A heavy oil hydrodemetallization transition catalyst, its preparation and method of grading application

Abstract

The present application provides a heavy oil hydrodemetallization transition catalyst, a preparation method and a grading application method thereof, the catalyst comprising a carrier and an active component, the carrier being gamma Al2O3-SiO2 containing alkali metal or alkaline earth metal oxide, and the active component being NiO and MoO3. The heavy oil hydrodemetallization transition catalyst can pre-decompose metal-containing residue macromolecules, improve the accessibility of metal-containing molecules to the active centers of the catalyst, and make nickel and vanadium be removed as much as possible and deposited in the demetallization agent bed layer through a reasonable grading method, so as to further improve the metal removal rate, reduce the migration of nickel and vanadium after removal, effectively protect the main catalyst, and effectively prolong the operation cycle of the residue oil hydrogenation device.

Description

Technical Field

[0001] This invention belongs to the field of heavy oil processing, and relates to a catalyst and its preparation method, particularly to a heavy oil hydrodemetallization transition catalyst and its preparation and gradation application method. Background Technology

[0002] Globally, crude oil resources are increasingly becoming heavier and of lower quality (high sulfur, high acid, etc.), resulting in a massive volume of low-quality heavy oil. The efficient processing and utilization of heavy oil has become a major challenge for the refining industry. With changing market demands and increasingly stringent environmental requirements, efficient residue oil processing technologies must adapt to the demand for lower-quality feedstocks while actively addressing challenges such as changes in oil product demand structure and gradually increasing environmental requirements. The efficient processing and full utilization of residue oil has become a focus of attention for the global refining industry.

[0003] Residue hydrotreating is an important technology for the clean and efficient utilization of residue resources. The process mainly involves hydrodemetallization, hydrodesulfurization, hydronitrogenation, and removal of residual carbon. Hydrotreated heavy oil is primarily used as feedstock for catalytic cracking and as a blending component for low-sulfur marine fuel. Currently, residue hydrotreating technologies include fixed-bed, fluidized-bed, slurry-bed, and moving-bed technologies. Among these four types, fixed-bed hydrotreating is the most mature, easy to operate, and has relatively low investment costs, making it the most widely used residue hydrotreating process.

[0004] Fixed-bed hydrotreating of residual oil typically employs catalyst gradation packing technology, categorized by main function as protective agents, demetallizers, desulfurizers, and carbon removal agents. Catalyst particle size and porosity generally decrease along the flow path, while activity increases. The primary purpose of gradation packing is to gradually remove impurities from the residual oil, extending the unit's operating cycle. Our analysis of deactivated catalysts revealed significant deposits of nickel and vanadium on the main catalysts (desulfurizers and carbon removal agents), indicating that the performance of demetallizers in typical gradation systems needs improvement. Increasing the active metal content of the demetallizer can improve the metal removal rate to some extent, but it can easily lead to caking of certain demetallizer beds due to excessive metal deposition, resulting in a rapid increase in reactor pressure drop and shortening the unit's operating cycle. Therefore, improving the metal removal rate in the demetallizer bed and reducing nickel and vanadium deposition on the main catalyst, thereby enabling the main catalyst to perform better, urgently requires enhancing the performance of demetallizer catalysts and optimizing the gradation method within the existing catalyst gradation system. Summary of the Invention

[0005] To address the technical problems existing in the prior art, this invention provides a heavy oil hydrotreating demetallization transition catalyst and its preparation and grading application method. The demetallization transition catalyst and grading method improve the accessibility of metal-containing molecules to the catalyst active center by pre-deconstructing the metal-containing residue oil macromolecules, thereby further improving the metal removal rate, reducing the post-removal shift of metal nickel and vanadium, effectively protecting the main catalyst, and effectively extending the operating cycle of the residue oil hydrotreating unit.

[0006] To achieve the above technical effects, the present application adopts the following technical solutions:

[0007] One of the purposes of the present application is to provide a heavy oil hydrodemetallization transition catalyst, which comprises a carrier and an active component, the carrier is γAl2O3-SiO2 containing alkali metal or alkaline earth metal oxide, and the active component is NiO and MoO3.

