A method for hydroprocessing of residual oil

Abstract

The present application provides a method for residue hydroprocessing. The method comprises: providing an inlet diffuser and a distribution tray in one or more hydrogenation reactors, wherein the inlet diffuser and the distribution tray constitute an upper space; filling a hydroprocessing catalyst M in the upper space; the hydroprocessing catalyst M comprises a carrier and a hydrogenation active metal component, the carrier is a sphere with a diameter of 3.5-10.0 mm, the outer surface of the carrier has a plurality of non-intercommunicating large pores, and the cross-sectional area of the large pores gradually decreases from outside to inside along the radial direction, and the longest depth of the large pores is 30%-99% of the radius of the spherical carrier. The method of the present application is suitable for treating residue oil with high content of iron and calcium impurities, not only can effectively remove and adhere iron and / or calcium impurities, but also has high overall activity of the catalyst, and can fully utilize the space in the reactor, accommodate more carbon deposition, delay the rise of bed pressure drop, and prolong the operation period of the device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of residual oil hydrogenation, and particularly relates to a hydrogenation treatment method of heavy and poor residual oil with high contents of iron and calcium impurities. BACKGROUND

[0002] With the crude oil becoming heavier and poorer, more and more heavy oil and residual oil need to be processed. The processing of heavy oil and residual oil not only needs to crack them into low-boiling-point products such as naphtha, middle distillate and vacuum gas oil, but also needs to improve their hydrogen-carbon ratio, which needs to be realized through decarburization or hydrogenation methods. The decarburization processes include coking, solvent deasphalting, heavy oil catalytic cracking, etc.; the hydrogenation processes include hydrocracking, hydrofining, hydroprocessing, etc. The hydrogenation process can not only hydrogenate and convert residual oil to improve the yield of liquid products, but also remove heteroatoms in the products, so the products have good quality and have obvious advantages. Therefore, various oil refining enterprises build new residual oil hydroprocessing devices to process heavier and poorer residual oil to obtain better benefits.

[0003] The feedstock cracking rate of heavy oil and residual oil hydroprocessing technology is relatively low, and the main purpose is to provide feedstock for downstream feedstock lightening devices such as catalytic cracking or coking devices. Through hydroprocessing, the contents of impurities such as sulfur, nitrogen, metal, etc. and the carbon residue value in poor residual oil are significantly reduced, so that the feedstock acceptable by the downstream feedstock lightening device can be obtained.

[0004] For a catalytic cracking device, if the contents of iron and / or calcium in the feedstock are too high, the accessibility of heavy oil molecules to the active centers of the catalyst will be reduced, resulting in a decrease in the conversion rate of heavy oil. Moreover, the contents of iron and / or calcium in the feedstock being too high will also cause the formation of nodular protrusions on the surface of the catalyst, resulting in a decrease in the bulk density, and further affecting the circulation of the catalyst between the reactor and the regenerator, and even affecting the processing load of the device. In addition, iron has a dehydrogenation effect, resulting in a high hydrogen / methane ratio in dry gas. In summary, the contents of iron and / or calcium in the feedstock being too high will result in a decrease in the conversion rate of heavy oil, a poor product selectivity, an impact on the processing load of the device, and further an impact on the economic benefits of the whole plant. Therefore, it is urgent to control the contents of iron and / or calcium in the feedstock of the catalytic cracking device.

[0005] In the fixed-bed residual oil hydrogenation process, since the feedstock is all heavy oil or residual oil containing metal impurities, the metal impurities will be deposited on the surface and in the pores of the catalyst during the demetallization process, especially iron and / or calcium will be mainly deposited on the outer surface of the catalyst, which will rapidly reduce the void fraction of the catalyst bed layer and cause the bed pressure drop to rise, thereby affecting the operation cycle of the device.

[0006] CN1335368A discloses a residue oil treatment method. The method is as follows: before passing through hydrogenation reaction, heavy oil and residue oil raw materials are first subjected to a pretreatment process of adsorption filtration, so that suspended particles carried by the raw materials can be removed, and ferrous sulfide generated by naphthenic acid iron in crude oil and most of substances prone to coking can be removed, so as to reduce fouling of a residue oil hydrogenation reactor and prolong the operation cycle of the device. However, the method needs to additionally increase a pretreatment device, and before hydrotreatment, naphthenic acid iron has not reacted and is still dissolved in the raw materials, so that the iron removal effect is poor.

[0007] CN103289734A discloses a high-metal, high-sulfur and high-nitrogen poor-quality heavy oil hydrotreatment process and catalyst grading combination, which contains two series-connected up-flow iron and calcium removal reactors, a fixed-bed metal removal reactor, a fixed-bed sulfur removal reactor and a fixed-bed nitrogen removal reactor, wherein the up-flow iron and calcium removal reactor is filled with a hydrogenation iron and calcium removal catalyst, and from the center of the catalyst particles to the outer surface, the active metal component of the hydrogenation iron and calcium removal catalyst is in an "egg yolk" distribution, so as to prolong the operation cycle of the device. The method can adjust the distribution of removed iron and calcium on the catalyst to a certain extent, but still cannot solve the problem that iron and calcium impurities are easily deposited on the outer surface of the catalyst, which causes rapid pressure drop increase and affects the operation cycle of the device. SUMMARY

[0008] In view of the deficiencies in the prior art, the present application provides a residue oil hydrotreatment method. The method of the present application is particularly suitable for treating residue oil with high iron and calcium impurity content, can effectively remove and attach iron and / or calcium impurities, has high overall activity of the catalyst, can fully utilize the space in the reactor, accommodate more carbon deposits, delay the increase of bed pressure drop and prolong the operation cycle of the device.

[0009] The present application provides a residue oil hydrotreatment method, which comprises: providing an inlet diffuser and a distribution plate in one or more hydrogenation reactors, wherein an upper space is formed by the inlet diffuser and the distribution plate; filling a hydrotreatment catalyst M in the upper space; the hydrotreatment catalyst M comprises a carrier and a hydrogenation active metal component, the carrier is a sphere with a diameter of 3.5-10.0 mm, wherein the outer surface of the carrier has a plurality of non-intercommunicating large pores, and the cross-sectional area of the large pores gradually decreases from the outside to the inside along the radial direction, wherein the bottom area of each large pore is 0.05%-5% of the surface area of the sphere, the total bottom area of the large pores is 5%-50% of the surface area of the sphere, and the longest depth of the large pores, measured along the length of the pores in the radial direction of the sphere, is 30%-99% of the radius of the spherical carrier, preferably 55%-96%.

[0010] The upper space formed by the inlet diffuser and the distribution plate can be provided with one or more containers; further preferably, a fouling accumulator and / or a filter distributor.

[0011] In the method for residue hydroprocessing, the loading volume of the catalyst M accounts for 20% to 90% of the effective volume of the upper space, preferably 30% to 60%.

[0012] In the method for residue hydroprocessing, in the hydroprocessing catalyst M, the cross section of the macropore in the carrier refers to the spherical surface formed by the spherical center of the carrier as the spherical center, and the face corresponding to the macropore on the spherical surface is the cross section.

[0013] Further, the macropore on the surface of the carrier extends from the outer surface to the spherical center.

[0014] Further, the bottom surface of the macropore in the carrier is at least one of circular, elliptical, polygonal, and irregular on the outer surface of the sphere.

[0015] Further, the macropore of the carrier is a conical pore or a pyramid pore, and preferably the angle of the top angle of the conical pore or the pyramid pore is 5 to 50 degrees.

[0016] The formula for calculating the surface area of the sphere is S=πD², and D is the diameter of the sphere.

