Hydrogenation catalyst grading method for prolonging operation period of residual oil hydrogenation device and residual oil hydrotreating method

Abstract

The invention provides a hydrogenation catalyst grading method for prolonging the operation period of a residual oil hydrogenation device and a residual oil hydrotreating method. The hydrogenation catalyst grading method comprises the following steps: respectively dividing four hydrogenation reactors which are connected in series into a filling area at the bottom and a reaction area above the filling area, and filling the filling areas of one or more hydrogenation reactors at the front section of the four hydrogenation reactors which are connected in series with a metal agent, filling the filling areas of one or more hydrogenation reactors at the rear section with a carbon residue containing agent; the reaction zones of the four hydrogenation reactors connected in series form a total reaction zone, and the total reaction zone is sequentially filled with a hydrogenation protection catalyst, a hydrodemetallization catalyst, a hydrodesulfurization catalyst and a hydrogenation carbon residue removal catalyst along the material flow direction. The hydrogenation catalyst grading method provided by the invention is suitable for a fixed bed residual oil hydrogenation process, and the operation period of a residual oil hydrogenation device is prolonged.

Description

Technical Field

[0001] The invention relates to a hydrogenation catalyst grading method for extending the operating period of a residual oil hydrogenation device and a residual oil hydrogenation treatment method, belonging to the technical field of residual oil hydrogenation. Background Art

[0002] In the petroleum refining industry, as crude oil becomes heavier and inferior, the residual oil hydrogenation process has gradually become a crucial process. The market competition is fierce, and the crude oil processing process has meager profits. For refining companies, reducing the cost of crude oil processing is becoming increasingly important. The fixed-bed residual oil hydrogenation process uses poor raw materials, so the catalyst life is short and the catalyst needs to be replaced every year. The amount used is large, which brings an economic burden to refining companies. Therefore, technical personnel in the industry use a variety of methods to improve the residual oil hydrogenation process to extend the operation cycle of the device in order to achieve the purpose of reducing the cost of the process.

[0003] At present, the main method to extend the operation cycle of the fixed-bed residue oil hydrogenation unit is to improve the residue oil hydrogenation unit. The first method is to remove the reactor full of metal impurities and carbon deposits, such as switching the protection reactor. The second method is to remove metal impurities and carbon deposits online, such as using a cleaning agent to clean carbon deposits. The third method is to increase the porosity of the catalyst bed so that the existing catalyst can accommodate more metal impurities and carbon deposits, such as using an upflow reactor. However, these methods require the addition of a hydrogenation reactor, which is not only expensive but also difficult to operate.

[0004] In recent years, extending the operating cycle of the device by improving the performance and gradation of the residual oil hydrogenation catalyst has become a research hotspot in the industry. CN113856695A discloses a residual oil hydrogenation catalyst gradation method. The method extends the operating cycle of the residual oil hydrogenation device by optimizing the components of the residual oil hydrogenation catalyst, especially optimizing the structure-activity relationship of the demetallizing agent. However, the effect of extending the operating cycle of the method is limited, mainly because the residual oil hydrogenation catalyst needs to take into account both hydrogenation activity and stability. If the catalyst operating cycle is increased by increasing the pore volume, the hydrogenation catalytic activity will be affected. Therefore, for the existing catalyst system based on alumina carrier and active metal, there is a maximum value of the operating cycle, and it is difficult to break through the upper limit.

[0005] CN107875978B discloses a gradation loading method for hydrogenation catalysts. This method is mainly aimed at high iron and high calcium residual oil, and the operation cycle is improved by adjusting the placement and quantity of different types of residual oil hydrogenation catalysts. However, for general residual oils that are not high iron and high calcium, this gradation method has too low activity and a fast heating speed, which not only fails to improve the operation cycle, but also affects the operation cycle and stability.

[0006] CN109701452B discloses a grading method for paraffin-based residual oil hydroprocessing catalysts. This method is mainly for paraffin-based residual oil, and the operation cycle is improved by adjusting the placement and quantity of different types of residual oil hydrogenation catalysts. However, this grading method is too active for general non-paraffin-based residual oil, and the catalyst still deactivates quickly, which not only fails to improve the operation cycle, but also affects the operation cycle and stability.

[0007] Therefore, developing a novel residue hydrogenation catalyst grading method to increase the operating cycle of the residue hydrogenation catalyst, thereby improving the economic efficiency of the residue hydrogenation unit, is still one of the problems to be solved urgently in the field. Summary of the invention

[0008] In order to solve the above technical problems, the purpose of the present invention is to provide a hydrogenation catalyst grading method and a residue oil hydrotreating method for extending the operating cycle of a residue oil hydrotreating unit. The hydrogenation catalyst grading method provided by the present invention is suitable for a fixed bed residue oil hydrotreating process and can extend the operating cycle of a residue oil hydrotreating unit.

[0009] In order to achieve the above-mentioned object, the first aspect of the present invention provides a hydrogenation catalyst grading method for extending the operation period of a residual oil hydrogenation unit, which comprises: four hydrogenation reactors connected in series are respectively divided into a filling area at the bottom and a reaction area above the filling area, a metal agent is filled in the filling area of ​​one or several hydrogenation reactors in the front section of the four hydrogenation reactors connected in series, and a carbon residue agent is filled in the filling area of ​​one or several hydrogenation reactors in the rear section, and the filling areas of the four hydrogenation reactors connected in series are all filled with a metal agent or a carbon residue agent;

[0010] The reaction zones of the four hydrogenation reactors connected in series constitute a total reaction zone, in which a hydrogenation protection catalyst, a hydrogenation demetallization catalyst, a hydrogenation desulfurization catalyst and a hydrogenation decarbonization catalyst are sequentially loaded along the direction of the flow.

[0011] Wherein, the metal-containing agent at least includes a first aluminum oxide, and the first aluminum oxide is an aluminum oxide containing mesopores and macropores;

[0012] The carbon residue accommodating agent at least includes a second aluminum oxide, and the second aluminum oxide is aluminum oxide containing only mesopores.

[0013] In the above-mentioned hydrogenation catalyst grading method, preferably, the reaction zone of the one or several hydrogenation reactors in the front section is filled with one or several of the hydrogenation protection catalyst, the hydrogenation demetallization catalyst and the hydrogenation desulfurization catalyst in sequence along the logistics direction, and the reaction zone of the one or several hydrogenation reactors in the rear section is filled with one or several of the hydrogenation demetallization catalyst, the hydrogenation desulfurization catalyst and the hydrogenation decarbonization catalyst in sequence along the logistics direction.

[0014] In the above-mentioned hydrogenation catalyst grading method, preferably, the metal agent includes three types of metal agents with equivalent diameters of fine, medium and coarse. The equivalent diameter of the fine metal agent is 2.5-3.5 mm, the equivalent diameter of the medium metal agent is 5.5-6.5 mm, and the equivalent diameter of the coarse metal agent is 11.5-12.5 mm.

[0015] In the above-mentioned hydrogenation catalyst grading method, preferably, the metal agent is loaded in the following manner: three types of metal agents of equivalent diameters, namely, coarse, medium and fine, are loaded in the loading area of ​​the hydrogenation reactor from bottom to top. More preferably, the metal agent is loaded in the following manner: the coarse metal agent is loaded above the outlet collector of the hydrogenation reactor; and the bed volumes of the neutral and fine metal agents are respectively the same as the bed volumes of the coarse metal agent.

[0016] In the above-mentioned hydrogenation catalyst grading method, preferably, the loading amount of the metal-containing agent in one hydrogenation reactor is 0.5% to 3.0% of the volume of one hydrogenation reactor; more preferably, the loading amount of the metal-containing agent in one hydrogenation reactor is 1.5% to 2.5% of the volume of one hydrogenation reactor.

[0017] In the above-mentioned hydrogenation catalyst grading method, preferably, the carbon residue tolerant agent includes three types of carbon residue tolerant agents with equivalent diameters of fine, medium and coarse. The equivalent diameter of the fine carbon residue tolerant agent is 2.5-3.5 mm, the equivalent diameter of the medium carbon residue tolerant agent is 5.5-6.5 mm, and the equivalent diameter of the coarse carbon residue tolerant agent is 11.5-12.5 mm.