[0008] In the present application, γAl2O3-SiO2 containing alkali metal or alkaline earth metal oxide is used as the carrier, and NiO and MoO3 are used as the active component, which has the advantages of being able to handle poor quality heavy oil with high metal content and high carbon residue, pre-treating and deconstructing the macromolecular components of heavy oil, significantly reducing the difficulty of removing heavy metals nickel and vanadium, and improving the metal removal efficiency of the demetallization agent.

[0009] As a preferred technical solution of the present application, the mass content of γAl2O3 in the carrier is 60.0-75.0%, the mass content of SiO2 is 10.0-20.0%, and the balance is alkali metal or alkaline earth metal oxide.

[0010] Among them, the mass content of γAl2O3 can be 60.0%, 62.0%, 65.0%, 68.0%, 70.0%, 72.0% or 75.0%, etc., and the mass content of SiO2 can be 10.0%, 11.0%, 12.0%, 13.0%, 14.0%, 15.0%, 16.0%, 17.0%, 18.0%, 19.0% or 20.0%, etc., but not limited to the listed values, and other values not listed in the above value range are also applicable.

[0011] As a preferred technical solution of the present application, the mass content of NiO in the catalyst is 1.0-3.5%, such as 1.0%, 1.2%, 1.5%, 1.8%, 2.0%, 2.2%, 2.5%, 2.8%, 3.0%, 3.2% or 3.5%, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0012] Preferably, the mass content of MoO3 in the catalyst is 4.5-10.0%, such as 4.5%, 5.0%, 5.5%, 6.0%, 7.0%, 8.0%, 9.0% or 10.0%, etc., but not limited to the listed values, and other values not listed in the value range are also applicable.

[0013] As a preferred technical solution of the present application, the catalyst further comprises an auxiliary agent.

[0014] Preferably, the auxiliary agent is phosphorus.

[0015] Preferably, the content of phosphorus pentoxide in the catalyst is 0.5-2.0% in terms of oxide content, such as 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8% or 2.0%, etc., but not limited to the listed values, and other values not listed in the range are also applicable.

[0016] Preferably, the alkali metal or alkaline earth metal oxide in the carrier is an auxiliary agent.

[0017] Preferably, the content of alkali metal or alkaline earth metal oxide in the catalyst is 2.0-6.5%, such as 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0% or 6.5%, etc., but not limited to the listed values, and other values not listed in the range are also applicable.

[0018] In the present application, the γ-Al2O3 precursor is pseudoboehmite, with a pore volume of 1.2-1.45 ml / g, a BET specific surface area of 260-285 m 2 / g, and a peptization of >21%. The SiO2 has a pore volume of 0.5-0.68 ml / g, a BET specific surface area of 450-650 m 2 / g, and a mesopore ratio of 85.0-95.5%.

[0019] The second object of the present application is to provide a preparation method of the heavy oil hydrodemetallization transition catalyst described in the first object, which comprises:

[0020] The carrier γ-Al2O3-SiO2 is prepared by using SiO2 and pseudoboehmite containing alkali metal or alkaline earth metal elements.

[0021] The active components are NiO and MoO3 loaded by impregnation, and the catalyst is obtained after calcination.

[0022] As a preferred technical solution of the present application, the preparation method of the SiO2 containing alkali metal or alkaline earth metal elements comprises: loading an alkali metal or alkaline earth metal salt solution to the carrier SiO2 by an equal volume impregnation method.

[0023] Preferably, the alkali metal or alkaline earth metal salt solution comprises any one or a combination of at least two of nitrate or chloride of sodium, potassium, magnesium or calcium.

[0024] In the present application, the preparation method of the carrier SiO2 comprises: preparing a gel slurry by using a silicon-containing solution, an inorganic acid solution and a modified metal salt at a certain temperature, placing the gel slurry in a hydrothermal reactor for aging treatment, and the slurry aging pH is preferably 5-7; filtering and washing the aged gel slurry, and drying and crushing the filter cake to obtain the carrier SiO2.

