S is 4%-15%, the content of Se element calculated as Se is 0.5%-5.0%, and the content of the carrier is 55%-80%.

6. The method according to claim 5, characterized in that Based on the mass of the hydrodecarbonization catalyst, the content of molybdenum calculated as Mo is 12.5%-16.5%, the content of nickel calculated as Ni is 2.0%-5.0%, the content of sulfur element calculated as S is 6%-12%, the content of Se element calculated as Se is 1.0%-4.0%, and the content of the carrier is 55%-70%.

7. The method according to claim 1, characterized in that The hydrodenitrogenation catalyst is characterized by a TEM-EDS method, and the sulfur content at the corners of the Ni-Mo-S active phase accounts for less than 4.0% of the total sulfur content in the Ni-Mo-S active phase.

8. The method according to claim 7, characterized in that The hydrodenitrogenation catalyst is characterized by a TEM-EDS method, and the sulfur content at the corners of the Ni-Mo-S active phase accounts for 0.5%-3.0% of the total sulfur content in the Ni-Mo-S active phase.

9. The method according to claim 1, characterized in that The hydrodenitrogenation catalyst has, based on the mass of the hydrodenitrogenation catalyst, a molybdenum content calculated as Mo of 10%-20%, a nickel content calculated as Ni of 1.5%-6.5%, a Ga content calculated as Ga of 0.4%-4.0%, a sulfur content calculated as S of 8%-15%, and a carrier content of 55%-75%.

10. The method according to claim 9, characterized in that The hydrodenitrogenation catalyst has, based on the mass of the hydrodenitrogenation catalyst, a molybdenum content calculated as Mo of 13%-18%, a nickel content calculated as Ni of 2.0%-6%, a Ga content calculated as Ga of 0.8%-3.0%, a sulfur content calculated as S of 9%-14%, and a carrier content of 55%-70%.

11. The method according to claim 1, characterized in that The preparation method of the hydrogenation carbon residue removal catalyst comprises: (1) Sulfiding the oxidized hydrogenation catalyst to obtain a sulfurized hydrogenation catalyst; (2) desulfurizing the sulfided hydrogenation catalyst obtained in step (1); (3) reacting the catalyst treated in step (2) with a mixed gas of hydrogen selenide and hydrogen to obtain a hydrogenation carbon removal catalyst; Wherein, in step (2), the desulfurization treatment is a mild desulfurization treatment, which is carried out in at least one of the following ways: (a) desulfurizing the sulfided hydrogenation catalyst obtained in step (1) using hydrogen gas containing hydrogen sulfide; (b) desulfurizing the sulfided hydrogenation catalyst obtained in step (1) using a sulfiding liquid in the presence of hydrogen; In method (a), the volume ratio of hydrogen sulfide to hydrogen is 200:1-800:1; In method (b), the mass fraction of sulfur compounds in the sulfiding liquid is 0.1%-0.6%; In step (2), the desulfurization treatment temperature is 180-370°C, the treatment time is 4-24 hours, and the total pressure is 2.0-18.0 MPa; The preparation method of the hydrodenitrogenation catalyst comprises: (I) performing a primary sulfurization on the oxidized hydrogenation catalyst to obtain a sulfurized hydrogenation catalyst; (II) desulfurizing the sulfided hydrogenation catalyst obtained in step (I); (III) contacting the catalyst treated in step (II) with an organic solution containing Ga element and a stabilizer to react and obtain a hydrodenitrogenation catalyst; Wherein, in step (II), the desulfurization treatment is a mild desulfurization treatment, which is carried out in at least one of the following ways: (i) desulfurizing the sulfided hydrogenation catalyst obtained in step (1) using hydrogen gas containing hydrogen sulfide; (ii) desulfurizing the sulfided hydrogenation catalyst obtained in step (1) using a sulfiding liquid in the presence of hydrogen; In method (i), the volume ratio of hydrogen sulfide to hydrogen is 200:1-800:1; In method (ii), the mass fraction of sulfur compounds in the sulfiding liquid is 0.1%-0.6%; In step (II), the desulfurization treatment temperature is 180-370°C, the treatment time is 4-24 hours, and the total pressure is 2.0-18.0 MPa; In step (III), the stabilizer is one or more of triethanolamine, diethanolamine, monoethanolamine, and aniline.

12. The method according to claim 11, characterized in that In step (1), the sulfurization treatment is a full sulfurization treatment, and the conditions of the sulfurization treatment are as follows: the temperature is 240-400 ° C, the sulfurization time is 3-8 hours, the hydrogen pressure during the sulfurization process is 2.0-12.0 MPa, and the hydrogen flow rate is 2.0-15.0 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

13. The method according to claim 12, characterized in that In step (1), the sulfurization treatment is a full sulfurization treatment, and the conditions of the sulfurization treatment are as follows: the temperature is 280-380°C, the sulfurization time is 3-8h, the hydrogen pressure during the sulfurization process is 3.0-10.0 MPa, and the hydrogen flow rate is 3.0-10.0 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

14. The method according to claim 11, characterized in that In step (2), the desulfurization treatment temperature is 200-300°C, the treatment time is 6-16 hours, and the total pressure is 4.0-15.0 MPa.

15. The method according to claim 14, characterized in that The temperature of the desulfurization treatment in step (2) is 50-100° C. lower than the temperature of the sulfurization treatment in step (1).