[0017] Further, the cross-sectional area of the macropore gradually decreases from the outside to the inside along the radial direction, which means that the cross-sectional area of each macropore gradually decreases along the radial direction from the outside to the inside within the entire interval range, but it is allowed to remain constant within one or more intervals. The interval refers to the distance between any two cross sections within the entire interval of the macropore, and the interval length of any interval does not exceed 1 / 4 of the longest depth of the macropore.

[0018] Further, the cross-sectional area of the macropore of the carrier gradually decreases from the outside to the inside along the radial direction, and the smallest cross-sectional area accounts for less than 10% of the area of the bottom surface, preferably less than 5%, and further preferably less than 2%.

[0019] Further, the cross-sectional area of the macropore of the carrier gradually decreases from the outside to the inside along the radial direction, and the cross-sectional area from the bottom surface to 1 / 2 of the longest depth accounts for 20% to 70% of the area of the bottom surface, preferably 25% to 65%.

[0020] Further, the cross-sectional area of the macropore gradually decreases from the outside to the inside along the radial direction, and the cross-sectional area from the bottom surface to 1 / 2 of the longest depth accounts for 30% to 80% of the cross-sectional area from the bottom surface to 1 / 4 of the longest depth, preferably 45% to 75%.

[0021] Further, the cross-sectional area of the macropore gradually decreases from the outside to the inside along the radial direction, and the cross-sectional area from the bottom surface to 3 / 4 of the longest depth accounts for 40% to 80% of the cross-sectional area from the bottom surface to 1 / 2 of the longest depth, preferably 55% to 75%.

[0022] Further, the width of the minimum cross section of the large pores is not more than 30 μm.

[0023] The large pores are distributed on the surface of the carrier, and the minimum wall thickness between any two adjacent large pores is 1 / 8 to 1 / 5 of the diameter of the sphere. Preferably, the large pores on the surface of the carrier are the same, i.e., the shapes and sizes are substantially the same, and the same guide mode can be used to form the large pores.

[0024] In the method for residue oil hydroprocessing, the carrier of the hydroprocessing catalyst M is spherical, and is provided with conical large pores with the vertex pointing to the center of the sphere and the bottom surface on the surface of the sphere. The diameter of the spherical carrier is 3.5 to 10.0 mm, the area of the bottom surface of each conical large pore is 0.05% to 4.5% of the surface area of the sphere, the total area of the bottom surfaces of the conical large pores is 5% to 50% of the surface area of the sphere, the height of the conical large pores is 50% to 99% of the radius of the spherical carrier, preferably 55% to 96%, the angle of the vertex angle of the conical large pores is 5 to 50 degrees, and the conical large pores are uniformly distributed on the surface of the sphere.

[0025] Further, the carrier of the hydroprocessing catalyst M is provided with 4 to 40 conical large pores, preferably 8 to 40.

[0026] The hydroprocessing catalyst M of the present application uses Al2O3-SiO2 as the carrier, and the weight content of SiO2 is 20% to 50%, preferably 30% to 40%, based on the weight of the carrier.

[0027] In the method for residue oil hydroprocessing, the carrier of the hydroprocessing catalyst M preferably further contains the oxide of a first metal component, and the first metal component is NiO. The molar ratio of the oxide of the first metal component NiO to Al2O3 is 0.001:1 to 0.13:1, preferably 0.005:1 to 0.05:1.

[0028] In the method for residue oil hydroprocessing, the carrier of the hydroprocessing catalyst M has the following properties: the specific surface area is 100 to 200 m 2 / g, the pore volume is 0.70 mL / g or more, preferably 0.75 to 1.15 mL / g, the pore volume of pores with a diameter of 20 to 100 nm accounts for 35% to 60% of the total pore volume, and the average pore diameter is 15 nm or more, preferably 17 to 30 nm.

[0029] In the method for residue hydroprocessing of the present application, in the hydroprocessing catalyst M, the active metal component comprises a second metal component, i.e. a Group ⅥB metal, and a third metal element, i.e. a Group Ⅷ metal element, wherein the Group ⅥB metal is preferably Mo, and the Group Ⅷ metal is preferably Ni and / or Co.

[0030] In the method for residue hydroprocessing of the present application, in the hydroprocessing catalyst M, the content of the second metal component, calculated as oxide, is 0.10% to 10.0%, preferably 0.5% to 7.5%, based on the weight of the catalyst, the total content of the first metal component and the third metal component, calculated as oxide, is 0.03% to 5.0%, preferably 0.05% to 3.0%, the content of silicon oxide is 25.0% to 35.0%, and the content of aluminum oxide is 55.0% to 65.0%.

[0031] In the present application, the catalyst M can be packed in a disordered manner. The catalyst M can be packed in an independent fouler, or in the entire filter distribution tray. If there are multiple reactors, the catalyst M can be packed in one or more of the reactors, and the catalyst M packed in each reactor can be the same or different, and the packing height and amount of the catalyst M in each reactor can be the same or different.

[0032] In the method for residue hydroprocessing of the present application, under the hydroprocessing reaction conditions, the residue feedstock and hydrogen are sequentially passed through one or more hydroprocessing reactors connected in series, and are contacted with the catalysts as described above for reaction.

[0033] In the method for residue hydroprocessing of the present application, the operating conditions of each reactor are independently as follows: the reaction pressure is 5 to 25 MPa, the reaction temperature is 300 to 430℃, the liquid hourly space velocity is 0.05 to 5.0 h -1 , and the hydrogen to oil volume ratio is 150:1 to 1000:1.

[0034] Compared with the prior art, the method for residue hydroprocessing of the present application has the following advantages:

[0035] 1、The inventor of the present application found through a large number of studies that the iron and calcium in the residual oil can be divided into two categories: organic and inorganic. The inorganic iron and calcium is easy to remove, but the organic iron and calcium is not easy to remove. Even if ferrous sulfide and calcium sulfide are generated, they are attached to the surface of the catalyst and are extremely easy to fall off and penetrate the catalyst bed with the stream. The falling off of ferrous sulfide and calcium sulfide fragments and particulate matter into the downstream catalyst bed not only causes the porosity of the downstream catalyst bed to decrease and the bed pressure drop to increase, but also causes the radial temperature difference of the local stream in the bed, and further affects the operation of the downstream device (such as a catalytic cracking device). In addition, since the feed filter of the residual oil hydrogenation device can generally only filter out mechanical impurities with a particle size greater than 25 µm, mechanical impurities with a particle size less than 25 µm will enter the reactor and attach to the outer surface and pore of the catalyst, so that the activity of the catalyst cannot be fully utilized. At the same time, the mechanical impurities also become the nuclei for coke deposition, and the presence of the mechanical impurities increases the amount of coke deposition, occupies the space between the catalyst particles, reduces the flow capacity of the stream, and continuously increases the bed pressure drop as the mechanical impurities accumulate. Therefore, the inventor of the present application has invented a method for grading catalyst M and reasonably applied it to solve this problem.