[0025] The silicon-containing solution is one or more of silica sol, water glass, silicon tetrachloride, etc., and the inorganic acid solution is any one or a combination of at least two of sulfuric acid solution, nitric acid solution, hydrochloric acid solution, etc. The modified metal salt is any one or a combination of at least two of soluble metal salts of transition metals manganese, titanium, molybdenum, germanium, tin, zirconium, etc.

[0026] As a preferred technical solution of the present application, the preparation method of the carrier γAl2O3-SiO2 includes:

[0027] The γAl2O3, the SiO2 containing alkali metal or alkaline earth metal elements, a forming aid, and deionized water are mixed to form a shaped carrier;

[0028] The shaped carrier is dried and calcined to obtain the carrier γAl2O3-SiO2;

[0029] Preferably, the forming aid includes any one or a combination of at least two of Tianqing powder, carboxymethyl cellulose, hydroxypropyl methyl cellulose, or hydroxyethyl cellulose.

[0030] Preferably, the calcination temperature is 600-780°C, and further preferably 650-770°C, and the calcination time is 6-8h. The calcination temperature can be 600°C, 620°C, 650°C, 680°C, 700°C, 720°C, 750°C, or 780°C, etc., and the time can be 6h, 6.2h, 6.5h, 6.8h, 7h, 7.2h, 7.5h, 7.8h, or 8h, etc., but is not limited to the listed values, and other values not listed in the above ranges are also applicable.

[0031] As a preferred technical solution of the present application, the method for loading active components by impregnation includes an equal-volume impregnation method or an excess-impregnation method, and is preferably an equal-volume solution impregnation method.

[0032] Preferably, the equal-volume impregnation method includes immersing the carrier in a solution with an equal volume of the carrier pores, which is composed of nickel salt, molybdenum salt, and phosphorus-containing inorganic acid.

[0033] Preferably, the nickel salt includes any one or a combination of at least two of nickel nitrate, basic nickel carbonate, nickel acetate, or nickel citrate.

[0034] Preferably, the molybdenum salt includes molybdenum trioxide and / or ammonium heptamolybdate tetrahydrate.

[0035] Preferably, the phosphorus-containing inorganic acid includes any one or a combination of at least two of phosphoric acid, metaphosphoric acid, hypophosphorous acid, or phosphorous acid.

[0036] Preferably, the temperature of the post-impregnation calcination is 400-500°C, further preferably 410-450°C, and the calcination time is 4-6h. The calcination temperature can be 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C or 500°C, and the time can be 4h, 4.2h, 4.5h, 4.8h, 5h, 5.2h, 5.5h, 5.8h or 5h, but is not limited to the listed values, and other values not listed in the above ranges are also applicable.

[0037] A third object of the present application is to provide a method for applying the heavy oil hydrodemetallization transition catalyst provided in one of the objects, which is applied to a fixed-bed hydroprocessing reaction in which at least three hydroprocessing reactors are connected in series, preferably a fixed-bed hydroprocessing reaction in which five hydroprocessing reactors are connected in series.

[0038] As a preferred technical solution of the present application, the method for applying the catalyst includes:

[0039] (1) The catalyst loading form in the first residue hydroprocessing reactor is that the reactor is loaded from top to bottom with at least one guard catalyst and one demetallization catalyst, and preferably 4-5 kinds of guard catalysts and demetallization catalysts are loaded in order of decreasing size and increasing activity;

[0040] Among them, the loading volume of the guard catalyst accounts for 20-30% of the total volume of the reactor, and the loading volume of the demetallization catalyst accounts for 70-80% of the total volume of the reactor;

[0041] (2) The catalyst loading form in the second residue hydroprocessing reactor is that the reactor is loaded from top to bottom with at least one demetallization catalyst, and preferably 3-4 kinds of demetallization catalysts are loaded in order of decreasing size and increasing activity;

[0042] (3) The catalyst loading form in the third residue hydroprocessing reactor is that the reactor is loaded from top to bottom with the heavy oil hydrodemetallization transition catalyst and at least one demetallization catalyst;

[0043] Among them, the loading volume of the heavy oil hydrodemetallization transition catalyst accounts for 15-25% of the total volume of the reactor, and the loading volume of the demetallization catalyst accounts for 75-85% of the total volume of the reactor.