[0018] In the above hydrogenation catalyst grading method, preferably, the carbon residue tolerant agent is loaded in the following manner: coarse, medium and fine carbon residue tolerant agents of three equivalent diameters are loaded in the loading area of ​​the hydrogenation reactor from bottom to top. More preferably, the carbon residue tolerant agent is loaded in the following manner: the coarse carbon residue tolerant agent is loaded above the outlet collector of the hydrogenation reactor; and the bed volumes of the medium and fine carbon residue tolerant agents are respectively the same as the bed volumes of the coarse carbon residue tolerant agent.

[0019] In the above-mentioned hydrogenation catalyst grading method, preferably, the loading amount of the carbon residue tolerant agent in one hydrogenation reactor is 0.5% to 3.0% of the volume of one hydrogenation reactor; more preferably, the loading amount of the carbon residue tolerant agent in one hydrogenation reactor is 1.5% to 2.5% of the volume of one hydrogenation reactor.

[0020] In the present invention, the equivalent diameter refers to the maximum value of the straight-line distance between any two points on the catalyst geometry.

[0021] In the above hydrogenation catalyst grading method, preferably, the first alumina comprises mesopores of 5 to 20 nm and macropores of 100 to 500 nm, and the mesopore volume is 0.60 cm 3 / g and above, the pore size presents a bimodal distribution.

[0022] In the above-mentioned hydrogenation catalyst grading method, preferably, the metal-containing agent also includes a first active component loaded on the first alumina; the first active component includes a first main active component and a first auxiliary active component, the first main active component includes molybdenum oxide and / or tungsten oxide, and the first auxiliary active component includes nickel oxide and / or cobalt oxide; based on the total weight of the metal-containing agent as 100%, the total loading amount of the first active component is 5% to 15%.

[0023] In the above-mentioned hydrogenation catalyst grading method, preferably, the first alumina further contains one or a combination of boron, germanium, zirconium and phosphorus, etc. More preferably, based on the total weight of the first alumina being 100%, the content of one or a combination of boron, germanium, zirconium and phosphorus, etc., is 0.1% to 10%.

[0024] In the above-mentioned hydrogenation catalyst grading method, preferably, the first main active component is molybdenum oxide, and the first auxiliary active component is nickel oxide.

[0025] In the above hydrogenation catalyst grading method, preferably, based on the total weight of the metal agent as 100%, the loading amount of the first main active component is 6% to 9%, and the loading amount of the first auxiliary active component is 1% to 3%.

[0026] In the above-mentioned hydrogenation catalyst grading method, preferably, the bulk density of the metal agent is 0.20 to 0.60 g / cm 3 , with a specific surface area of ​​100 to 160 m 2 / g.

[0027] In the above hydrogenation catalyst grading method, preferably, the pore volume of mesopores with a pore size of 5 to 15 nm in the second alumina accounts for 85% to 95% of the total mesopore volume, and the total mesopore volume is 0.50 cm 3 / g or above.

[0028] In the above-mentioned hydrogenation catalyst grading method, preferably, the residual carbon tolerant agent also includes a second active component loaded on the second alumina; the second active component includes a second main active component and a second auxiliary active component, the second main active component includes molybdenum oxide and / or tungsten oxide, and the second auxiliary active component includes nickel oxide and / or cobalt oxide; based on the total weight of the residual carbon tolerant agent as 100%, the total loading amount of the second active component is 10% to 25%.

[0029] In the above hydrogenation catalyst grading method, preferably, the second alumina further contains one or a combination of boron, germanium, zirconium and phosphorus. More preferably, based on the total weight of the second alumina being 100%, the content of one or a combination of boron, germanium, zirconium and phosphorus is 0.1% to 10%.

[0030] In the above-mentioned hydrogenation catalyst grading method, preferably, the second main active component is molybdenum oxide, and the second auxiliary active component is nickel oxide.

[0031] In the above hydrogenation catalyst grading method, preferably, based on the total weight of the carbon residue tolerant agent being 100%, the loading amount of the second main active component is 12% to 15%, and the loading amount of the second auxiliary active component is 2% to 4%.

[0032] In the above-mentioned hydrogenation catalyst grading method, preferably, the bulk density of the carbon residue absorbing agent is 0.40 to 0.75 g / cm 3 , with a specific surface area of ​​150 to 250 m 2 / g.

[0033] In the above-mentioned hydrogenation catalyst grading method, in order to achieve the goal of effectively extending the operation cycle, the present invention provides different grading schemes according to the different contents of metal Ni+V in the residual oil raw material. Preferably, when the Ni+V content in the residual oil raw material is ≤40μg / g, the metal-containing agent is loaded in the filling area of ​​the first hydrogenation reactor along the logistics direction, and the carbon-containing agent is loaded in the filling area of ​​the second, third and fourth hydrogenation reactors; when the Ni+V content in the residual oil raw material is >40μg / g and ≤70μg / g, the metal-containing agent is loaded in the filling area of ​​the first and second hydrogenation reactors along the logistics direction, and the carbon-containing agent is loaded in the filling area of ​​the third and fourth hydrogenation reactors; when the Ni+V content in the residual oil raw material is >70μg / g and ≤100μg / g, the metal-containing agent is loaded in the filling area of ​​the first, second and third hydrogenation reactors along the logistics direction, and the carbon-containing agent is loaded in the filling area of ​​the fourth hydrogenation reactor.

[0034] In the present invention, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydroremoval of carbon residue catalyst can adopt the corresponding catalysts in the field of residual oil hydrogenation disclosed in the prior art. Preferably, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydroremoval of carbon residue catalyst can adopt the PHR series residual oil hydrogenation catalyst developed by the Petrochemical Research Institute of China Petroleum Group.

[0035] In the above-mentioned hydrogenation catalyst grading method, preferably, the loading amount of the hydrogenation protection catalyst is 2% to 10% of the total volume of the four hydrogenation reactors connected in series, the loading amount of the hydrodemetallization catalyst is 35% to 70% of the total volume of the four hydrogenation reactors connected in series, the loading amount of the hydrodesulfurization catalyst is 10% to 40% of the total volume of the four hydrogenation reactors connected in series, the loading amount of the hydrodecarbonization catalyst is 10% to 40% of the total volume of the four hydrogenation reactors connected in series, and the remainder of the total volume of the four hydrogenation reactors connected in series is the loading amount of the metal containing agent and the carbon containing agent.

[0036] In the above-mentioned hydrogenation catalyst grading method, preferably, the hydrogenation reactor is a fixed bed downflow reactor.

[0037] The second aspect of the present invention provides a residual oil hydroprocessing method, which comprises: under hydroprocessing reaction conditions, allowing the residual oil feedstock and hydrogen to pass through four hydrogenation reactors connected in series in sequence, and contacting with the catalyst loaded in the hydrogenation reactor according to the above-mentioned hydrogenation catalyst grading method for extending the operating cycle of the residual oil hydrogenation device to carry out a hydrogenation reaction, so as to obtain a hydroprocessing product.

[0038] In the above-mentioned residue oil hydroprocessing method, preferably, the residue oil raw material includes one or a combination of atmospheric residue oil, vacuum residue oil, deasphalted oil, coal tar and coal liquefaction heavy oil.

[0039] In the above-mentioned residue oil hydroprocessing method, preferably, the S content in the residue oil feedstock is 4.5 wt% or less, the MCR is 18 wt% or less, and the Ni+V content is 100 μg / g or less.

[0040] In the above-mentioned residue oil hydroprocessing method, preferably, the hydroprocessing reaction conditions include: hydrogen partial pressure of 10.0MPa to 18.0MPa, hydrogen to oil volume ratio of 200 to 2000, liquid hourly volume space velocity of 0.10 to 1.0h -1 , the reaction temperature of the first hydrogenation reactor is 310-420°C, and the reaction temperature of the other hydrogenation reactors is 300-420°C. More preferably, the hydroprocessing reaction conditions include: hydrogen partial pressure of 13.0MPa-15.0MPa, hydrogen-to-oil volume ratio of 420-1500, liquid hourly volume space velocity of 0.14-0.45h -1 The reaction temperature of the first hydrogenation reactor is 360-420°C, and the reaction temperature of the other hydrogenation reactors is 315-410°C.

[0041] It should be noted that the hydroprocessing reaction conditions of each hydrogenation reactor may be the same or different, as long as they are within the above range.