[0036] 2、The top of the conventional downflow fixed bed residual oil hydrogenation reactor has an inlet diffuser and a distribution plate, and there is a large space between the diffuser and the distribution plate, which is not filled with catalyst and is in an idle state. The method of the present application fills the idle space with hydroprocessing catalyst M. Since the hydroprocessing catalyst M has a suitable particle size, pore structure and unique channel structure, it can remove the iron and calcium impurities in the residual oil, effectively deposit and adhere to the macropores on the outer surface of the catalyst, thereby reducing the influence of the iron and calcium impurities on the downstream high-activity desulfurization and denitrification and de-carbon catalyst bed and the downstream device. At the same time, the hydroprocessing catalyst M also has high metal removal activity, further removes the metal impurities Ni and V, and also has certain desulfurization and de-carbon activity. Therefore, by adding the hydroprocessing catalyst M, the total catalyst loading volume does not need to be increased, and good overall activity and stability can be achieved, which avoids rapid increase of the bed pressure drop and is beneficial to prolonging the operation period of the hydrogenation device. In addition, since there is sufficient space in the container, the residual oil stream will flow between the catalyst M particles in the early stage of device operation, and after the catalyst M particles are filled with dirt and coke in the later stage of device operation, the residual oil stream will pass through the gap around the container, so the loading of the catalyst M will not cause the bed pressure drop to rise.

[0037] 3、The surface of the hydrogenation treatment catalyst M adopted by the present application has a certain number and size of large channels, the large channels are not interconnected and not through, and the cross-sectional area of the large channels gradually decreases from the outside to the inside along the radial direction, and the channel shape is preferably conical (conical or pyramidal). The large channels on the catalyst particles can greatly reduce the distance and resistance of the residue molecules to diffuse into the interior of the catalyst particles. The non-interconnected and non-through channels avoid the direct flow of the residue stream out of the channels, increase the residence time of the residue stream in the channels, and increase the deposition probability of particles and scale. The inventors have creatively found through a large number of experiments that the channel of the catalyst carrier of the present application has a conical structure, and the front end of the conical channel is an acute angle. The particles and scale after the reaction are easy to bridge within a distance of 20-30 μm of the channel, form a micron-level grid, gradually expand in the large channel from the inside to the outside, and greatly improve the deposition and adhesion efficiency of scale such as iron. The generally prepared through channels are all above 0.1 mm, and it is not easy to provide a bridging space of 20-30 μm, and at the same time, because it is a through channel, the flow is washed, and the deposition difficulty of the scale is increased, so that the deposition and adhesion efficiency of the scale is reduced. At the same time, in the method of the present application, a small amount of nickel salt is preferably added to the catalyst carrier, so that a proper nickel-aluminum spinel structure is generated in the calcination process, which further improves the strength and water resistance of the catalyst, and does not affect the catalytic performance.

[0038] 4、The method of the present application is especially suitable for the hydrogenation treatment of residue oil containing iron, and the content of organic iron and inorganic iron in the residue oil can be above 5 μg / g or above 20 μg / g in terms of iron, and the calcium content can be above 5 μg / g or above 20 μg / g. The catalyst loading method of the present application not only can effectively remove and adhere iron and / or calcium impurities, but also has high overall activity of the catalyst, and can prolong the operation cycle of the device. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1 It is a schematic cross-sectional view of the preparation process of the catalyst carrier M of the residue oil hydrogenation treatment catalyst of the present application;

[0040] Figure 2 It is a schematic view of a hemispherical cavity mold for forming a mold shell;

[0041] Figure 3 It is a schematic cross-sectional view of the prepared catalyst carrier M;

[0042] Figure 4 It is a schematic view of the prepared catalyst carrier M in three dimensions;

[0043] Figure 5 It is a schematic view of a fixed-bed residue oil hydrogenation reactor installed with a fouling device;

[0044] Figure 6 It is a schematic view of a fixed-bed residue oil hydrogenation reactor installed with a filter distribution tray;

[0045] Reference signs are explained as follows:

[0046] 1. mold shell; 2. paste material; 3. conical large pore forming guide; 4. cavity; 5. conical "thorn"; 6. conical pore; 7. inlet diffuser; 8. distribution plate; 9. fouler; 10. filter distribution plate. DETAILED DESCRIPTION

[0047] The technical solutions of the present application are further described in detail below in combination with examples, but the examples do not limit the protection scope of the present application. In the present application, wt% is mass fraction.

[0048] In the present application, the specific surface area, pore volume, pore size and pore distribution are measured by low-temperature liquid nitrogen adsorption method.

[0049] The hydroprocessing catalyst M of the present application can be prepared by the following method, which comprises:

[0050] (1) adding an acidic peptizing agent to a silicon source for acidification treatment;

[0051] (2) adding pseudoboehmite and a solidifying agent to the material obtained in step (1) to prepare a paste material;

[0052] (3) adding the paste material obtained in step (2) into a mold, and then heating the mold containing the paste material for a certain time to solidify and form the paste material;

[0053] (4) taking out the material of step (3) from the mold, and then washing, drying and calcining to obtain a catalyst carrier;

[0054] (5) impregnating the catalyst carrier obtained in step (4) with a catalyst active metal component, and then drying and calcining to obtain the hydroprocessing catalyst M.

[0055] In the preparation method of the hydroprocessing catalyst M of the present application, a first metal oxide is preferably introduced into the carrier, and the first metal source (nickel source) can be introduced in step (1) and / or step (2), and the preferred introduction method is as follows: adding a nickel source to the material obtained in step (1) and dissolving it in the material. The nickel source can be a soluble nickel salt, and the soluble nickel salt can be one or more of nickel nitrate, nickel sulfate and nickel chloride, and nickel nitrate is preferred.

[0056] In the preparation method of the hydroprocessing catalyst M, the silicon source in step (1) is one or more of water glass and silica sol, wherein the mass content of silicon calculated as silicon oxide is 20% to 40%, preferably 25% to 35%; the acidic glue solvent is one or more of nitric acid, formic acid, acetic acid and citric acid, preferably nitric acid, and the mass concentration of the acidic glue solvent is 55% to 75%, preferably 60% to 65%; the addition amount of the acidic glue solvent is in a molar ratio of hydrogen ions to silicon dioxide of 1:1.0 to 1:1.5; and the pH value of the silicon source after acidification treatment is 1.0 to 4.0, preferably 1.5 to 2.5.

[0057] In the preparation method of the hydroprocessing catalyst M, the dry basis weight of the pseudoboehmite in step (2) is 70% or more, and after high-temperature calcination to convert into γ-Al2O3, the properties are as follows: the pore volume is 0.95 mL / g or more, preferably the pore volume is 0.95 to 1.2 mL / g, the specific surface area is 270 m 2 / g or more, preferably the specific surface area is 270 to 330 m 2 / g. The solidifying agent is one or more of urea and organic ammonium salt. The organic ammonium salt is hexamethonium tetraammonium. The addition amount of the solidifying agent is in a molar ratio of nitrogen atoms to silicon dioxide of 1:1.5 to 1:2.0; and the solid content in the paste material is 25% to 45% by weight of silicon dioxide and aluminum oxide, preferably 28% to 40%, and the paste material should have a certain flowability of plastic body.

[0058] In the preparation method of the hydroprocessing catalyst M, the mold in step (3) comprises a shell with a spherical cavity and a guide film that can match the required pore shape, and the shell is made of rigid material and can have any shape, preferably a symmetrical geometric shape such as a sphere. The mold with a spherical shape and a guide film structure that can form a conical pore is taken as an example for description. The spherical shell can be composed of two identical hemispheres or four quarter spheres. The diameter of the spherical cavity can be adjusted according to the size of the catalyst particles, so that the diameter of the final spherical carrier is 3.5 to 10.0 mm. The material of the guide film is selected from materials that can be removed by heating or burning, such as graphite, wood, paper, paraffin or petroleum resin, etc. The structure of the guide film matches the three-dimensional conical pore in the carrier, and has a conical "thorn" towards the center of the sphere. The thickness d of the guide film excluding the conical "thorn" part is 0 to 2 mm, and the conical "thorn" in the guide film is centrally symmetric. Thus, a guide film capable of generating a conical pore is formed.