[0044] The volume of the protective agent filling in the first residue hydrogenation reactor accounts for 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30% of the total volume of the reactor, and the volume of the demetallization agent filling accounts for 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79% or 80% of the total volume of the reactor. The volume of the heavy oil hydrogenation demetallization transition catalyst filling in the third residue hydrogenation reactor accounts for 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25% of the total volume of the reactor, and the volume of the demetallization agent filling accounts for 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84% or 85% of the total volume of the reactor, but is not limited to the listed values, and other values not listed in the above numerical range are also applicable.

[0045] Preferably, the fourth reactor is filled with at least one desulfurization transition agent and one desulfurization agent from top to bottom; wherein the volume of the desulfurization transition agent filling accounts for 20% to 40% of the total volume of the reactor, and the volume of the desulfurization agent filling accounts for 60% to 80% of the total volume of the reactor.

[0046] Preferably, the fourth reactor is filled with at least one desulfurization transition agent and one desulfurization agent from top to bottom; wherein the volume of the desulfurization transition agent filling accounts for 20% to 40% of the total volume of the reactor, and the volume of the desulfurization agent filling accounts for 60% to 80% of the total volume of the reactor.

[0047] Preferably, the fifth reactor is filled with at least one desulfurization catalyst.

[0048] In the present application, the gradation application method of the heavy oil hydrogenation demetallization transition catalyst has the advantages of further pretreating macromolecules containing nickel and vanadium which are difficult to remove, forming an effective "relay" removal effect with the subsequent gradation demetallization agent, promoting metal removal, and improving the overall efficiency of the catalyst gradation system.

[0049] Compared with the prior art, the present application has at least the following beneficial effects:

[0050] (1) The present application provides a heavy oil hydrogenation demetallization transition catalyst and a preparation and gradation application method thereof, which can effectively improve the removal rate of nickel and vanadium in the demetallization agent bed under the same reaction conditions;

[0051] (2) The application provides a heavy oil hydrodemetallization transition catalyst and a preparation and grading application method thereof, the hydrodemetallization transition catalyst can pre-decompose metal-containing residual oil macromolecules, decomposes the macromolecules into relatively small molecules, improves the accessibility of metal-containing molecules to active centers on a subsequent demetallization agent, further improves a metal removal rate, reduces post-removal of metal nickel and vanadium, effectively protects a main catalyst, and effectively prolongs a heavy oil hydrogenation device opening operation period. DETAILED DESCRIPTION

[0052] In order to facilitate the understanding of the present application, the present application lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0053] Embodiment 1

[0054] The embodiment provides a heavy oil hydrodemetallization transition catalyst preparation and a grading application method thereof. The pseudo-boehmite is selected by mainly using the following parameters: pore volume 1.35 ml / g, BET specific surface area 268 m 2 / g, peptization index 22%. The SiO2 is selected by mainly using the following parameters: pore volume 0.55 ml / g, BET specific surface area 580 m 2 / g, mesopore ratio 88%. The carrier SiO2 is added into a magnesium nitrate solution with a concentration of 1.5 mol / L for equal-volume impregnation to prepare a mesoporous carrier SiO2 containing 6.0% of magnesium oxide.

[0055] 10 kg of the pseudo-boehmite, 3.8 kg of the mesoporous carrier SiO2 containing 6.0% of magnesium oxide, 0.3 kg of Tianqing powder, 0.2 kg of carboxymethyl cellulose, and 10 kg of deionized water are kneaded on a kneader for 20 minutes, and then are extruded into a four-leaf clover-shaped carrier with a diameter of 1.3±0.1 mm on an extruder. The carrier is fully dried at 120 DEG C, and then is calcined at 750 DEG C for 6 h to obtain a γ-Al2O3-SiO2 carrier.

