Residual oil hydrotreating method
阅读说明：本技术 一种渣油加氢处理的方法 (Residual oil hydrotreating method ) 是由 耿新国 王永林 刘铁斌 李洪广 金建辉 韩坤鹏 于 2019-10-30 设计创作，主要内容包括：本发明提供了一种渣油加氢处理的方法。该方法包括：在一个或多个加氢反应器内设有入口扩散器和分配盘,其中由入口扩散器和分配盘构成上部空间；在所述上部空间内装填加氢处理催化剂M；所述的加氢处理催化剂M包括载体和加氢活性金属组分,所述载体为球体,直径为3.5～10.0mm,载体外表面具有多个不互通的大孔道,且大孔道的截面积沿径向由外向内逐级减小,大孔道的最长深度为球形载体半径的30%～99%。本发明的方法适用于处理铁、钙杂质含量高的渣油,不但可有效地脱除和附着铁和/或钙杂质,催化剂整体活性高,而且还能充分利用反应器内空间,容纳更多积炭,延缓床层压降上升,延长装置的运转周期。(The invention provides a residual oil hydrotreating method. The method comprises the following steps: an inlet diffuser and a distribution disc are arranged in one or more hydrogenation reactors, wherein an upper space is formed by the inlet diffuser and the distribution disc; filling a hydrotreating catalyst M in the upper space; the hydrotreating catalyst M comprises a carrier and a hydrogenation active metal component, wherein the carrier is a sphere, the diameter of the carrier is 3.5-10.0 mm, the outer surface of the carrier is provided with a plurality of large channels which are not communicated, the sectional area of each large channel is gradually reduced from outside to inside along the radial direction, and the longest depth of each large channel is 30-99% of the radius of the spherical carrier. The method is suitable for treating residual oil with high content of iron and calcium impurities, can effectively remove and attach the iron and/or calcium impurities, has high overall activity of the catalyst, can fully utilize the space in the reactor, contains more carbon deposit, delays the pressure drop rise of a bed layer, and prolongs the operation period of the device.)
1. A process for the hydroprocessing of residua comprising: an inlet diffuser and a distribution disc are arranged in one or more hydrogenation reactors, wherein an upper space is formed by the inlet diffuser and the distribution disc; loading said headspace with a hydroprocessing catalyst M; the hydrotreating catalyst M comprises a carrier and a hydrogenation active metal component, wherein the carrier is a sphere, the diameter of the carrier is 3.5-10.0 mm, the outer surface of the carrier is provided with a plurality of large channels which are not communicated, the sectional area of each large channel is gradually reduced from outside to inside along the radial direction, the area of the bottom surface of each large channel is 0.05-5% of the surface area of the sphere, the area of the total bottom surface of the large channels is 5-50% of the surface area of the sphere, and the longest depth of each large channel is 30-99% of the radius of the spherical carrier, preferably 55-96% of the length of the pore channel along the radius direction of the sphere.
2. The method of claim 1, wherein the headspace comprised of the inlet diffuser and the distribution tray is provided with one or more containers; preferably, a scale and/or filter distributor is provided.
3. The process according to claim 1 or 2, characterized in that the loading volume of the catalyst M is comprised between 20% and 90%, preferably between 30% and 60%, of the headspace effective volume.
4. The method according to claim 1, wherein the hydrotreating catalyst M has macropores extending from the outer surface toward the center of the sphere.
5. The method of claim 1, wherein the bottom surface of the macro-channels in the hydrotreating catalyst M is at least one of circular, elliptical, polygonal, and irregular on the outer surface of the sphere.
6. The method according to claim 5, wherein the macropores in the hydrotreating catalyst M are conical or pyramidal, and preferably, the angle of the vertex angle of the conical or pyramidal pore is 5 to 50 degrees.
7. The process according to claim 1, wherein the minimum cross-sectional area of the macropores in the hydrotreating catalyst M is 10% or less, preferably 5% or less, and more preferably 2% or less of the area of the bottom surface of the macropores.
8. The method of claim 1, wherein the cross-sectional area of the macro-channels from the bottom to the longest depth 1/2 in the hydrotreating catalyst M is 20% to 70%, preferably 25% to 65%, of the area of the bottom of the macro-channels.
9. The process of claim 1, wherein the cross-sectional area of the macro-channels from the bottom to the longest depth 1/2 is 30% to 80%, preferably 45% to 75%, of the cross-sectional area from the bottom to the longest depth 1/4 in the hydroprocessing catalyst M.
10. The process of claim 1, wherein the cross-sectional area of the macro-channels from the bottom to the longest depth 3/4 is 40% to 80%, preferably 55% to 75%, of the cross-sectional area from the bottom to the longest depth 1/2 in the hydroprocessing catalyst M.