[0059] The structure of the guide film matches the pore in the carrier, and a conical pore is generated after the guide film is removed.

[0060] In the preparation method of the hydroprocessing catalyst M, in step (3), first, the partial spherical shells are fixed to each other to form two complete hemispherical cavities, four guide molds are spliced into two hemispherical shapes and are respectively placed in the two complete hemispherical cavities, at this time, the paste material is injected or pressed into the two hemispherical cavities, after filling the entire cavity, the two hemispheres are combined together to form a complete sphere and are fixed.

[0061] In the preparation method of the hydroprocessing catalyst M, in step (3), the mold containing the paste material is heated at a temperature of 70-200°C, preferably 100-150°C, and the constant temperature time is 30-240 minutes, preferably 50-120 minutes, so that the material is solidified.

[0062] In the preparation method of the hydroprocessing catalyst M, in step (4), the mold is removed, that is, the shell is removed, because the paste material in the mold releases alkaline gas after being heated, so that the paste material is solidified and shrinks and is automatically removed from the spherical shell. In step (4), the washing is washing the spherical material removed from the spherical shell to neutral with deionized water, because the quarter sphere is used as the guide mold, in the washing process, the guide mold and the sphere are automatically separated due to the flushing, disturbance and soaking of the deionized water, and the sphere leaves the required large pores. The drying temperature is 100-150°C, and the drying time is 4-10 hours. The calcination temperature is 500-900°C, preferably 550-800°C, and the calcination time is 2-8 hours.

[0063] In the preparation method of the hydroprocessing catalyst M, in step (5), the drying and calcination conditions of the carrier impregnated with the active metal component of the catalyst are as follows: drying at 100-150°C for 4-10 hours, and then calcining at 400-600°C for 2-6 hours.

[0064] The method for hydroprocessing of residual oil is suitable for hydroprocessing of residual oil containing iron and / or calcium. Preferably, the content of organic iron and inorganic iron in the residual oil feedstock is 5 μg / g or more, more preferably 20 μg / g or more, and the calcium content is 5 μg / g or more, more preferably 20 μg / g or more. The residual oil is at least one of atmospheric residual oil and vacuum residual oil, and can also be heavy oil containing residual oil components, such as thick oil, etc. The residual oil feedstock can contain various conventional impurities, such as sulfur, nitrogen, asphaltene, metal impurities and carbon residue, etc. The properties of the residual oil feedstock can be: the sulfur content is not more than 4 wt%, the nitrogen content is not more than 0.7 wt%, the metal content (Ni+V) is not more than 140 µg / g, the carbon residue value is not more than 17 wt%, and the asphaltene content is not more than 5 wt%. The residual oil feedstock can be blended with straight-run wax oil and / or vacuum wax oil, or can be blended with secondary processing wax oil and / or catalytic cracking oil, etc.

[0065] The method of the present application adopts a downflow feeding hydrogenation reactor, and the material first contacts the catalyst M after entering the reactor.

[0066] In the present application, the number of hydrogenation reactors is 1-7, preferably 2-5.

[0067] The hydrogenation treatment catalyst M of the present application is described in detail below with reference to the accompanying drawings.

[0068] The present application is described by taking the external shape as spherical and the guide film as being able to form a conical channel. Figures 1-4 As shown in the figure, when preparing the residue oil hydrogenation treatment catalyst carrier of the present application, the mold comprises a shell 1 with a spherical cavity (see Figure 1 ) and a guide film 3 capable of forming a conical channel (see Figure 1 ). The present application is described by taking the external shape as spherical, and the spherical shell can be composed of two identical hemispheres. The diameter of the spherical cavity is D (see Figure 1 ). The guide film is made of a material that can be removed by heating or burning, such as graphite, wood, paper, paraffin or petroleum resin, etc. The structure of the guide film matches the three-dimensional conical channel in the carrier, and has a conical "thorn" 5 towards the center of the sphere. The thickness of the guide film excluding the conical "thorn" 5 part is d, and the conical "thorn" in the guide film is centrally symmetric. See Figure 1 and Figure 3 . The conical channel 6 produced after removing the guide film.

[0069] In the method of the present application, first, the partial spherical shells are fixed to each other to become two complete hemispherical cavities 4 (see Figure 2 ), and the guide film capable of forming a three-dimensional conical channel is placed in one hemispherical cavity 4. At this time, the paste-like material 2 is pressed into the two hemispherical cavities 4, and after filling the entire cavity, the two hemispheres are combined together to form a complete sphere and are fixed. The guide film forms a conical channel 6, as shown in Figure 3 . The three-dimensional schematic diagram of the catalyst carrier prepared by the present application is shown in Figure 4 .

[0070] The catalyst M of the present application can be loaded in a fouler or in a filter distribution tray. The catalyst M of the present application can be loaded in a fouler or a filter distribution tray, and the volume of the catalyst M loaded in the fouler or the filter distribution tray is equal to the effective volume of the catalyst M loaded in the upper space.

[0071] Example 1

[0072] Take 400g of water glass with 30wt% of silicon oxide content into a beaker, start the stirring device, slowly add 150g of nitric acid solution with 62% of mass concentration into the beaker, then add nickel nitrate, after stirring and dissolving, the pH value of the water glass solution in the beaker is 2.0, then add 385.3g of pseudo-boehmite (with the following properties: pore volume 1.05mL / g, specific surface area 306m 2 / g, dry base 70wt%) into the above solution, control the molar ratio of nickel oxide and aluminum oxide in the carrier to be 0.06:1, after stirring uniformly, add 35g of solidifying agent urea, after the urea is completely dissolved, add deionized water, so that the material in the beaker is in a paste state with a certain flowability, and the solid content calculated based on silicon dioxide and aluminum oxide is 33%.

[0073] The paste material is pressed into two identical hemispheres with spherical cavities. A guide film is placed in one of the hemispheres, which is made of wood. The guide film of the spherical carrier matches the carrier and can form a conical channel structure. The guide film is divided into four quarter spheres, and it has six conical "spines" pointing towards the center of the sphere. The tips of the conical "spines" point to the center of the sphere, and the bases are connected to the surface of the quarter sphere. The conical channels of the carrier are uniformly distributed on the surface of the sphere.

[0074] The paste material is pressed into the cavities of the two hemispheres, and after filling the entire cavity, the two hemispheres are combined to form a complete sphere and fixed.

[0075] The mold containing the paste material is heated to 120°C and kept at this temperature for 60 minutes. The paste material releases ammonia gas when heated, causing it to solidify and shrink, and then automatically demolds into a spherical gel. The spherical gel is then washed with deionized water until it is neutral. The spherical gel is dried at 120°C for 5 hours, and then calcined at 750°C for 3 hours to obtain the spherical catalyst carrier A of the present application. The diameter of the obtained catalyst carrier A is 3.5mm, the number of conical channels is 24, the height of the conical channels is 1.6mm, the angle of the conical channel tip is 20 degrees, the area of the conical channel base is 0.754% of the surface area of the sphere, and the total area of the conical base is 18% of the surface area of the sphere.

[0076] The carrier A is immersed in a Mo-Ni-P solution, dried at 120°C for 6 hours, and then calcined at 500°C for 3 hours to obtain the catalyst M1 of the present application. The properties of the catalyst are shown in Table 1.

[0077] Example 2

[0078] The preparation process is the same as in Example 1, except that the amount of nickel nitrate is increased, and the molar ratio of nickel oxide and aluminum oxide in the carrier is controlled to be 0.10:1. The properties of the prepared catalyst carrier B and catalyst M2 are shown in Table 1.