[0056] The obtained carrier is subjected to active metal component loading by using a saturation impregnation method. The impregnated carrier is fully dried at 120 DEG C, and then is calcined at 410 DEG C for 4 h to obtain the heavy oil hydrodemetallization transition catalyst of the embodiment, and the loadings (mass fractions) of active metals MoO3, NiO and P2O5 are 5.5%, 1.2% and 1.1%, respectively.

[0057] The grading application method of the demetallization transition catalyst prepared by using the above method is as follows: 25% (volume ratio, the same below) of the protective agent and 75% of the demetallization agent are loaded from top to bottom in the first reactor, and four demetallization catalysts with different sizes and different activities are loaded from top to bottom in the second reactor.

[0058] The third reactor is filled from top to bottom with the demetallization transition catalyst prepared in this embodiment and a demetallization agent. The volume of the demetallization transition catalyst accounts for 15% of the total volume of the reactor, and the volume of the demetallization agent accounts for 85% of the total volume of the reactor.

[0059] The fourth reactor is filled from top to bottom with a desulfurization transition catalyst and a desulfurization agent, and the volume of the desulfurization transition catalyst accounts for 30% of the total volume of the reactor. The fifth reactor is filled with a de-carbon residue catalyst.

[0060] The five reactors are connected in series, and after the catalysts are activated by sulfuration, the residual oil is subjected to hydrogenation reaction. The reaction temperature is 380 DEG C, the reaction pressure is 16.0 MPa, the hydrogen / oil volume ratio is 800:1, the liquid hourly space velocity is 0.2 h-1, and the hydrogenation reaction is carried out under the conditions of a hydrogen pressure of 16.0 MPa, a hydrogen / oil volume ratio of 800:1, and a liquid hourly space velocity of 0.2 h-1. -1 .

[0061] Compared with the conventional residual oil fixed-bed hydrogenation catalyst grading method, the demetallization transition catalyst prepared by using the method can significantly improve the removal effect of nickel and vanadium in residual oil.

[0062] Embodiment 2

[0063] The embodiment provides a heavy oil hydrogenation demetallization transition catalyst preparation and grading application method. Pseudo-boehmite is selected, and main physical parameters thereof are as follows: pore volume 1.30 ml / g, BET specific surface area 255 m 2 / g, and peptization index 25%. SiO2 main physical parameters are as follows: pore volume 0.58 ml / g, BET specific surface area 595 m 2 / g, and mesopore ratio 90.0%. The carrier SiO2 is added into a 2.0 mol / L magnesium nitrate solution for equal-volume impregnation to prepare mesoporous carrier SiO2 containing 8% magnesium oxide.

[0064] 10 kg of the pseudo-boehmite, 3.5 kg of the mesoporous carrier SiO2 containing 8% magnesium oxide, 0.3 kg of Tianqing powder, 0.3 kg of hydroxypropyl cellulose, and 10 kg of deionized water are mixed, kneaded, formed, and calcined, and the carrier impregnation and calcination methods are the same as those in Embodiment 1. The heavy oil hydrogenation demetallization transition catalyst in this embodiment is obtained, and the active metal MO3, NiO, and P2O5 loadings (mass fraction) are 7.5%, 2.0%, and 2.0%, respectively.

[0065] The embodiment prepares a desulfurization transition catalyst grading application method and reaction condition, which are the same as those in Embodiment 1.

[0066] Embodiment 3

[0067] The embodiment provides a heavy oil hydrogenation desulfurization transition catalyst preparation and grading application method. Pseudo-boehmite is selected, and main physical parameters thereof are as follows: pore volume 1.25 ml / g, BET specific surface area 245 m 2 / g, and the mesopore ratio is 85%. The carrier SiO2 is dipped into a calcium nitrate solution with a concentration of 2.2 mol / L in an equal volume to prepare mesoporous carrier SiO2 containing 6.0% calcium oxide. 2 / g, and the mesopore ratio is 85%. The carrier SiO2 is dipped into a calcium nitrate solution with a concentration of 2.2 mol / L in an equal volume to prepare mesoporous carrier SiO2 containing 6.0% calcium oxide.