[0042] The present invention provides a hydrogenation catalyst grading method for extending the operating cycle of a residual oil hydrogenation unit, and a residual oil hydrogenation treatment method. In view of the demand for extending the operating cycle of a residual oil hydrogenation unit in the petroleum refining industry, the present invention proposes to replace the porcelain balls at the bottom of the hydrogenation reactor with metal-containing agents and carbon-containing agents, and form a new gradation with the existing hydrogenation protection catalyst, hydrogenation demetallization catalyst, hydrogenation desulfurization catalyst and hydrogenation decarbonization catalyst in the hydrogenation reactor. The equivalent diameter of the metal-containing agent and the carbon-containing agent of the present invention is the same as or similar to the diameter of the porcelain balls at the bottom of the original hydrogenation reactor, and the strength meets the basic requirements for supporting the main agent of the residual oil hydrogenation catalyst (i.e., hydrogenation protection catalyst, hydrogenation demetallization catalyst, hydrogenation desulfurization catalyst and hydrogenation decarbonization catalyst). Moreover, the grading method of the hydrogenation catalyst of the present invention can accommodate more metal impurities and carbon deposits, greatly extending the operating cycle of the residual oil hydrogenation unit.

[0043] The technical solution of the present invention has at least the following beneficial effects:

[0044] First, the present invention mainly develops the hydrogenation catalyst grading method of the present invention based on the phenomenon of high accumulation of metal impurities and high carbon deposition caused by changes in the flow direction of the bottom logistics of the fixed bed downflow reactor. Under the synergistic effect of the catalyst grading of the present invention, not only can the metal impurities and carbon deposition at the bottom of the reactor be effectively removed, but also the ability of the entire residual oil hydrogenation system to efficiently remove and accommodate metal impurities and carbon deposition can be improved;

[0045] Second, compared with the conventional residue oil hydrogenation catalyst grading system, the hydrogenation catalyst grading system of the present invention has increased metal tolerant agents and residual carbon tolerant agents, thereby improving the metal impurity and carbon deposition tolerance of the residue oil hydrogenation catalyst system, extending the operation cycle of the residue oil hydrogenation unit, increasing the operation efficiency of the residue oil hydrogenation unit, and improving the economic efficiency, thereby achieving the effect of reducing costs and increasing efficiency for heavy oil processing enterprises. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 A schematic diagram of a method for filling a metal agent in a filling area at the bottom of a hydrogenation reactor provided in a specific embodiment of the present invention.

[0047] Figure 2 A schematic diagram of a filling method of a carbon residue containing agent in a filling area at the bottom of a hydrogenation reactor provided in a specific embodiment of the present invention. DETAILED DESCRIPTION

[0048] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0049] The first aspect of the present invention provides a hydrogenation catalyst grading method for extending the operation cycle of a residual oil hydrogenation unit, comprising: dividing four hydrogenation reactors connected in series into a filling area at the bottom and a reaction area above the filling area, filling a metal agent in the filling area of ​​one or several hydrogenation reactors at the front section of the four hydrogenation reactors connected in series, and filling a carbon residue agent in the filling area of ​​one or several hydrogenation reactors at the rear section, and the filling areas of the four hydrogenation reactors connected in series are all filled with a metal agent or a carbon residue agent;

[0050] The reaction zones of the four hydrogenation reactors connected in series constitute a total reaction zone, in which a hydrogenation protection catalyst, a hydrogenation demetallization catalyst, a hydrogenation desulfurization catalyst and a hydrogenation decarbonization catalyst are sequentially loaded along the logistics direction;

[0051] Wherein, the metal-containing agent at least includes a first aluminum oxide, and the first aluminum oxide is an aluminum oxide containing mesopores and macropores;

[0052] The carbon residue accommodating agent at least includes a second aluminum oxide, and the second aluminum oxide is aluminum oxide containing only mesopores.

[0053] In the present invention, conventional porcelain balls are not loaded in the four hydrogenation reactors connected in series.

[0054] In the present invention, one or several hydrogenation reactors in the front section are generally hydrogenation reactors with high metal impurity content, and one or several hydrogenation reactors in the rear section are generally hydrogenation reactors with high carbon deposit content.

[0055] In the present invention, the reaction zones of the one or several hydrogenation reactors in the front section are sequentially filled with one or several of a hydrogenation protection catalyst, a hydrogenation demetallization catalyst and a hydrogenation desulfurization catalyst along the logistics direction, and the reaction zones of the one or several hydrogenation reactors in the rear section are sequentially filled with one or several of a hydrogenation demetallization catalyst, a hydrogenation desulfurization catalyst and a hydrogenation decarbonization catalyst along the logistics direction.

[0056] In the existing fixed-bed residue oil hydrogenation process, the basic principle of catalyst grading is that the catalyst pore size is from large to small along the logistics direction, the active component content is from low to high, and the catalyst particle size is from large to small. However, the results of industrial application show that when the traditional fixed-bed residue oil hydrogenation unit processes the Middle East vacuum residue oil that meets the upper limit of the feed conditions (wherein the S content is 4.5% by weight, the MCR is 18% by weight, and the Ni+V content is 100μg / g), even if the best catalyst grading in the prior art is adopted, the longest operation cycle of the unit will not exceed 10,000 hours (about 14 months). The reason is that the residue oil hydrogenation catalyst bed is forced to stop production due to the deposition of metal impurities and carbon deposition, which causes the pressure drop to rise to the upper limit. In order to maximize economic benefits, today's refineries often require residue oil hydrogenation units to process vacuum residue oil close to the upper limit of feed conditions, so the technical demand for extending the operation cycle is more urgent.

[0057] The inventors of this case have found through in-depth research that the metal Ni and V deposited in the catalyst in the fixed-bed residue oil hydrogenation reactor and the carbon deposits are not evenly distributed in the catalyst bed, especially in the bottom of the reactor. The main reason is that the flow direction of the bottom logistics of the fixed-bed downflow reactor changes, gradually transitioning from axial flow to radial flow, resulting in a significant increase in the amount of metal impurities and carbon deposits deposited. Therefore, the present invention replaces the porcelain balls at the bottom of the reactor that cannot accommodate metal impurities and carbon deposits with metal-containing agents and residual carbon-containing agents, and forms a new gradation with the existing protective agents, demetallizing agents, desulfurizing agents and residual carbon-removing agents in the reactor. The metal-containing agent of the present invention includes alumina with mesopores and macropores, which has a high capacity to accommodate metal; the residual carbon-containing agent includes alumina with only mesopores, which has a high capacity to accommodate residual carbon. Therefore, the grading method of the present invention greatly improves the capacity of the full series of catalysts to accommodate metal impurities and carbon deposits, delays the increase in bed pressure drop, and thus achieves the effect of greatly extending the operating cycle of the residue oil hydrogenation unit, so as to meet the requirements of extending the operating cycle of the common atmospheric and vacuum residue oil hydrogenation units in the petroleum refining industry.

[0058] In some specific embodiments of the present invention, the metal-containing agent includes three types of metal-containing agents with equivalent diameters of fine, medium and coarse; the equivalent diameter of the fine metal-containing agent is 2.5 to 3.5 mm; the equivalent diameter of the medium metal-containing agent is 5.5 to 6.5 mm; and the equivalent diameter of the coarse metal-containing agent is 11.5 to 12.5 mm.

[0059] In some specific embodiments of the present invention, the metal-containing agent is loaded in the following manner: coarse, medium and fine metal-containing agents of three equivalent diameters are loaded in the loading area of ​​the hydrogenation reactor in sequence from bottom to top. Preferably, the metal-containing agent is loaded in the following manner: the coarse metal-containing agent is loaded above the outlet collector of the hydrogenation reactor (the loading amount of the coarse metal-containing agent can reach the junction of the bottom surface and the side wall of the hydrogenation reactor), and more preferably, the distance between the upper surface of the bed of the coarse metal-containing agent and the lowest point of the bottom surface of the hydrogenation reactor is 150 to 300 mm; the bed volumes of the neutral and fine metal-containing agents are respectively the same as the bed volumes of the coarse metal-containing agent. According to a specific embodiment of the present invention, the loading method of the metal-containing agent in the loading area of ​​the hydrogenation reactor is as follows: Figure 1 shown. Figure 1 The main catalyst includes one or more of a hydrogenation protection catalyst, a hydrodemetallization catalyst and a hydrodesulfurization catalyst.