[0079] The diameter of the obtained catalyst carrier B is 8 mm, the number of the conical channels is 40, the height of the conical channels is 3.5 mm, the angle of the conical channel vertex is 15 degrees, the bottom area of the conical channel is 0.43% of the surface area of the sphere, and the total area of the conical bottom is 17% of the surface area of the sphere.

[0080] Example 3

[0081] The preparation process is the same as that in Example 1, except that 46.6 g of hexamethyl tetrammonium is added as the solidifying agent, and the properties of the prepared catalyst carrier C and catalyst M3 are shown in Table 1.

[0082] The diameter of the obtained catalyst carrier C is 6 mm, the number of the conical channels is 40, the height of the conical channels is 2.5 mm, the angle of the conical channel vertex is 25 degrees, the bottom area of the conical channel is 1.17% of the surface area of the sphere, and the total area of the conical bottom is 46.85% of the surface area of the sphere.

[0083] Example 4

[0084] The preparation process is the same as that in Example 1, except that no nickel nitrate is added, and the properties of the prepared catalyst carrier D and catalyst M4 are shown in Table 1.

[0085] Example 5

[0086] 800 g of water glass with a silicon oxide content of 30 wt% is weighed into a beaker, a stirring device is started, 299 g of a 62% mass concentration nitric acid solution is slowly added to the beaker, and then nickel nitrate is added. After stirring and dissolving, the pH value of the water glass solution in the beaker is 2.0. Then 575 g of pseudo-boehmite (properties: pore volume 1.05 mL / g, specific surface area 306 m 2 / g, dry basis 70 wt%) is added to the above solution, the molar ratio of nickel oxide to aluminum oxide in the carrier is controlled to be 0.06:1, and then 75 g of a solidifying agent urea is added after stirring uniformly. After the urea is completely dissolved, deionized water is added to make the material in the beaker into a paste with a certain flowability, and the solid content calculated based on silicon dioxide and aluminum oxide is 35%.

[0087] The guide film of the spherical carrier is matched with the carrier to form a conical channel structure. The guide film is divided into a quarter of a sphere, and it has two conical "thorns" pointing towards the center of the sphere. The vertex of the conical "thorn" points to the center of the sphere, and the bottom surface is connected to the surface of the quarter of the sphere. The conical channels of the carrier are uniformly distributed on the surface of the sphere.

[0088] The paste material is pressed into the cavities of the two hemispheres, and after filling the entire cavity, the two hemispheres are combined together to form a complete sphere and are fixed.

[0089] The mold containing the paste material was heated to 120°C and kept at this temperature for 60 minutes. The paste material in the mold was cured and shrunk automatically to become a spherical gel after releasing ammonia gas. The spherical gel was washed with deionized water until it was neutral. The spherical gel was dried at 120°C for 5 hours and calcined at 800°C for 3 hours to obtain the spherical catalyst carrier E of the present application. The diameter of the obtained catalyst carrier F was 5 mm. The number of conical channels was 8. The height of the conical channels was 1.8 mm. The angle of the conical channel vertex was 45 degrees. The bottom area of the conical channel was 3.66% of the surface area of the sphere. The total area of the conical bottom was 29.29% of the surface area of the sphere.

[0090] The carrier E was impregnated with a Mo-Ni-P solution, dried at 120°C for 6 hours and calcined at 550°C for 3 hours to obtain the catalyst M5 of the present application. The properties of the catalyst are shown in Table 1.

[0091] Comparative Example 1

[0092] 400 g of water glass with a silica content of 30 wt% was weighed into a beaker. The stirring device was started. 150 g of a 62 wt% nitric acid solution was slowly added to the beaker. Then, 42.9 g of nickel nitrate was added. After stirring and dissolving, the pH value of the water glass solution in the beaker was 2.0. Then, 385.3 g of pseudoboehmite (properties: pore volume 1.05 mL / g, specific surface area 306 m 2 / g, dry basis 70 wt%) was added to the above solution. After stirring, 35 g of urea was added as a solidifying agent. After the urea was completely dissolved, deionized water was added to make the material in the beaker into a paste with a certain flowability. The solid content of the paste was 33% based on silica and alumina.

[0093] The paste material was pressed into two identical molds with a semispherical hollow structure. The diameter of the spherical cavity was the same as that of Example 1. There was no guide film. After filling the entire cavity, the two semispheres were combined to form a complete sphere and fixed.

[0094] The mold containing the paste material was heated to 120°C and kept at this temperature for 60 minutes. The paste material in the mold was cured and shrunk automatically to become a spherical gel after releasing ammonia gas. The spherical gel was washed with deionized water until it was neutral. The spherical gel was dried at 120°C for 5 hours and calcined at 750°C for 3 hours to obtain the spherical catalyst carrier F of the present comparative example. The diameter of the obtained catalyst carrier G was 3.5 mm.

[0095] The carrier F was impregnated with a Mo-Ni-P solution, dried at 120°C for 6 hours and calcined at 500°C for 3 hours to obtain the catalyst F of the present comparative example C . The properties of the catalyst are shown in Table 1.

[0096] Comparative Example 2

[0097] Take 400 g of water glass with 30 wt% of silica content into a beaker, start the stirring device, slowly add 150 g of nitric acid solution with 62% of mass concentration into the beaker, then add 42.9 g of nickel nitrate, after stirring and dissolving, the pH value of the water glass solution in the beaker is 2.0, then add 385.3 g of pseudo-boehmite (with the following properties: pore volume 1.05 mL / g, specific surface area 306 m 2 / g, dry basis 70 wt%) into the above solution, after stirring, add 35 g of solidifying agent urea, after the urea is completely dissolved, add deionized water to make the material in the beaker into a paste with a certain flowability, and the solid content calculated based on silica and alumina is 33%.

[0098] Press the paste material into two identical semispherical hollow structure rigid body molds, adjust the diameter of the spherical cavity so that the diameter of the final catalyst carrier is 8 mm, without a guide film. After filling the entire cavity, combine the two hemispheres together to form a complete sphere and fix it.

[0099] Heat the mold containing the paste material to 120°C and keep the temperature constant for 60 minutes. Since the paste material in the mold releases ammonia gas after being heated, the paste material solidifies and shrinks to automatically demold into a spherical gel. Then wash the spherical gel with deionized water until it is neutral, dry it at 120°C for 5 hours, and calcine it at 750°C for 3 hours to obtain the spherical catalyst carrier G of the present comparative example. The diameter of the obtained catalyst carrier G is 8 mm.

[0100] Immerse the carrier G in a Mo-Ni-P solution, dry it at 120°C for 6 hours, and calcine it at 500°C for 3 hours to obtain the catalyst G C of the present comparative example. The properties of the catalyst are shown in Table 1.

[0101] Table 1 Properties of the catalyst carriers and catalysts prepared in the examples and comparative examples of the present application

[0102] Catalyst support number A B C D E F G Pore volume, mL / g 0.824 0.815 0.814 0.822 0.823 0.816 0.814 Specific surface area, m 2 / g]] 144 146 147 143 145 147 143 Average pore diameter, nm 22.6 22.7 22.5 22.6 22.6 22.2 22.6 Pore distribution, % <8.0 nm 0.7 0.8 0.6 0.7 0.8 1 1.1 8-20 nm 62.6 62.3 62.5 62.7 62.3 63.4 63.6 20-100 nm 36.7 36.9 36.9 36.6 36.9 35.6 35.3 Catalyst number M1 M2 M3 M4 M5 F C ]]> G C ]]> Metal content, wt% MoO3 4.7 4.6 4.7 4.7 4.6 4.7 4.6 NiO 2.5 2.7 2.5 1.3 2.1 2.5 2.4 Side pressure strength, N / pellet 41 43 36 38 49 86 92

[0103] Examples 6-10 (fouler)

[0104] This example is divided into a conventional catalyst loading part and a catalyst M loading part in the upper space.