[0068] The pseudo-boehmite 10 kg, mesoporous carrier SiO2 containing 6.0% calcium oxide 4.2 kg, Tianqing powder 0.3 kg, carboxymethyl cellulose 0.2 kg, and deionized water 10 kg are mixed, kneaded, shaped, and calcined according to the method of Example 1. The carrier dipping and calcination methods are the same as those of Example 1, and a heavy oil hydrodemetallization transition catalyst is obtained, with the active metal MO3, NiO, and P2O5 loadings (mass fraction) being 5.5%, 1.2%, and 1.1%, respectively.

[0069] The preparation method of the demetallization transition catalyst and the method of using the catalyst in a grading manner are the same as those of Example 3.

[0070] Example 4

[0071] The present example provides a method for preparing a heavy oil hydrodemetallization transition catalyst and a method of using the catalyst in a grading manner. Pseudo-boehmite is selected, with the main physical property parameters being: pore volume 1.25 ml / g, BET specific surface area 245 m 2 / g, and the mesopore ratio is 85%. The carrier SiO2 is dipped into a calcium nitrate solution with a concentration of 2.2 mol / L in an equal volume to prepare mesoporous carrier SiO2 containing 6.0% calcium oxide. 2 / g, and the mesopore ratio is 85%. The carrier SiO2 is dipped into a calcium nitrate solution with a concentration of 2.2 mol / L in an equal volume to prepare mesoporous carrier SiO2 containing 6.0% calcium oxide.

[0072] The pseudo-boehmite 10 kg, mesoporous carrier SiO2 containing 6.0% calcium oxide 4.2 kg, Tianqing powder 0.3 kg, carboxymethyl cellulose 0.2 kg, and deionized water 10 kg are mixed, kneaded, shaped, and calcined according to the method of Example 1. The carrier dipping and calcination methods are the same as those of Example 1, and a heavy oil hydrodemetallization transition catalyst is obtained, with the active metal MO3, NiO, and P2O5 loadings (mass fraction) being 5.5%, 1.2%, and 1.1%, respectively.

[0073] The preparation method of the demetallization transition catalyst and the method of using the catalyst in a grading manner are the same as those of Example 3.

[0074] Comparative Example 1

[0075] The comparative example 1 was prepared without mesoporous SiO2, magnesium oxide and calcium oxide in the hydrodemetallization transition catalyst. The same pseudo-boehmite 10 kg, tanqing powder 0.3 kg, carboxymethyl cellulose 0.2 kg, deionized water 10 kg as in example 1 were selected, and the kneading, molding and calcination methods were referred to example 1. The carrier impregnation, calcination method and active metal loading were the same as example 1.

[0076] The catalyst grading method of the comparative example 2 was used to replace the demetallization transition catalyst in example 1, and the rest of the catalyst proportion, reaction raw materials and reaction conditions were the same as example 1.

[0077] Comparative example 2

[0078] The comparative example 3 used conventional heavy oil hydrogenation catalysts and their grading methods, i.e. without using demetallization transition catalyst, and compared the catalyst grading method in example 1, and the third reactor was only filled with demetallization catalyst. The other catalysts, reaction raw materials and reaction conditions were the same as example 1.

[0079] Comparative example 3

[0080] The reaction process in the comparative example 4 was only set up with three reactors, the catalyst loading method in the first and second reactors was the same as example 1, and the third reactor was filled from top to bottom with the demetallization transition catalyst prepared in example 2 and a demetallization agent, wherein the volume of the demetallization transition catalyst accounted for 15% of the total volume of the reactor, and the demetallization agent accounted for 85%. The reaction raw materials and conditions were the same as example 1.

[0081] Comparative example 4

[0082] The reaction process in the comparative example 4 was only set up with three reactors, the catalyst loading method in the first and second reactors was the same as example 1, and the third reactor was only filled with the same demetallization agent as in comparative example 3, and the other catalysts, reaction raw materials and reaction conditions were the same as example 1.

[0083] Test and results

[0084] The main index analysis method of the hydrogenated heavy oil is as follows:

[0085] Sulfur content test method: GB / T17040 Petroleum Products-Sulfur Content Determination Method (Energy Dispersive X-ray Fluorescence Spectrometry).