[0060] In some specific embodiments of the present invention, the loading amount of the metal-containing agent (including metal-containing agents of three equivalent diameters, namely, coarse, medium and fine) in a hydrogenation reactor is 0.5% to 3.0%, preferably 1.5% to 2.5% of the volume of the hydrogenation reactor.

[0061] In some specific embodiments of the present invention, the carbon residue containing agent includes three types of carbon residue containing agents with equivalent diameters of fine, medium and coarse. The equivalent diameter of the fine carbon residue containing agent is 2.5-3.5 mm, the equivalent diameter of the medium carbon residue containing agent is 5.5-6.5 mm, and the equivalent diameter of the coarse carbon residue containing agent is 11.5-12.5 mm.

[0062] In some specific embodiments of the present invention, the carbon residue containing agent is loaded in the following manner: coarse, medium and fine carbon residue containing agents of three equivalent diameters are loaded in the loading area of ​​the hydrogenation reactor in sequence from bottom to top. Preferably, the carbon residue containing agent is loaded in the following manner: the coarse carbon residue containing agent is loaded above the outlet collector of the hydrogenation reactor (the upper surface of the bed of the coarse carbon residue containing agent may be perpendicular to the tangent line at the intersection of the hydrogenation reactor wall). More preferably, the upper surface of the bed of the coarse carbon residue containing agent is 150 to 300 mm away from the lowest point of the bottom surface of the hydrogenation reactor; the bed volumes of the neutral and fine carbon residue containing agents are respectively the same as the bed volumes of the coarse carbon residue containing agent. According to specific embodiments of the present invention, the loading method of the carbon residue containing agent in the loading area of ​​the hydrogenation reactor is as follows: Figure 2 shown. Figure 2 The main catalyst includes one or more of a hydrodemetallization catalyst, a hydrodesulfurization catalyst and a hydrodecarbonization catalyst.

[0063] In some specific embodiments of the present invention, the amount of the carbon residue tolerant agent (including carbon residue tolerant agents of three equivalent diameters, namely, coarse, medium and fine) in a hydrogenation reactor is 0.5% to 3.0%, preferably 1.5% to 2.5% of the volume of the hydrogenation reactor.

[0064] In the present invention, the equivalent diameter refers to the maximum value of the straight-line distance between any two points on the catalyst geometry.

[0065] In some specific embodiments of the present invention, the first alumina comprises mesopores of 5 to 20 nm and macropores of 100 to 500 nm, and the mesopore volume is 0.60 cm 3 / g and above, the pore size presents a bimodal distribution.

[0066] In some specific embodiments of the present invention, the metal-containing agent further includes a first active component loaded on the first alumina; the first active component includes a first main active component and a first auxiliary active component, the first main active component includes molybdenum oxide and / or tungsten oxide, and the first auxiliary active component includes nickel oxide and / or cobalt oxide; based on the total weight of the metal-containing agent as 100%, the total loading amount of the first active component is 5% to 15%. The metal-containing agent of the present invention may include an active component, and thus has a certain catalytic hydrogenation function.

[0067] In some specific embodiments of the present invention, the second aluminum oxide further contains one or a combination of boron, germanium, zirconium and phosphorus. Preferably, based on the total weight of the second aluminum oxide being 100%, the content of one or a combination of boron, germanium, zirconium and phosphorus is 0.1% to 10%. The second aluminum oxide can be modified by introducing one or a combination of boron, germanium, zirconium and phosphorus using methods in the prior art.

[0068] In some specific embodiments of the present invention, the second main active component is molybdenum oxide, and the second auxiliary active component is nickel oxide.

[0069] In some specific embodiments of the present invention, based on the total weight of the metal-containing agent being 100%, the loading amount of the second main active component is 6% to 9%, and the loading amount of the second auxiliary active component is 1% to 3%.

[0070] In some specific embodiments of the present invention, the bulk density of the metal agent is 0.20-0.60 g / cm 3 , with a specific surface area of ​​100 to 160 m 2 / g.

[0071] In some specific embodiments of the present invention, the shape of the metal-containing agent can be a four-leaf clover shape, a bar shape, a sphere shape, etc. The metal-containing agent with a certain shape can be prepared by conventional molding methods, such as but not limited to extrusion molding.

[0072] The present invention has no particular limitation on the method for preparing the metal-containing agent, as long as the above-mentioned specific metal-containing agent can be prepared.

[0073] According to some preferred embodiments of the present invention, the method for preparing the metal-containing agent comprises:

[0074] Firstly, the first alumina with the required physical and chemical properties is prepared from pseudo-boehmite as raw material by molding and drying and roasting, and then the first main active component and the first auxiliary active component are selectively prepared into an impregnation solution, and the metal-containing agent is prepared by an equal volume impregnation method.

[0075] In some specific embodiments of the present invention, the pore volume of mesopores with a pore size of 5 to 15 nm in the second alumina accounts for 85% to 95% of the total mesopore volume, and the total mesopore volume is 0.50 cm 3 The mesopores contained in the second alumina are mainly distributed in the range of 5 to 15 nm and are distributed in a concentrated manner.

[0076] In some specific embodiments of the present invention, the residual carbon tolerant agent also includes a second active component loaded on the second alumina; the second active component includes a second main active component and a second auxiliary active component, the second main active component includes molybdenum oxide and / or tungsten oxide, and the second auxiliary active component includes nickel oxide and / or cobalt oxide; based on the total weight of the residual carbon tolerant agent as 100%, the total loading amount of the second active component is 10% to 25%.

[0077] In some specific embodiments of the present invention, the second aluminum oxide further contains one or a combination of boron, germanium, zirconium and phosphorus. Preferably, based on the total weight of the second aluminum oxide being 100%, the content of one or a combination of boron, germanium, zirconium and phosphorus is 0.1% to 10%. The second aluminum oxide can be modified by introducing one or a combination of boron, germanium, zirconium and phosphorus using methods in the prior art.

[0078] In some specific embodiments of the present invention, the second main active component is molybdenum oxide, and the second auxiliary active component is nickel oxide.

[0079] In some specific embodiments of the present invention, based on the total weight of the carbon residue containing agent being 100%, the loading amount of the second main active component is 12% to 15%, and the loading amount of the second auxiliary active component is 2% to 4%.

[0080] In some specific embodiments of the present invention, the bulk density of the carbon residue containing agent is 0.40-0.75 g / cm 3 , with a specific surface area of ​​150 to 250 m 2 / g.

[0081] In some specific embodiments of the present invention, the shape of the carbon residue containing agent can be a four-leaf clover shape, a strip shape, a sphere shape, etc. The carbon residue containing agent having a certain shape can be prepared by conventional molding methods, such as but not limited to extrusion molding.

[0082] The present invention has no particular limitation on the preparation method of the carbon residue accommodating agent, as long as the above-mentioned specific carbon residue accommodating agent can be prepared.

[0083] According to some preferred embodiments of the present invention, the method for preparing the carbon residue containing agent comprises:

[0084] Firstly, a second alumina having physical and chemical properties meeting the requirements is prepared from pseudo-boehmite by molding, drying and roasting, and then a second main active component and a second auxiliary active component are selectively prepared into an impregnation solution, and the residual carbon retaining agent is prepared by an equal volume impregnation method.

[0085] Fixed-bed residue oil hydrogenation units usually use four hydrogenation reactors. In the process of industrial application, the conventional residue oil hydrogenation catalyst grading often occurs that when the metal Ni+V content in the residue oil raw material is high, the catalyst bed of one or several reactors in the front section will reach the upper limit of pressure drop first due to excessive accumulation of metal impurities; while when processing residue oil raw materials with low metal Ni+V content, one or several reactors in the rear section will reach the upper limit of pressure drop first due to excessive accumulation of carbon impurities.

[0086] In order to delay the reactor pressure drop from reaching the upper limit, the present invention loads a metal agent at the bottom of one or several reactors with high metal impurity content in the front section (i.e., the filling area), and loads a residual carbon agent at the bottom of one or several reactors with high carbon deposit content in the rear section (i.e., the filling area).