11. The process according to claim 1, wherein the width of the largest cross-section of the macropores in the hydroprocessing catalyst M does not exceed 30 μ M.
12. The method according to claim 1, wherein in the hydrotreating catalyst M, the distribution of macropores on the surface of the carrier is realized, wherein the minimum wall thickness between any two adjacent macropores accounts for 1/8-1/5 of the diameter of a sphere; preferably, the macropores on the surface of the carrier are the same; preferably, the macropores of the carrier are uniformly distributed on the surface of the sphere.
13. The method of claim 1, wherein the carrier of the hydrotreating catalyst M is spherical, and has conical large channels with the apex pointing to the center of the sphere and the bottom on the surface of the sphere, the diameter of the spherical carrier is 3.5 to 10.0mm, wherein the area of the bottom of each conical large channel is 0.05 to 4.5% of the surface area of the sphere, the area of the total bottom of the conical large channels is 5 to 50% of the surface area of the sphere, the height of each conical large channel is 50 to 99%, preferably 55 to 96%, of the radius of the spherical carrier, the angle of the apex angle of each conical large channel is 5 to 50%, and the conical channels of the carrier are uniformly distributed on the surface of the sphere.
14. The method as claimed in claim 13, wherein the carrier of the hydrotreating catalyst M is provided with 4 to 40, preferably 8 to 40, conical macropores.
15. The process according to claim 1, characterized in that the support of the hydrotreating catalyst M is Al2O3-SiO2As a carrier, wherein SiO2The weight content is 20-50%, preferably 30-40%.
16. The method of claim 15, wherein the carrier of the hydrotreating catalyst M further contains a first metal component oxide, and the first metal component oxide is NiO; the first metal component oxide NiO and Al2O3Is 0.001: 1-0.13: 1, preferably 0.005: 1-0.05: 1.
17. the process according to any one of claims 1 to 16, wherein the hydrotreating catalyst support M has the following properties: the specific surface area is 100-200 m2The pore volume is more than 0.70mL/g, preferably 0.75-1.15 mL/g, the pore volume occupied by the pore diameter of 20-100 nm is 35-60% of the total pore volume, and the average pore diameter is more than 15nm, preferably 17-30 nm.
18. The process according to claim 1, wherein the active metal component of the hydrotreating catalyst M comprises a second metal component, i.e. a group vib metal element, preferably Mo, and a third metal component, i.e. a group viii metal element, preferably Ni and/or Co.
19. The method of claim 18, wherein the second metal component is present in an amount of 0.10% to 10.0%, preferably 0.5% to 7.5%, calculated as oxide, based on the weight of the catalyst, the total amount of the first metal component and the third metal component is present in an amount of 0.03% to 5.0%, preferably 0.05% to 3.0%, the amount of silica is 25.0% to 35.0%, and the amount of alumina is 55.0% to 65.0%, calculated as oxide.
20. The process of claim 1 wherein the residua feedstock and hydrogen are reacted sequentially through one or more hydrogenation reactors and in contact with the catalyst under hydroprocessing reaction conditions; the operating conditions of each reactor are independently: reaction pressure5 to 25MPa, the reaction temperature is 300 to 430 ℃, and the liquid hourly space velocity is 0.05 to 5.0h-1The volume ratio of hydrogen to oil is 150: 1-1000: 1.
21. The process of claim 20, wherein the residua feedstock contains iron and/or calcium, and wherein the organic and inorganic iron content, as iron, is at least 5 μ g/g, and further at least 20 μ g/g, and the calcium content is at least 5 μ g/g, and further at least 20 μ g/g.
Technical Field
The invention belongs to the technical field of residual oil hydrogenation, and particularly relates to a heavy inferior residual oil hydrotreating method with high iron and calcium impurity content.
Background
As crude oil gets heavier and worse, more and more heavy oil and residual oil need to be processed. The processing treatment of heavy oil and residual oil not only needs to crack the heavy oil and residual oil into low boiling point products, such as naphtha, middle distillate oil, vacuum gas oil and the like, but also needs to improve the hydrogen-carbon ratio of the heavy oil and residual oil, and the processing treatment needs to be realized by a decarburization or hydrogenation method. Wherein the decarbonization process comprises coking, solvent deasphalting, heavy oil catalytic cracking and the like; the hydrogenation process comprises hydrocracking, hydrofining, hydrotreating and the like. The hydrogenation process can not only hydrogenate and convert residual oil and improve the yield of liquid products, but also remove heteroatoms in the residual oil, has good product quality and has obvious advantages. Therefore, each oil refining enterprise creates a residual oil hydrotreater in succession to process heavier and inferior residual oil so as to obtain better benefit.