[0086] Carbon residue test method: GB / T268 Petroleum Products-Carbon Residue Determination Method (Conradson Method).

[0087] Nitrogen content test method: SH / T0657 Trace Nitrogen in Liquid Petroleum Hydrocarbons-Determination Method (Oxidative Combustion and Chemiluminescence Method).

[0088] Metal content analysis method: SH / T0715 Determination of nickel, vanadium and iron content in crude oil and residual fuel oil (ICP).

[0089] The main properties of the residual oil feedstock used in the above examples and comparative examples are: sulfur content 4.33wt%, total nitrogen content 2700μg / g, carbon residue 13.84%, metal (Ni+V) content 95.5μg / g. The test results of the examples and comparative examples are shown in Table 1.

[0090] Table 1

[0091]

[0092] (1) The present application provides a method for preparing and grading the use of heavy oil hydrodesulfurization transition agent. As can be seen from Examples 1-4, Comparative Example 1 and Comparative Example 2, the demetallization transition catalyst prepared by the present application can significantly improve the heavy oil hydrodemetallization effect, and other indicators of hydrocracking heavy oil are also significantly improved.

[0093] (2) As can be seen from Comparative Example 3 and Comparative Example 4, the desulfurization transition agent prepared by the present application can significantly improve the removal rate of metal nickel and vanadium, so that as much nickel and vanadium as possible are removed and deposited in the demetallization agent bed, reducing the post-removal delay and protecting the performance of the main catalysts for hydrodesulfurization and hydrodecarbon.

[0094] (3) The comparison of different examples shows that the formulation of the demetallization transition catalyst and the grading application scheme are different, and the effect of heavy oil hydrofining is different. The carrier and catalyst preparation method can be optimized within the scope of the present application, and the excellent heavy oil hydrodemetallization effect can be obtained according to the grading application method of the present application.

[0095] The applicant declares that the above examples are used to illustrate the detailed process equipment and process flow of the present application, but the present application is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present application must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the scope of protection and disclosure of the present application.

Claims

1. A heavy oil hydrodemetallization transition catalyst characterized by, The catalyst comprises a carrier and an active component, the carrier is γAl2O3-SiO2 containing alkali metal or alkaline earth metal oxide, and the active component is NiO and MoO3; The mass content of γAl2O3 in the carrier is 60.0-75.0%, the mass content of SiO2 is 10.0-20.0%, and the balance is alkali metal or alkaline earth metal oxide; The mass content of NiO in the catalyst is 1.0-3.5%; The mass content of MoO3 in the catalyst is 4.5-10.0%; The preparation method of the catalyst comprises: The carrier γAl2O3-SiO2 is prepared by using SiO2 containing alkali metal or alkaline earth metal elements and pseudo-boehmite; The active component is NiO and MoO3 loaded by impregnation method, and the catalyst is obtained after calcination.

2. The catalyst according to claim 1, characterized in that, The catalyst further comprises an additive.

3. The catalyst of claim 2, wherein The additive is phosphorus.

4. The catalyst of claim 3, wherein The mass content of diaphosphorus pentoxide in the catalyst is 0.5-2.0% in terms of oxide content.

5. The catalyst of claim 1, wherein The alkali metal or alkaline earth metal oxide in the carrier is an additive.

6. The catalyst of claim 1, wherein The mass content of alkali metal or alkaline earth metal oxide in the catalyst is 2.0-6.5%.

7. A process for the preparation of the catalyst according to any one of claims 1 to 6, characterized in that, The preparation method comprises: The carrier γAl2O3-SiO2 is prepared by using SiO2 containing alkali metal or alkaline earth metal elements and pseudo-boehmite; The active component is NiO and MoO3 loaded by impregnation method, and the catalyst is obtained after calcination.

8. The production method according to claim 7, characterized by, The preparation method of the SiO2 containing alkali metal or alkaline earth metal elements comprises:

9. The production method according to claim 8, characterized by, The alkali metal or alkaline earth metal salt solution comprises any one or a combination of at least two of magnesium or calcium nitrate or chloride.