[0087] In order to achieve the goal of effectively extending the operation cycle, the present invention provides different grading schemes according to the different contents of metal Ni+V in the residual oil raw material. When the Ni+V content in the residual oil raw material is ≤40μg / g, preferably, the metal-containing agent is loaded in the filling area of ​​the first hydrogenation reactor along the logistics direction, and the residual carbon-containing agent is loaded in the filling area of ​​the second, third and fourth hydrogenation reactors. When the Ni+V content in the residual oil raw material is >40μg / g and ≤70μg / g, preferably, the metal-containing agent is loaded in the filling area of ​​the first and second hydrogenation reactors along the logistics direction, and the residual carbon-containing agent is loaded in the filling area of ​​the third and fourth hydrogenation reactors. When the Ni+V content in the residual oil raw material is >70μg / g and ≤100μg / g, preferably, the metal-containing agent is loaded in the filling area of ​​the first, second and third hydrogenation reactors along the logistics direction, and the residual carbon-containing agent is loaded in the filling area of ​​the fourth hydrogenation reactor.

[0088] In the present invention, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydroremoval of carbon residue catalyst can adopt the corresponding catalysts in the field of residual oil hydrogenation disclosed in the prior art. In some preferred embodiments of the present invention, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydroremoval of carbon residue catalyst adopt the PHR series residual oil hydrogenation catalyst developed by the Petrochemical Research Institute of CNPC.

[0089] In some specific embodiments of the present invention, the loading amount of the hydrogenation protection catalyst is 2% to 10% of the total volume of the four hydrogenation reactors connected in series, the loading amount of the hydrogenation demetallization catalyst is 35% to 70% of the total volume of the four hydrogenation reactors connected in series, the loading amount of the hydrogenation desulfurization catalyst is 10% to 40% of the total volume of the four hydrogenation reactors connected in series, the loading amount of the hydrogenation decarbonization catalyst is 10% to 40% of the total volume of the four hydrogenation reactors connected in series, and the remainder of the total volume of the four hydrogenation reactors connected in series is the loading amount of the metal containing agent and the carbon containing agent.

[0090] In some specific embodiments of the present invention, the hydrogenation reactor is a fixed bed downflow reactor. A downflow reactor refers to a reactor in which the flow of materials flows from top to bottom. In the residual oil hydrogenation process, the flow pattern of the materials at the bottom of the downflow reactor changes from axial flow to radial flow. The hydrogenation catalyst grading method of the present invention is applicable to a fixed bed downflow reactor.

[0091] The second aspect of the present invention provides a residual oil hydroprocessing method, which comprises: under hydroprocessing reaction conditions, allowing the residual oil feedstock and hydrogen to pass through four hydrogenation reactors connected in series in sequence, and contacting with the catalyst loaded in the hydrogenation reactor according to the above-mentioned hydrogenation catalyst grading method for extending the operating cycle of the residual oil hydrogenation device to carry out a hydrogenation reaction, so as to obtain a hydroprocessing product.

[0092] In some specific embodiments of the present invention, the residual oil raw material includes one or a combination of atmospheric residue oil, vacuum residue oil, deasphalted oil, coal tar and coal liquefaction heavy oil, etc. Preferably, the residual oil raw material is vacuum residue oil.

[0093] In some specific embodiments of the present invention, the S content in the residual oil feedstock is less than 4.5 wt%, the MCR is less than 18 wt%, and the Ni+V content is less than 100 μg / g.

[0094] In some specific embodiments of the present invention, the hydroprocessing reaction conditions include: hydrogen partial pressure of 10.0 MPa to 18.0 MPa, hydrogen to oil volume ratio of 200 to 2000, liquid hourly volume space velocity of 0.10 to 1.0 h -1 , the reaction temperature of the first hydrogenation reactor is 310-420°C, and the reaction temperature of the other hydrogenation reactors is 300-420°C. Preferably, the hydroprocessing reaction conditions include: hydrogen partial pressure of 13.0MPa-15.0MPa, hydrogen-to-oil volume ratio of 420-1500, liquid hourly volume space velocity of 0.14-0.45h -1 The reaction temperature of the first hydrogenation reactor is 360-420°C, and the reaction temperature of the other hydrogenation reactors is 315-410°C.

[0095] It should be noted that the hydroprocessing reaction conditions of each hydrogenation reactor may be the same or different, as long as they are within the above range.

[0096] The technical scheme of the present invention is specifically described below through examples and comparative examples, but the present invention is not limited to these examples and can of course be implemented in various modifications within the scope of the gist of the present invention.

[0097] The main agent of the hydrogenation catalyst used in the embodiments and comparative examples is a PHR series residue oil hydrogenation catalyst developed by the Petrochemical Research Institute of China National Petroleum Corporation and produced by the Catalyst Plant of Fushun Petrochemical Company of PetroChina; wherein the hydrogenation protection catalyst is PHR-404, the hydrodemetallization catalysts are PHR-101, PHR-102, PHR-103 and PHR-104, the hydrodesulfurization catalysts are PHR-201, PHR-202 and PHR-203, and the hydroremoval of residual carbon catalyst is PHR-301.

[0098] The residual oil raw material A used in the examples and comparative examples is a mixed vacuum residual oil from the Middle East, and the residual oil raw material B is an atmospheric residual oil from the Middle East. The properties of the residual oil raw material A and the residual oil raw material B are shown in Table 1.

[0099] Example 1

[0100] The present embodiment provides a hydrogenation catalyst grading method for extending the operating cycle of a residual oil hydrogenation unit. The hydrogenation catalyst grading method uses four fixed bed downflow reactors with a volume of 300 ml each in series. The four reactors are reactor a, reactor b, reactor c and reactor d from the front section to the back section. The four hydrogenation reactors in series are divided into a filling area at the bottom and a reaction area above the filling area. The filling areas of reactor a, reactor b and reactor c are filled with 2 ml of three equivalent diameters of coarse, medium and fine metal agents from bottom to top, and the filling area of ​​reactor d is filled with 2 ml of three equivalent diameters of coarse, medium and fine carbon residue agents from bottom to top. The equivalent diameter of the fine metal agent is 3 mm, the equivalent diameter of the medium metal agent is 6 mm, and the equivalent diameter of the coarse metal agent is 12 mm. The equivalent diameter of the fine carbon residue agent is 3 mm, the equivalent diameter of the medium carbon residue agent is 6 mm, and the equivalent diameter of the coarse carbon residue agent is 12 mm.

[0101] The reaction zones of reactor a, reactor b, reactor c and reactor d constitute a total reaction zone, in which hydrogenation protection catalyst PHR-404, hydrogenation demetallization catalysts PHR-101, PHR-102, PHR-103 and PHR-104, hydrogenation desulfurization catalysts PHR-201, PHR-202 and PHR-203 and hydrogenation decarbonization catalyst PHR-301 are sequentially loaded along the logistics direction. The filling amount of PHR-404 accounts for 5% of the total volume of the four reactors; the total filling amount of PHR-101, PHR-102, PHR-103 and PHR-104 accounts for 53% of the total volume of the four reactors, and the filling volume ratio of PHR-101, PHR-102, PHR-103 and PHR-104 is 1:1:5:5; the total filling amount of PHR-201, PHR-202, PHR-203 and PHR-301 accounts for 40% of the total volume of the four reactors, and the filling volume ratio of PHR-201, PHR-202, PHR-203 and PHR-301 is 1:1:1:3.

[0102] Among them, the metal-containing agent includes a first alumina and a first active component loaded on the first alumina; the first active component includes a first main active component and a first auxiliary active component, the first main active component is molybdenum oxide, and the first auxiliary active component is nickel oxide; based on the total weight of the metal-containing agent as 100%, the total loading amount of the first active component is 10%, wherein the loading amount of the first main active component is 8%, and the loading amount of the first auxiliary active component is 2%.

[0103] The first alumina contains mesopores of 5 to 20 nm and macropores of 100 to 500 nm, and the mesopore volume is 0.60 to 0.70 cm 3 / g, and the pore size shows a bimodal distribution.

[0104] The bulk density of the metal agent is 0.58-0.60 g / cm 3 , with a specific surface area of ​​120 to 140 m 2 / g.

[0105] The metal-containing agent is in the shape of a four-leaf clover.

[0106] The preparation method of the metal-containing agent comprises the following steps: firstly, a pure alumina carrier (i.e., a first alumina) having physical and chemical properties that meet the requirements is prepared using pseudo-boehmite as a raw material by means of extrusion molding and drying and roasting, then a first main active component and a first auxiliary active component are prepared into an impregnation solution, and an equal volume impregnation method is used to prepare the metal-containing agent.