[0105] Conventional catalyst loading: Four conventional downflow fixed bed hydrogenation reactors were used, the first reactor (R1) was provided with a bed of hydrogenation guard catalyst, the second reactor (R2) was provided with a bed of hydrodemetallization catalyst, the third reactor (R3) was provided with a bed of hydrodesulfurization catalyst, and the fourth reactor (R4) was provided with a bed of hydrodenitrogenation catalyst and a bed of hydrodesulfurization catalyst, the volume ratio of catalysts loaded in R1, R2, R3 and R4 was 20:25:25:30. The loading of catalysts in Examples 6-10 was the same as that in Example 5, as shown in Table 3.

[0106] Catalyst M loading in the upper space: at the top of the conventional loaded R1, R2, R3 and R4 reactors, a bed of hydroprocessing catalyst M was loaded, the bed of hydroprocessing catalyst M was loaded in the upper space formed by the inlet diffuser 7 and the distribution plate 8. Figure 5 The inlet diffuser 7 and the distribution plate 8 were provided in the hydrogenation reactor, and the upper space was formed by the inlet diffuser 7 and the distribution plate 8, and the hydroprocessing catalyst M was loaded in the upper space. The catalyst M was loaded by using a plurality of fouling accumulators 9, the bottom and the periphery of the fouling accumulators were made of grid net with a spacing or hole diameter less than 3.5 mm, and there were gaps between the plurality of fouling accumulators, which could allow the raw oil overflowing from the side wall voids of the fouling accumulators and / or the top of the fouling accumulators to pass through. In Examples 6-10, the hydroprocessing catalysts M1-M5 prepared in Examples 1-5 were loaded respectively, and the specific catalyst types and the loading amounts in each reactor are shown in Table 4.

[0107] The properties of the residual oil feedstocks treated in this example are shown in Table 2, the operation conditions used are shown in Table 6, and the specific reaction results are shown in Table 7.

[0108] Comparative Examples 3-4

[0109] The same as Example 6, except that the catalyst M was replaced by catalysts Fc and Gc respectively. The specific catalyst types and the loading amounts in each reactor are shown in Table 4. The operation conditions used are shown in Table 6, and the specific reaction results are shown in Table 7.

[0110] Comparative Example 5

[0111] The same as Example 6, except that the catalyst in the catalyst M was replaced by conventional hydrodemetallization catalyst FZC-204A. The properties of the catalyst are shown in Table 5, and the loading amounts of the catalyst in each reactor are shown in Table 4. The operation conditions used are shown in Table 6, and the specific reaction results are shown in Table 7.

[0112] Comparative Example 6

[0113] The same as Example 6, except that no catalyst M was provided, and the top of the conventional reactor was in an idle state. The operation conditions used are shown in Table 6, and the specific reaction results are shown in Table 7.

[0114] Examples 11-15 (filter distribution plate)

[0115] This example is divided into a conventional catalyst loading section and a catalyst M loading section in the upper space.

[0116] The conventional catalyst loading section is the same as in Example 6-10.

[0117] Catalyst M loading in the upper space: In the top of the conventional loaded R1, R2, R3 and R4 reactors, a hydrogenation reactor is provided with an inlet diffuser 7 and a distribution plate 8, wherein the inlet diffuser 7 and the distribution plate 8 form an upper space; the hydrotreating catalyst M is loaded in the upper space. A layer of filter distribution plate 10 is used to load the catalyst M, the bottom and the periphery of the filter distribution plate are made of a grid net with a spacing or hole diameter less than 3.5 mm, and the periphery of the filter distribution plate is spaced apart from the reactor wall by a certain gap. In Examples 11-15, the hydrotreating catalysts M1-M5 prepared in Examples 1-5 are loaded respectively, and the specific catalyst types and the loading amounts in each reactor are shown in Table 8. Figure 5

[0118] The properties of the residual oil feedstock treated in this example are shown in Table 2, the operation conditions used are shown in Table 6, and the specific reaction results are shown in Table 9.

[0119] Comparative Examples 7-8

[0120] The same as Example 11, except that catalysts Fc and Gc are used instead of catalyst M1 respectively. The specific catalyst types and the loading amounts in each reactor are shown in Table 8. The operation conditions used are shown in Table 6, and the specific reaction results are shown in Table 9.

[0121] Comparative Example 9

[0122] The same as Example 11, except that the conventional hydrodemetallization catalyst FZC-204A is used instead of catalyst M1. The properties of the specific catalyst are shown in Table 5, and the loading amounts of the catalyst in each reactor are shown in Table 8. The operation conditions used are shown in Table 6, and the specific reaction results are shown in Table 9.

[0123] Table 2 Properties of the feedstock

[0124] Item Raw material A S, wt% 3.25 N, μg / g 3982 Carbon residue (CCR), wt% 13.63 Density (20°C), kg / m 3 ]] 991.8 Viscosity (100°C), mm 2 / s]] 136.0 Ni+V, μg / g 118. 0 Fe, μg / g 25 Ca, μg / g 22

[0125] Table 3 Catalyst loading in Examples 6-10 and Comparative Examples 3-6

[0126] R1 R2 R3 R4 Examples 6~10 FZC-100B: FZC-12B : FZC-13B = 2:3:4 FZC-28A: FZC-204A = 4:1 FZC-33B: FZC-34A = 6:4 FZC-34A: FZC-41A = 2:8

[0127] Table 4 Catalyst loading in Examples 6-10 and Comparative Examples 3-6

[0128] Example number R1 R2 R3 R4 Example 6 M1 loading volume occupies 50% of R1 upper space volume M1 loading volume occupies 50% of R2 upper space volume M1 loading volume occupies 50% of R3 upper space volume M1 loading volume occupies 50% of R4 upper space volume Example 7 M2 loading volume occupies 50% of R1 upper space volume M2 loading volume occupies 50% of R2 upper space volume M2 loading volume occupies 50% of R3 upper space volume M2 loading volume occupies 50% of R4 upper space volume Example 8 M3 loading volume occupies 50% of R1 upper space volume M3 loading volume occupies 50% of R2 upper space volume M3 loading volume occupies 50% of R3 upper space volume M3 loading volume occupies 50% of R4 upper space volume Example 9 M4 loading volume occupies 50% of R1 upper space volume M4 loading volume occupies 50% of R2 upper space volume M4 loading volume occupies 50% of R3 upper space volume M4 loading volume occupies 50% of R4 upper space volume Example 10 M5 loading volume occupies 50% of R1 upper space volume M5 loading volume occupies 50% of R2 upper space volume M5 loading volume occupies 50% of R3 upper space volume M5 loading volume occupies 50% of R4 upper space volume Comparative Example 3 Fc loading volume occupies 50% of R1 upper space volume Fc loading volume occupies 50% of R2 upper space volume Fc loading volume occupies 50% of R3 upper space volume Fc loading volume occupies 50% of R4 upper space volume Comparative Example 4 Gc loading volume occupies 50% of R1 upper space volume Gc loading volume occupies 50% of R2 upper space volume Gc loading volume occupies 50% of R3 upper space volume Gc loading volume occupies 50% of R4 upper space volume Comparative Example 5 FZC-204A loading volume occupies 50% of R1 upper space volume FZC-204A loading volume occupies 50% of R2 upper space volume FZC-204A loading volume occupies 50% of R3 upper space volume FZC-204A loading volume occupies 50% of R4 upper space volume Comparative Example 6 No catalyst is loaded in the top No catalyst is loaded in the top No catalyst is loaded in the top No catalyst is loaded in the top