10. The preparation method according to claim 7, characterized in that, The preparation method of the carrier γAl2O3-SiO2 comprises: The pseudo-boehmite, SiO2 containing alkali metal or alkaline earth metal elements, molding aid, and deionized water are mixed to form a molded carrier; The molded carrier is dried and calcined to obtain the carrier γAl2O3-SiO2.

11. The method of claim 10, wherein, The molding aid comprises any one or a combination of at least two of sesbania powder, carboxymethyl cellulose, hydroxypropyl methyl cellulose, or hydroxyethyl cellulose.

12. The method of claim 10, wherein, The calcination temperature is 600-780 ℃.

13. The method of claim 12, wherein, The calcination temperature is 650-770 ℃.

14. The method of claim 10, wherein, The calcination time is 6-8 h.

15. The method of claim 7, wherein the method further comprises, The method for loading the active component by impregnation comprises equal-volume impregnation or excess impregnation.

16. The method of claim 15, wherein, The method for loading the active component by impregnation is equal-volume solution impregnation.

17. The method of claim 16, wherein the method further comprises, The equal-volume impregnation method comprises immersing the carrier in a solution with the same volume as the pores of the carrier, which is composed of nickel salt, molybdenum salt, and phosphorus-containing inorganic acid.

18. The method of claim 17, wherein, The nickel salt comprises any one or a combination of at least two of nickel nitrate, basic nickel carbonate, nickel acetate, or nickel citrate.

19. The method of claim 17, wherein, The molybdenum salt comprises molybdenum trioxide and / or ammonium heptamolybdate tetrahydrate.

20. The method of claim 17, wherein, The phosphorus-containing inorganic acid comprises any one or a combination of at least two of phosphoric acid, metaphosphoric acid, hypophosphorous acid, or phosphorous acid.

21. The method of claim 7, wherein, The calcination temperature after impregnation is 400-500 ℃.

22. The method of claim 21, wherein, The calcination temperature after impregnation is 410-450 ℃.

23. The method of claim 7, wherein the method further comprises, The calcination time after impregnation is 4-6 h.

24. A method for applying the gradation of the heavy oil hydrodemetallization transition catalyst according to any one of claims 1 to 6, characterized by, The grading application method is applied to fixed bed hydrogenation reaction of at least 3 hydrogenation reactors in series.

25. The method of gradation application of claim 24, wherein, The grading application method is applied to fixed bed hydrogenation reaction of 5 hydrogenation reactors in series.

26. The method of claim 25, wherein the graded application is characterized by, The grading application method comprises: (1) The internal catalyst loading form of the first residue hydrogenation reactor is that the reactor is loaded from top to bottom with at least one protective agent and one metal removal agent, and the protective agent and the metal removal agent are loaded in 4-5 kinds according to the size from large to small and the activity from weak to strong. Among them, the loading volume of the protective agent accounts for 20-30% of the total volume of the reactor, and the loading volume of the metal removal agent accounts for 70-80% of the total volume of the reactor. (2) The internal catalyst loading form of the second residue hydrogenation reactor is that the reactor is loaded from top to bottom with at least one metal removal agent, and the metal removal agent is loaded in 3-4 kinds according to the size from large to small and the activity from weak to strong. (3) The internal catalyst loading form of the third residue hydrogenation reactor is that the reactor is loaded from top to bottom with the heavy oil hydrogenation metal removal transition catalyst and at least one metal removal agent. Among them, the loading volume of the heavy oil hydrogenation metal removal transition catalyst accounts for 15-25% of the total volume of the reactor, and the loading volume of the metal removal agent accounts for 75-85% of the total volume of the reactor.

27. The method of claim 25, wherein the graded application is characterized by, The grading application method comprises: the fourth reactor is loaded from top to bottom with at least one desulfurization transition agent and one desulfurization agent; wherein the loading volume of the desulfurization transition agent accounts for 20-40% of the total volume of the reactor, and the loading volume of the desulfurization agent accounts for 60-80% of the total volume of the reactor.

28. The method of claim 25, wherein the graded application is characterized by, The grading application method comprises: the fifth reactor is loaded with at least one residual carbon removal catalyst.

Images