[0107] The residual carbon accommodating agent includes a second alumina and a second active component loaded on the second alumina; the second active component includes a second main active component and a second auxiliary active component, the second main active component is molybdenum oxide, and the second auxiliary active component is nickel oxide; based on the total weight of the residual carbon accommodating agent as 100%, the total loading amount of the second active component is 17%, wherein the loading amount of the second main active component is 14%, and the loading amount of the second auxiliary active component is 3%.

[0108] The second alumina contains only mesopores, the pore volume of mesopores with a pore diameter of 5 to 15 nm accounts for 90% of the total mesopore volume, and the total mesopore volume is 0.50 to 0.60 cm 3 / g.

[0109] The bulk density of the carbon residue containing agent is 0.70-0.75 g / cm 3 , with a specific surface area of ​​180 to 200 m 2 / g.

[0110] The shape of the carbon residue containing agent is a four-leaf clover.

[0111] The preparation method of the carbon residue accommodating agent comprises the following steps: firstly, a pure alumina carrier (i.e., a second alumina) having physical and chemical properties that meet the requirements is prepared using pseudo-boehmite as a raw material by means of extrusion molding and drying and roasting, and then a second main active component and a second auxiliary active component are prepared into an impregnation solution, and an equal volume impregnation method is used to prepare a metal accommodating agent.

[0112] This embodiment also provides a residue oil hydroprocessing method, which comprises: under hydroprocessing reaction conditions, allowing the residue oil raw material A and hydrogen to pass through the above-mentioned four series-connected reactors a, b, c and d in turn, and contact with the catalyst loaded in the reactors a, b, c and d according to the above-mentioned hydrogenation catalyst grading method to carry out hydrogenation reaction, so as to obtain hydrogenated residue oil.

[0113] Among them, the residual oil raw material A and hydrogen adopt a top-down flow mode in each reactor.

[0114] The hydroprocessing reaction conditions include: hydrogen partial pressure of 15.0 MPa, hydrogen-to-oil volume ratio of 700:1, liquid hourly volume space velocity of 0.217 h -1 , the reaction temperature is 380° C. The reaction conditions of reactors a, b, c and d are the same.

[0115] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 12,000 hours.

[0116] Example 2

[0117] The present embodiment provides a hydrogenation catalyst grading method for extending the operating cycle of a residual oil hydrogenation unit. The hydrogenation catalyst grading method uses four fixed bed downflow reactors with a volume of 300 ml each in series. The four reactors are reactor a, reactor b, reactor c and reactor d from the front section to the back section. The four hydrogenation reactors in series are divided into a filling area at the bottom and a reaction area above the filling area. The filling area of ​​reactor a is filled with 2 ml of three equivalent diameters of coarse, medium and fine metal agents from bottom to top, and the filling areas of reactors b, reactor c and reactor d are filled with 2 ml of three equivalent diameters of coarse, medium and fine carbon residue agents from bottom to top. The equivalent diameter of the fine metal agent is 3 mm, the equivalent diameter of the medium metal agent is 6 mm, and the equivalent diameter of the coarse metal agent is 12 mm. The equivalent diameter of the fine carbon residue agent is 3 mm, the equivalent diameter of the medium carbon residue agent is 6 mm, and the equivalent diameter of the coarse carbon residue agent is 12 mm.

[0118] The reaction zones of reactor a, reactor b, reactor c and reactor d constitute a total reaction zone, in which hydrogenation protection catalyst PHR-404, hydrogenation demetallization catalysts PHR-101, PHR-102, PHR-103 and PHR-104, hydrogenation desulfurization catalysts PHR-201, PHR-202 and PHR-203 and hydrogenation decarbonization catalyst PHR-301 are sequentially loaded along the logistics direction. The filling amount of PHR-404 accounts for 5% of the total volume of the four reactors; the total filling amount of PHR-101, PHR-102, PHR-103 and PHR-104 accounts for 40% of the total volume of the four reactors, and the filling volume ratio of PHR-101, PHR-102, PHR-103 and PHR-104 is 1:1:5:5; the total filling amount of PHR-201, PHR-202, PHR-203 and PHR-301 accounts for 53% of the total volume of the four reactors, and the filling volume ratio of PHR-201, PHR-202, PHR-203 and PHR-301 is 1:1:1:3.

[0119] The metal absorbing agent and carbon residue absorbing agent of this embodiment and their preparation methods are the same as those in embodiment 1.

[0120] The residual oil feedstock B was treated by the hydrogenation catalyst grading method of this embodiment, and the residual oil hydrogenation treatment process conditions were the same as those in Example 1.

[0121] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor d increased to 0.7 MPa. The calculated operating time was 15,000 hours.

[0122] Example 3

[0123] The present embodiment provides a hydrogenation catalyst grading method for extending the operating cycle of a residual oil hydrogenation unit. The hydrogenation catalyst grading method uses four fixed bed downflow reactors with a volume of 300 ml each in series. The four reactors are reactor a, reactor b, reactor c and reactor d from the front section to the back section. The four hydrogenation reactors in series are divided into a filling area at the bottom and a reaction area above the filling area. The filling areas of reactor a, reactor b and reactor c are filled with 2 ml of three equivalent diameters of coarse, medium and fine metal agents from bottom to top, and the filling area of ​​reactor d is filled with 2 ml of three equivalent diameters of coarse, medium and fine carbon residue agents from bottom to top. The equivalent diameter of the fine metal agent is 3 mm, the equivalent diameter of the medium metal agent is 6 mm, and the equivalent diameter of the coarse metal agent is 12 mm. The equivalent diameter of the fine carbon residue agent is 3 mm, the equivalent diameter of the medium carbon residue agent is 6 mm, and the equivalent diameter of the coarse carbon residue agent is 12 mm. The loading method of the main catalyst (ie, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydroremoval of carbon residue catalyst) is the same as that in Example 1.

[0124] The difference between this embodiment and embodiment 1 is that: the active component content of the metal tolerant agent and the residual carbon tolerant agent is appropriately increased; the loading amount of the first main active component in the metal tolerant agent is 9%, and the loading amount of the second auxiliary active component is 3%; the loading amount of the second main active component in the residual carbon tolerant agent is 15%, and the loading amount of the second auxiliary active component is 4%.

[0125] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, and the residual oil hydrogenation treatment process conditions were the same as those in Example 1.

[0126] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 11,900 hours.

[0127] Example 4

[0128] The present embodiment provides a hydrogenation catalyst grading method for extending the operating cycle of a residual oil hydrogenation unit. The hydrogenation catalyst grading method uses four fixed bed downflow reactors with a volume of 300 ml each in series. The four reactors are reactor a, reactor b, reactor c and reactor d from the front section to the back section. The four hydrogenation reactors in series are divided into a filling area at the bottom and a reaction area above the filling area. The filling areas of reactor a, reactor b and reactor c are filled with 2 ml of three equivalent diameters of coarse, medium and fine metal agents from bottom to top, and the filling area of ​​reactor d is filled with 2 ml of three equivalent diameters of coarse, medium and fine carbon residue agents from bottom to top. The equivalent diameter of the fine metal agent is 3 mm, the equivalent diameter of the medium metal agent is 6 mm, and the equivalent diameter of the coarse metal agent is 12 mm. The equivalent diameter of the fine carbon residue agent is 3 mm, the equivalent diameter of the medium carbon residue agent is 6 mm, and the equivalent diameter of the coarse carbon residue agent is 12 mm. The loading method of the main catalyst (ie, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydroremoval of carbon residue catalyst) is the same as that in Example 1.

[0129] The difference between this embodiment and embodiment 1 is that: the specific surface area of ​​the metal-containing agent and the carbon residue-containing agent is appropriately increased; the specific surface area of ​​the metal-containing agent is 140-160 m 2 / g; the specific surface area of ​​the residual carbon agent is 200~220m 2 / g.

[0130] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, and the residual oil hydrogenation treatment process conditions were the same as those in Example 1.

[0131] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 11,920 hours.

[0132] Example 5

[0133] This embodiment provides a hydrogenation catalyst grading method for extending the operating cycle of a residual oil hydrogenation unit. The hydrogenation catalyst grading method uses four fixed bed downflow reactors with a volume of 300 ml each connected in series. The four reactors are reactor a, reactor b, reactor c and reactor d from the front section to the back section. The catalyst grading and the physicochemical properties of the catalysts loaded in the four reactors are exactly the same as those in Example 1.