16. The method according to claim 11, characterized in that In method (a), the volume ratio of hydrogen sulfide to hydrogen is 300:1-600:1, and the total gas flow rate is 5-30 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

17. The method according to claim 16, characterized in that In method (a), the total gas flow rate is 10-20 mL min -1 ·g -1 Oxidative hydrogenation catalyst.

18. The method according to claim 11, characterized in that In method (b), the sulfiding liquid includes a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-nonyl polysulfide, and dimethyl sulfoxide; and the organic solvent is at least one of cyclohexane, n-heptane, aviation kerosene, and diesel.

19. The method according to claim 18, characterized in that In method (b), during the desulfurization process, the flow rate of the sulfiding liquid is 0.2-2.0 mL·h -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate is 5-30mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

20. The method according to claim 19, characterized in that In method (b), during the desulfurization process, the flow rate of the sulfiding liquid is 0.4-1.5 mL·h -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate is 10-20mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

21. The method according to claim 11, characterized in that In step (3), the reaction conditions are as follows: reaction temperature is 120-250° C., reaction time is 1-8 hours, and reaction pressure is 2.0-12.0 MPa.

22. The method according to claim 21, characterized in that In step (3), the reaction conditions are as follows: reaction temperature is 150-220°C, reaction time is 2-6 hours, and reaction pressure is 4.0-8.0 MPa.

23. The method according to claim 11, characterized in that In step (3), the volume fraction of hydrogen selenide in the mixed gas is 1%-20%, the volume fraction of hydrogen is 80%-99%, and the flow rate of the mixed gas is 5-40 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

24. The method according to claim 23, characterized in that In step (3), the volume fraction of hydrogen selenide in the mixed gas is 3%-15%, and the volume fraction of hydrogen is 85%-97%; the flow rate of the mixed gas is 10-30 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

25. The method according to claim 11, characterized in that In step (I), the primary vulcanization is full vulcanization, and the conditions of the primary vulcanization are as follows: temperature of 240-400°C, vulcanization time of 3-8h, hydrogen pressure of 2.0-12.0MPa, hydrogen flow rate of 2.0-15.0 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

26. The method according to claim 11, characterized in that In step (II), the desulfurization treatment is performed at a temperature of 200-300° C., a treatment time of 6-16 hours, and a total pressure of 4.0-15.0 MPa.

27. The method according to claim 26, characterized in that In step (II), the temperature of the desulfurization treatment is 50-100° C. lower than the temperature of the primary sulfidation in step (I).

28. The method according to claim 11, characterized in that In method (i), the volume ratio of hydrogen sulfide to hydrogen is 300:1-600:1, and the total gas flow rate is 5-30 mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

29. The method according to claim 28, characterized in that In method (i), the total gas flow rate is 10-20 mL min -1 ·g -1 Oxidative hydrogenation catalyst.

30. The method according to claim 11, characterized in that In method (ii), the sulfiding liquid comprises a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-nonyl polysulfide, and dimethyl sulfoxide; and the organic solvent is at least one of cyclohexane, n-heptane, aviation kerosene, and diesel. During the desulfurization treatment, the flow rate of the sulfiding liquid is 0.2-2.0 mL·h -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate is 5-30mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

31. The method according to claim 30, characterized in that In method (ii), during the desulfurization process, the flow rate of the sulfiding liquid is 0.4-1.5 mL·h -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate is 10-20mL·min -1 ·g -1 Oxidative hydrogenation catalyst.

32. The method according to claim 11, characterized in that In step (III), the organic solution containing the Ga element and the stabilizer comprises one or more of toluene, cyclohexane, decahydronaphthalene, tetrahydronaphthalene, and n-heptane, and the Ga-containing compound comprises one or more of gallium acetylacetonate and triethylgallium; wherein the mass content of the Ga-containing compound in the organic solution containing the Ga element and the stabilizer is 0.5%-5%, and the mass content of the stabilizer is 2%-8%.

33. The method according to claim 11, characterized in that In step (III), the reaction temperature is 80-200°C, the pressure is 0.2-4.0 MPa, the reaction time is 2-12 hours, and the flow rate of hydrogen is 2-20 mL·min -1 ·g -1 Oxidized hydrogenation catalyst; the flow rate of the organic solution containing Ga element and stabilizer is 2-10 mL·h -1 ·g -1 Oxidative hydrogenation catalyst.

34. The method according to claim 33, characterized in that In step (III), the reaction temperature is 100-160° C. and the pressure is 0.5-2.0 MPa.

35. The method according to claim 1, wherein The operating conditions of the fixed bed hydrogenation process are as follows: reaction temperature of 300-400°C, reaction pressure of 8.0-25.0 MPa, hydrogen-to-oil volume ratio of 500:1-1500:1, liquid hourly volume space velocity of 0.1-1.0 h -1 .

36. The method according to claim 1, wherein The total loading volume of the hydrodecarbonization catalyst and the hydrodenitrogenation catalyst accounts for more than 50% of the total catalyst loading volume; the loading volume ratio of the hydrodecarbonization catalyst to the hydrodenitrogenation catalyst is 1:3-3:

1.

37. The method according to claim 36, characterized in that The total loading volume of the hydrodecarbonization catalyst and the hydrodenitrogenation catalyst accounts for 60% to 85% of the total catalyst loading volume.

38. The method according to claim 1, wherein The nitrogen content of the residual oil raw material is above 2000 μg / g, and the residual carbon value is above 10 wt%.

39. The method according to claim 38, characterized in that The residual oil raw material has a nitrogen content of 2500-4500 μg / g and a carbon residue value of 15wt%-20wt%.

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