[0129] ​Table 5 Properties of catalysts used in Comparative Example 5 and Comparative Example 9 of the present application

[0130] Catalyst model number FZC-204A Particle shape Clover Particle diameter / mm 1.2 Particle length / mm 9.0 Strength / N. (mm) -1 ]] 20 Specific surface / m 2 .g -1 ]]> 171 Pore volume / cm 3 .g -1 ]]> 0.63 Wear rate / wt% 0.5 Chemical composition / wt% MoO3 11.5 NiO 2.5

[0131] Table 6 Operating conditions for each of Examples 6-15 and Comparative Examples 3-9

[0132] Resid feedstock Feedstock A Reaction pressure, MPa 15.7 Liquid hourly space velocity, h -1 ]]> 0.31 H2 / oil volume ratio 650 Reaction temperature, °C R1 385 R2 385 R3 385 R4 385

[0133] Table 7 Properties of residue hydroprocessing effluent oils for each example

[0134] Example 6 Example 7 Example 8 Example 9 Example 10 Operation time, h 5000 5000 5000 5000 5000 Density (20°C), g / cm 3 ]] 936.6 932.7 935.4 939.0 934.4 S, wt% 0.40 0.37 0.41 0.43 0.40 [N, μg.g -1 ]]> 1680 1610 1670 1770 1660 CCR, wt% 5.35 5.19 5.45 6.02 5.41 Ni + V, pg / g -1 ]]> 10.4 9.4 10.7 12.4 10.7 Fe, pg.g -1 ]]> 2.2 2.0 2.3 3.0 2.1 Ca, pg.g -1 ]]> 1.5 1.4 1.3 2.1 1.3 Total bed pressure drop, MPa 1.53 1.46 1.51 1.55 1.52

[0135] Table 7 (continued) Properties of residue hydroprocessing effluent oils for each example

[0136] Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Operation time, h 5000 5000 5000 5000 Density (20°C), g / cm 3 ]] 939.8 940.2 938.3 940.8 S, wt% 0.45 0.45 0.45 0.47 [N, μg.g -1 ]]> 1930 1950 1920 1990 CCR, wt% 5.88 5.91 5.87 5.95 Ni + V, pg / g -1 ]]> 13.4 13.5 13.3 14.6 Fe, pg.g -1 ]]> 6.5 6.6 6.4 8.6 Ca, pg.g -1 ]]> 5.6 5.8 5.4 7.6 Total bed pressure drop, MPa 1.70 1.72 1.75 1.86

[0137] Table 8 Catalyst loading for Examples 11-15 and Comparative Examples 7-9

[0138] Example number R1 R2 R3 R4 Example 11 M1 packing volume was 50% of the upper space volume of R1 M1 packing volume was 50% of the upper space volume of R2 M1 packing volume was 50% of the upper space volume of R3 M1 packing volume was 50% of the upper space volume of R4 Example 12 M2 packing volume was 50% of the upper space volume of R1 M2 packing volume was 50% of the upper space volume of R2 M2 packing volume was 50% of the upper space volume of R3 M2 packing volume was 50% of the upper space volume of R4 Example 13 M3 packing volume was 50% of the upper space volume of R1 M3 packing volume was 50% of the upper space volume of R2 M3 packing volume was 50% of the upper space volume of R3 M3 packing volume was 50% of the upper space volume of R4 Example 14 M4 packing volume was 50% of the upper space volume of R1 M4 packing volume was 50% of the upper space volume of R2 M4 packing volume was 50% of the upper space volume of R3 M4 packing volume was 50% of the upper space volume of R4 Example 15 M5 packing volume was 50% of the upper space volume of R1 M5 packing volume was 50% of the upper space volume of R2 M5 packing volume was 50% of the upper space volume of R3 M5 packing volume was 50% of the upper space volume of R4 Comparative Example 7 Fc packing volume was 50% of the upper space volume of R1 Fc packing volume was 50% of the upper space volume of R2 Fc packing volume was 50% of the upper space volume of R3 Fc packing volume was 50% of the upper space volume of R4 Comparative Example 8 Gc packing volume was 50% of the upper space volume of R1 Gc packing volume was 50% of the upper space volume of R2 Gc packing volume was 50% of the upper space volume of R3 Gc packing volume was 50% of the upper space volume of R4 Comparative Example 9 FZC-204A packing volume was 50% of the upper space volume of R1 FZC-204A packing volume was 50% of the upper space volume of R2 FZC-204A packing volume was 50% of the upper space volume of R3 FZC-204A packing volume was 50% of the upper space volume of R4

[0139] Table 9 Properties of residue hydroprocessing effluent oils for each example

[0140] Example 11 Example 12 Example 13 Example 14 Example 15 Operation time, h 5000 5000 5000 5000 5000 Density (20°C), g / cm 3 ]] 936.5 932.6 935.3 938.9 934.3 S, wt% 0.39 0.36 0.4 0.42 0.39 [N, μg.g -1 ]]> 1670 1600 1660 1760 1650 CCR, wt% 5.34 5.18 5.44 6.01 5.4 Ni + V, pg / g -1 ]]> 10.3 9.3 10.6 12.3 10.6 Fe, pg.g -1 ]] 2.1 1.9 2.2 2.9 2 Ca, pg.g -1 ]] 1.4 1.3 1.2 2 1.2 Total bed pressure drop, MPa 1.52 1.45 1.5 1.54 1.51

[0141] Table 9 (continued) Properties of residue hydroprocessing effluent oils for each example

[0142] Comparative Example 7 Comparative Example 8 Comparative Example 9 Operation time, h 5000 5000 5000 Density (20°C), g / cm 3 ]] 939.7 940.1 938.2 S, wt% 0.44 0.44 0.44 [N, μg.g -1 ]] 1920 1940 1910 CCR, wt% 5.87 5.9 5.86 Ni + V, pg / g -1 ]]> 13.3 13.4 13.2 Fe, pg.g -1 ]]> 6.4 6.5 6.3 Ca, pg.g -1 ]] 5.5 5.7 5.3 Total bed pressure drop, MPa Comparative Example 7 Comparative Example 8 Comparative Example 9 Operation time, h S, wt% CCR, wt% Total bed pressure drop, MPa Comparative Example 7 Comparative Example 8 Comparative Example 9 Operation time, h S, wt% CCR, wt% Total bed pressure drop, MPa 1.69 1.71 1.74

[0143] As can be seen from Tables 7 and 9, by using the method of residue hydroprocessing of the present application, there is a high removal rate of impurities and a small bed pressure drop, and especially iron and calcium are effectively removed. When catalyst M is catalyst Fc or Gc, the path of diffusion of the residue is lengthened because the hydroprocessing catalyst does not have channels, which affects the activity, and because of the lack of a pore volume carbon space for impurities in the conical channels, more inter-particle space is occupied by deposited carbon and other impurities, which reduces the bed void fraction and increases the pressure drop, affecting the activity and service life of the catalyst. Furthermore, when catalyst M is a conventional demetallization or desulfurization catalyst, it also cannot effectively remove the iron and calcium impurities in the residue feedstock. Compared with the conventional loading method without loading catalyst M at the top, loading catalyst M can enhance the volume carbon impurity removal performance, and also can delay the increase in pressure drop. This fully demonstrates that the method of the present application is particularly suitable for processing residue with a high content of iron and calcium impurities, not only can effectively remove and attach iron and / or calcium impurities, but also has high overall catalyst activity, and can also prolong the operating period of the device.