[0134] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, but the reaction conditions of the residual oil hydrogenation treatment were different from those in Example 1. The reaction conditions of this example included: a hydrogen partial pressure of 18.0 MPa, a hydrogen-to-oil volume ratio of 1000:1, and a liquid hourly volume space velocity of 0.217 h -1, the reaction temperature is 380°C, the other reaction conditions are exactly the same as in Example 1, and the reaction conditions in reactors a, b, c and d are the same.

[0135] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 12,000 hours.

[0136] Example 6

[0137] This embodiment provides a hydrogenation catalyst grading method for extending the operating cycle of a residual oil hydrogenation unit. The hydrogenation catalyst grading method uses four fixed bed downflow reactors with a volume of 300 ml each connected in series. The four reactors are reactor a, reactor b, reactor c and reactor d from the front section to the back section. The catalyst grading and the physicochemical properties of the catalysts loaded in the four reactors are exactly the same as those in Example 1.

[0138] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, but the reaction conditions of the residual oil hydrogenation treatment were different from those in Example 1. The reaction conditions of this example included: a hydrogen partial pressure of 15.0 MPa, a hydrogen-to-oil volume ratio of 700:1, and a liquid hourly volume space velocity of 0.5 h -1 , the reaction temperature is 390°C, the other reaction conditions are exactly the same as in Example 1, and the reaction conditions in reactors a, b, c and d are the same.

[0139] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 11,100 hours.

[0140] The properties of the hydrogenated residue oil provided by Examples 1 to 6 are shown in Table 1.

[0141] Table 1 Properties of the residual oil feedstock and the hydrogenated residual oil of Examples 1 to 6

[0142]

[0143]

[0144] It can be seen from the operating results of Examples 1 to 6 that, when producing hydrogenated residue oil of the same nature, by changing the physical properties of the metal-containing agent and the carbon residue-containing agent and the hydrogenation reaction conditions within the scope of the present invention, the hydrogenation catalyst grading method provided by the present invention can increase the operating time of the residue oil hydrogenation unit.

[0145] Comparative Example 1

[0146] This comparative example provides a hydrogenation catalyst grading method. The hydrogenation catalyst grading method uses 4 fixed bed downflow reactors with a volume of 300 ml each connected in series. The 4 reactors are reactor a, reactor b, reactor c and reactor d from the front section to the back section. The 4 hydrogenation reactors connected in series are divided into a filling area at the bottom and a reaction area above the filling area. The filling areas of reactor a, reactor b, reactor c and reactor d are filled in order from bottom to top. and The main catalyst (ie, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbonization catalyst) is loaded in the same manner as in Example 1.

[0147] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, and the residual oil hydrogenation treatment process conditions were the same as those in Example 1.

[0148] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 7000 hours.

[0149] Comparative Example 2

[0150] This comparative example provides a hydrogenation catalyst grading method. The hydrogenation catalyst grading method uses 4 fixed bed downflow reactors with a volume of 300 ml each connected in series. The 4 reactors are reactor a, reactor b, reactor c and reactor d from the front section to the back section. The 4 hydrogenation reactors connected in series are divided into a filling area at the bottom and a reaction area above the filling area. The filling areas of reactor a, reactor b, reactor c and reactor d are filled in order from bottom to top. and The main catalyst (ie, the hydrogenation protection catalyst, the hydrodemetallization catalyst, the hydrodesulfurization catalyst and the hydrodecarbonization catalyst) is loaded in the same manner as in Example 2.

[0151] The residual oil feedstock B was treated by the hydrogenation catalyst grading method, and the residual oil hydrogenation treatment process conditions were the same as those in Example 2.

[0152] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor d increased to 0.7 MPa. The calculated operating time was 8000 hours.

[0153] Comparative Example 3

[0154] This comparative example provides a hydrogenation catalyst grading method, which is the same as the main catalyst loading method in Example 1, and the difference from Example 1 is that 2 ml of carbon residue containing agents with equivalent diameters of 12 mm, 6 mm and 3 mm are loaded in the filling areas of reactor a, reactor b, reactor c and reactor d from bottom to top. The carbon residue containing agent is the same as that in Example 1.

[0155] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, and the residual oil hydrogenation treatment process conditions were the same as those in Example 1.

[0156] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 10,000 hours.

[0157] Comparative Example 4

[0158] This comparative example provides a hydrogenation catalyst grading method, which is the same as the main catalyst loading method of Example 1, and the difference from Example 1 is that: 2 ml of each of the metal agents with equivalent diameters of 12 mm, 6 mm and 3 mm are loaded in the filling areas of reactor a, reactor b, reactor c and reactor d from bottom to top. The metal agent is the same as that in Example 1.

[0159] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, and the residual oil hydrogenation treatment process conditions were the same as those in Example 1.

[0160] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 11,000 hours.

[0161] Comparative Example 5

[0162] This comparative example provides a hydrogenation catalyst grading method. The hydrogenation catalyst grading method is basically the same as that in Example 1, except that the pore volumes of the first alumina and the second alumina are lower than those in Example 1, but the preparation method, active components and content of the metal-containing agent and the carbon-containing agent, as well as other physical parameters are the same as those in Example 1. The first alumina contains mesopores of 5 to 20 nm and macropores of 100 to 500 nm, and the mesopore volume is 0.54 cm 3 / g, and the pore size shows a bimodal distribution. The second alumina contains only mesopores, and the pore volume of mesopores with a pore size of 5 to 15 nm accounts for 99% of the total mesopore volume, and the total mesopore volume is 0.44 cm 3 / g.

[0163] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, and the residual oil hydrogenation treatment process conditions were the same as those in Example 1.

[0164] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 10,600 hours.

[0165] Comparative Example 6

[0166] This comparative example provides a hydrogenation catalyst grading method, which is the same as the main catalyst loading method of Example 1, and the difference from Example 1 is that: 2 ml of carbon residue containing agents with equivalent diameters of 12 mm, 6 mm and 3 mm are loaded in the loading areas of reactor a, reactor b and reactor c from bottom to top, and 2 ml of metal containing agents with equivalent diameters of 12 mm, 6 mm and 3 mm are loaded in the loading area of ​​reactor d from bottom to top. The carbon residue containing agent and the metal containing agent are the same as those in Example 1.

[0167] The residual oil feedstock A was treated by the hydrogenation catalyst grading method, and the residual oil hydrogenation treatment process conditions were the same as those in Example 1.

[0168] At the beginning of operation, the pressure drop of each reactor was 0.18 MPa, and the operation was stopped until the pressure drop of reactor a increased to 0.7 MPa. The calculated operating time was 10,500 hours.

[0169] The properties of the hydrogenated residue oils provided by Comparative Examples 1 to 6 are shown in Table 2.

[0170] Table 2 Properties of the hydrotreated residues of Comparative Examples 1 to 6

[0171]

[0172]

[0173] It can be seen from the operating results of Examples 1-2 and Comparative Examples 1-2 that, when producing hydrogenated residue oil of the same nature, for residue oil raw materials A and B, the hydrogenation catalyst grading method of the present invention can increase the operating time of the residue oil hydrogenation unit.

[0174] It can be seen from the operation results of Example 1 and Comparative Examples 3 to 6 that, when the same properties of hydrogenated residual oil are produced, the metal-containing agent and the carbon-residue containing agent of the present invention are used to fill the filling area at the bottom of the reactor, and the two have a synergistic effect, and the effect of extending the operation time is obvious. However, using a metal-containing agent or a carbon-residue containing agent alone to fill the filling area at the bottom of the reactor, changing the filling order of the metal-containing agent and the carbon-residue containing agent in the reactor, and using a metal-containing agent or a carbon-residue containing agent with a lower mesopore volume to fill the filling area at the bottom of the reactor will reduce the operation cycle of the entire device.

Claims

1. A method for grading a hydrogenation catalyst for extending the operating cycle of a residual oil hydrogenation unit, comprising: The four hydrogenation reactors connected in series are respectively divided into a filling area at the bottom and a reaction area above the filling area, a metal agent is loaded in the filling area of ​​one or several hydrogenation reactors at the front section of the four hydrogenation reactors connected in series, and a carbon residue agent is loaded in the filling area of ​​one or several hydrogenation reactors at the rear section, and the filling areas of the four hydrogenation reactors connected in series are all loaded with the metal agent or the carbon residue agent; The reaction zones of the four hydrogenation reactors connected in series constitute a total reaction zone, in which a hydrogenation protection catalyst, a hydrogenation demetallization catalyst, a hydrogenation desulfurization catalyst and a hydrogenation decarbonization catalyst are sequentially loaded along the logistics direction; Wherein, the metal-containing agent at least includes a first aluminum oxide, and the first aluminum oxide is an aluminum oxide containing mesopores and macropores; The carbon residue accommodating agent at least includes a second aluminum oxide, and the second aluminum oxide is aluminum oxide containing only mesopores.