Claims

1. A method of residual hydroprocessing comprising: An inlet diffuser and a distribution tray are arranged in one or more hydrogenation reactors, wherein an upper space is formed by the inlet diffuser and the distribution tray; The hydrogenation treatment catalyst M is filled in the upper space; The hydrogenation treatment catalyst M comprises a carrier and a hydrogenation active metal component, the carrier is a sphere with a diameter of 3.5-10.0 mm, wherein the outer surface of the carrier has a plurality of non-intercommunicating large channels, and the cross-sectional area of the large channels gradually decreases from the outside to the inside along the radial direction, wherein the bottom area of each large channel is 0.05%-5% of the surface area of the sphere, the total bottom area of the large channels is 5%-50% of the surface area of the sphere, and the longest depth of the large channel, measured by the length of the channel along the radial direction of the sphere, is 30%-99% of the radius of the spherical carrier. The largest cross-sectional area of the large channel is 20%-70% of the bottom area of the large channel.

2. The method of claim 1, wherein, The largest cross-sectional area of the large channel is 25%-65% of the bottom area of the large channel.

3. The method of claim 1, wherein, The largest cross-sectional area of the large channel is 30%-80% of the cross-sectional area at 1 / 4 of the longest depth from the bottom.

4. The method of claim 3, wherein, The largest cross-sectional area of the large channel is 45%-75% of the cross-sectional area at 1 / 4 of the longest depth from the bottom.

5. The method according to any one of claims 1 to 4, characterized in that, The largest cross-sectional area of the large channel is 40%-80% of the cross-sectional area at 3 / 4 of the longest depth from the bottom.

6. The method of claim 5, wherein, The largest cross-sectional area of the large channel is 55%-75% of the cross-sectional area at 3 / 4 of the longest depth from the bottom.

7. The method of claim 1, wherein, The smallest cross-sectional area of the large channel is not more than 30 μm.

8. The method of claim 1, wherein, The distribution of the large channels on the surface of the carrier is that the minimum wall thickness between any two adjacent large channels is 1 / 8-1 / 5 of the diameter of the sphere.

9. The method according to claim 1 or 8, characterized in that, ​ 10. The method of claim 1 or 8, wherein, ​ 11. The method of claim 1, wherein, ​ 12. The method of claim 11, wherein, ​ 13. The method of claim 1, wherein, ​ 14. The method of claim 13, wherein, ​ 15. The method of claim 1, wherein, ​ 16. The method of claim 15, wherein, ​ 17. The method of claim 1, wherein, ​ 18. The method of claim 1, wherein, ​ 19. The method of claim 18, wherein, The macropores of the carrier surface are identical.

20. The method of claim 18, wherein, The macropores of the carrier are uniformly distributed on the surface of the sphere.

21. The method of claim 1, wherein, The carrier of the hydroprocessing catalyst M is spherical, and is provided with conical macropores with vertexes pointing to the center of the sphere and bases on the surface of the sphere, the diameter of the spherical carrier is 3.5-10.0 mm, wherein the base area of each conical macropore is 0.05%-4.5% of the surface area of the sphere, the total base area of the conical macropores is 5%-50% of the surface area of the sphere, the height of the conical macropores is 50%-99% of the radius of the spherical carrier, wherein the angle of the vertex angle of the conical macropores is 5-50 degrees, and the conical macropores of the carrier are uniformly distributed on the surface of the sphere.

22. The method of claim 21, wherein, The height of the conical macropores is 55%-96% of the radius of the spherical carrier.

23. The method of claim 21, wherein, The carrier of the hydroprocessing catalyst M is provided with 4-40 conical macropores.

24. The method of claim 23, wherein, The carrier of the hydroprocessing catalyst M is provided with 8-40 conical macropores.

25. The method of claim 1, wherein, The carrier of the hydroprocessing catalyst M is Al2O3-SiO2, wherein the weight content of SiO2 is 20%-50%.

26. The method of claim 25, wherein, The carrier of the hydroprocessing catalyst M is Al2O3-SiO2, wherein the weight content of SiO2 is 30%-40%.

27. The method of claim 25, wherein, The carrier of the hydroprocessing catalyst M further contains a first metal component oxide, the first metal component oxide is NiO, and the molar ratio of the first metal component oxide NiO to Al2O3 is 0.001:1-0.13:

1.

28. The method of claim 27, wherein, The carrier of the hydroprocessing catalyst M further contains a first metal component oxide, the first metal component oxide is NiO, and the molar ratio of the first metal component oxide NiO to Al2O3 is 0.005:1-0.05:

1.

29. The method of claim 1, wherein, The properties of the support of the hydroprocessing catalyst are as follows: a specific surface area of 100 to 200 m 2 / g, a pore volume of 0.70 mL / g or more, a pore volume of 20 to 100 nm in pore diameter of 35 to 60% of the total pore volume, and an average pore diameter of 15 nm or more.

30. The method of claim 29, wherein, The properties of the carrier of the hydroprocessing catalyst are as follows: pore volume is 0.75-1.15 mL / g, and average pore diameter is 17-30 nm.

31. The method of claim 1, wherein, The active metal component of the hydroprocessing catalyst M includes a second metal component, i.e. a Group ⅥB metal element, and a third metal component, i.e. a Group Ⅷ metal element.

32. The method of claim 31, wherein, The Group ⅥB metal element is Mo, and the Group Ⅷ metal element is Ni and / or Co.

33. The method of claim 31, wherein, The content of the second metal component in terms of oxide is 0.10%-10.0% based on the weight of the catalyst, the total content of the first metal component and the third metal component in terms of oxide is 0.03%-5.0%, the content of silicon oxide is 25.0%-35.0%, and the content of aluminum oxide is 55.0%-65.0%.

34. The method of claim 33, wherein, The content of the second metal component in terms of oxide is 0.5%-7.5% based on the weight of the catalyst, and the total content of the first metal component and the third metal component in terms of oxide is 0.05%-3.0%.

35. The method of claim 1, wherein, Under the hydroprocessing reaction conditions, the residue feedstock and hydrogen are sequentially passed through one or more hydrogenation reactors and react with the catalyst; the operating conditions of each reactor are independently selected from the group consisting of: a reaction pressure of 5-25 MPa, a reaction temperature of 300-430℃, a liquid hourly space velocity of 0.05-5.0 h -1 -1, and a hydrogen to oil volume ratio of 150:1-1000:

1.

1. A process for hydroprocessing a residue feedstock, comprising: contacting the residue feedstock with a catalyst under hydroprocessing reaction conditions to produce a hydroprocessed product, wherein the catalyst comprises a molecular sieve having a silica to alumina molar ratio of at least 200, a pore size of 4.5-5.5 angstroms, and a surface area of at least 350 m2 / g; and wherein the hydroprocessing reaction conditions are independently selected from the group consisting of: a reaction pressure of 5-25 MPa, a 36. The method of claim 35, wherein, The residue feedstock contains iron and / or calcium, wherein the content of organic iron and inorganic iron in terms of iron is 5 μg / g or more, and the content of calcium is 5 μg / g or more.

37. The method of claim 36, wherein, The content of organic iron and inorganic iron in terms of iron is 20 μg / g or more, and the content of calcium is 20 μg / g or more.

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