2. The hydrogenation catalyst grading method according to claim 1, wherein: The reaction zones of the one or several hydrogenation reactors in the front section are sequentially filled with one or several of hydrogenation protection catalyst, hydrogenation demetallization catalyst and hydrogenation desulfurization catalyst along the logistics direction, and the reaction zones of the one or several hydrogenation reactors in the rear section are sequentially filled with one or several of hydrogenation demetallization catalyst, hydrogenation desulfurization catalyst and hydrogenation decarbonization catalyst along the logistics direction.

3. The hydrogenation catalyst grading method according to claim 1, wherein: The metal agent includes three types of equivalent diameters of fine, medium and coarse metal agents. The equivalent diameter of the fine metal agent is 2.5-3.5 mm, the equivalent diameter of the medium metal agent is 5.5-6.5 mm, and the equivalent diameter of the coarse metal agent is 11.5-12.5 mm.

4. The hydrogenation catalyst grading method according to claim 3, wherein: The metal-containing agent is loaded in the following manner: the metal-containing agents of three equivalent diameters, namely, coarse, medium and fine, are loaded in the loading area of ​​the hydrogenation reactor in order from bottom to top; Preferably, the metal agent is loaded in the following manner: the coarse metal agent is loaded above the outlet collector of the hydrogenation reactor; the bed volume of the neutralized fine metal agent is respectively the same as the bed volume of the coarse metal agent; Preferably, the loading amount of the metal agent in a hydrogenation reactor is 0.5% to 3.0% of the volume of the hydrogenation reactor.

5. The hydrogenation catalyst grading method according to claim 1, wherein: The carbon residue containing agent includes three types of carbon residue containing agents with equivalent diameters of fine, medium and coarse. The equivalent diameter of the fine carbon residue containing agent is 2.5-3.5 mm, the equivalent diameter of the medium carbon residue containing agent is 5.5-6.5 mm, and the equivalent diameter of the coarse carbon residue containing agent is 11.5-12.5 mm.

6. The hydrogenation catalyst grading method according to claim 5, wherein: The carbon residue containing agent is loaded in the filling area of ​​the hydrogenation reactor in the following manner: loading carbon residue containing agents of three equivalent diameters, namely, coarse, medium and fine, in order from bottom to top; Preferably, the carbon residue containing agent is loaded in the following manner: the coarse carbon residue containing agent is loaded above the outlet collector of the hydrogenation reactor; the bed volume of the neutralized and fine carbon residue containing agents is respectively the same as the bed volume of the coarse carbon residue containing agent; Preferably, the amount of the carbon residue retaining agent in a hydrogenation reactor is 0.5% to 3.0% of the volume of the hydrogenation reactor.

7. The hydrogenation catalyst grading method according to claim 1, wherein: The first alumina contains mesopores of 5 to 20 nm and macropores of 100 to 500 nm, and the mesopore volume is 0.60 cm 3 / g and above, the pore size presents a bimodal distribution.

8. The hydrogenation catalyst grading method according to claim 1, wherein: The metal-containing agent further includes a first active component supported on the first alumina; the first active component includes a first main active component and a first auxiliary active component, the first main active component includes molybdenum oxide and / or tungsten oxide, and the first auxiliary active component includes nickel oxide and / or cobalt oxide; based on the total weight of the metal-containing agent as 100%, the total loading amount of the first active component is 5% to 15%; Preferably, the first aluminum oxide further contains one or a combination of boron, germanium, zirconium and phosphorus; Preferably, the first main active component is molybdenum oxide, and the first auxiliary active component is nickel oxide; Preferably, based on the total weight of the metal agent as 100%, the loading amount of the first main active component is 6% to 9%, and the loading amount of the first auxiliary active component is 1% to 3%; Preferably, the bulk density of the metal agent is 0.20-0.60 g / cm 3 , with a specific surface area of ​​100 to 160 m 2 / g.

9. The hydrogenation catalyst grading method according to claim 1, wherein: Preferably, the pore volume of mesopores with a pore size of 5 to 15 nm in the second alumina accounts for 85% to 95% of the total mesopore volume, and the total mesopore volume is 0.50 cm 3 / g or above.

10. The hydrogenation catalyst grading method according to claim 1, wherein: The residual carbon tolerant agent further comprises a second active component supported on the second alumina; the second active component comprises a second main active component and a second auxiliary active component, the second main active component comprises molybdenum oxide and / or tungsten oxide, and the second auxiliary active component comprises nickel oxide and / or cobalt oxide; based on the total weight of the residual carbon tolerant agent being 100%, the total loading amount of the second active component is 10% to 25%; Preferably, the second aluminum oxide further contains one or a combination of boron, germanium, zirconium and phosphorus; Preferably, the second main active component is molybdenum oxide, and the second auxiliary active component is nickel oxide; Preferably, based on the total weight of the carbon residue absorbing agent being 100%, the loading amount of the second main active component is 12% to 15%, and the loading amount of the second auxiliary active component is 2% to 4%; Preferably, the bulk density of the carbon residue retaining agent is 0.40 to 0.75 g / cm 3 , with a specific surface area of ​​150 to 250 m 2 / g.

11. The hydrogenation catalyst grading method according to claim 1, wherein: When the Ni+V content in the residual oil feedstock is ≤40 μg / g, the metal-containing agent is loaded in the filling area of ​​the first hydrogenation reactor along the logistics direction, and the carbon residue-containing agent is loaded in the filling areas of the second, third and fourth hydrogenation reactors; When the Ni+V content in the residual oil feedstock is greater than 40 μg / g and less than or equal to 70 μg / g, the metal-containing agent is loaded in the filling areas of the first and second hydrogenation reactors along the logistics direction, and the carbon residue-containing agent is loaded in the filling areas of the third and fourth hydrogenation reactors; When the Ni+V content in the residual oil feedstock is >70μg / g and ≤100μg / g, the metal-containing agent is loaded in the filling areas of the first, second and third hydrogenation reactors along the logistics direction, and the residual carbon-containing agent is loaded in the filling area of ​​the fourth hydrogenation reactor.

12. The hydrogenation catalyst grading method according to claim 1, wherein: The hydrogenation reactor is a fixed bed downflow reactor.

13. A residual oil hydroprocessing method, comprising: exist Under the conditions of hydroprocessing reaction, the residual oil feedstock and hydrogen are sequentially passed through four hydrogenation reactors connected in series, and are contacted with the catalyst loaded in the hydrogenation reactor according to the hydrogenation catalyst grading method for extending the operating cycle of the residual oil hydrogenation unit according to any one of claims 1 to 12 to carry out hydrogenation reaction, so as to obtain a hydroprocessed product.

14. The method for hydrotreating residual oil according to claim 13, wherein: The residual oil raw material includes one or a combination of atmospheric residual oil, vacuum residual oil, deasphalted oil, coal tar and coal liquefaction heavy oil; Preferably, the S content in the residual oil feedstock is 4.5 wt% or less, the MCR is 18 wt% or less, and the Ni+V content is 100 μg / g or less.

15. The residual oil hydroprocessing method according to claim 13, wherein: The hydroprocessing reaction conditions include: hydrogen partial pressure of 10.0 MPa to 18.0 MPa, hydrogen to oil volume ratio of 200 to 2000, liquid hourly volume space velocity of 0.10 to 1.0 h -1 , the reaction temperature of the first hydrogenation reactor is 310-420°C, and the reaction temperature of the other hydrogenation reactors is 300-420°C; Preferably, the hydroprocessing reaction conditions include: hydrogen partial pressure of 13.0 MPa to 15.0 MPa, hydrogen to oil volume ratio of 420 to 1500, liquid hourly volume space velocity of 0.14 to 0.45 h -1 The reaction temperature of the first hydrogenation reactor is 360-420°C, and the reaction temperature of the other hydrogenation reactors is 315-410°C.

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