The raw material cracking rate of heavy oil and residual oil hydrotreating technology is low, and the main purpose is to provide raw materials for downstream raw material lightening devices such as catalytic cracking or coking devices. The impurity content of sulfur, nitrogen, metal and the like in the inferior residual oil and the carbon residue value are obviously reduced through hydrotreating, so that the feed which can be accepted by a downstream raw material lightening device is obtained.
For a catalytic cracker, if the iron and/or calcium content of the feed is too high, the accessibility of heavy oil molecules to the catalyst sites is reduced, resulting in a reduced conversion of heavy oil. Moreover, too high a content of iron and/or calcium in the feed also causes formation of nodules on the catalyst surface, resulting in a decrease in bulk density, which in turn affects the catalyst circulation between the reactor and the regenerator, and in severe cases, the plant processing load. In addition, iron has a dehydrogenation effect, resulting in a high hydrogen/methane ratio in the dry gas. In conclusion, too high iron and/or calcium content in the feed will result in reduced heavy oil conversion, poor product selectivity, impact on plant processing load and thus on plant-wide economic efficiency. Therefore, it is imperative to control the iron and/or calcium content of the catalytic cracking feed.
In the fixed bed residual oil hydrogenation process, the feeding materials are heavy oil or residual oil raw materials containing metal impurities, the metal impurities can be deposited on the surface and in the pore channels of the catalyst in the process of removing the metal impurities, particularly iron and/or calcium are mainly deposited on the outer surface of the catalyst, so that the void ratio of a catalyst bed layer is rapidly reduced, the pressure drop of the bed layer is increased, and the operation period of the device is influenced.
CN1335368A discloses a residual oil treatment method. The method comprises the following steps: before hydrogenation reaction, heavy oil and residual oil are first treated through adsorption and filtering to eliminate suspended particles carried by the material and to eliminate ferrous sulfide and most coke-forming matter produced by iron naphthenate in the crude oil, so as to reduce scaling in residual oil hydrogenating reactor and prolong the running period of the apparatus. However, this method requires additional pretreatment equipment, and iron naphthenate is not reacted and still dissolved in the feedstock before the hydrotreating, and thus the iron removal effect is not good.
CN103289734A discloses a high-metal, high-sulfur and high-nitrogen inferior heavy oil hydrotreating process and catalyst grading combination, which comprises two series-connected upflow type de-ironing reactor, a fixed bed de-metallization reactor, a fixed bed desulfurization reactor and a fixed bed denitrification reactor, wherein the upflow type de-ironing reactor is filled with a hydrodeironing de-ironing de-metallization catalyst, and active metal components of the hydrodeironing de-metallization catalyst are distributed in a yolk shape from the center to the outer surface of catalyst particles, so as to prolong the operation period of the device. The method can adjust the distribution of the removed iron and calcium on the catalyst to a certain degree, but still cannot solve the problem that the iron and calcium impurities are easy to deposit on the outer surface of the catalyst, so that the pressure drop is increased too fast, and the running period of the device is influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a residual oil hydrotreating method. The method of the invention is especially suitable for treating residual oil with high content of iron and calcium impurities, not only can effectively remove and attach the iron and/or calcium impurities, has high overall activity of the catalyst, but also can fully utilize the space in the reactor, hold more carbon deposit, delay the pressure drop rise of a bed layer and prolong the operation period of the device.
The invention provides a method for hydrotreating residual oil, which comprises the following steps: an inlet diffuser and a distribution disc are arranged in one or more hydrogenation reactors, wherein an upper space is formed by the inlet diffuser and the distribution disc; filling a hydrotreating catalyst M in the upper space; the hydrotreating catalyst M comprises a carrier and a hydrogenation active metal component, wherein the carrier is a sphere, the diameter of the carrier is 3.5-10.0 mm, the outer surface of the carrier is provided with a plurality of large channels which are not communicated, the sectional area of each large channel is gradually reduced from outside to inside along the radial direction, the area of the bottom surface of each large channel is 0.05-5% of the surface area of the sphere, the area of the total bottom surface of the large channels is 5-50% of the surface area of the sphere, and the longest depth of each large channel is 30-99% of the radius of the spherical carrier, preferably 55-96% of the length of the pore channel along the radius direction of the sphere.
The upper space, constituted by the inlet diffuser and the distribution plate, may be provided with one or more containers; further preferred are foulers and/or filter distributors.
In the residual oil hydrotreating method, the filling volume of the catalyst M accounts for 20-90%, preferably 30-60% of the effective volume of the upper space.
In the method for hydrotreating residual oil, in the hydrotreating catalyst M, the cross section of the large pore passage in the carrier is a spherical surface formed by taking the spherical center of the carrier as the spherical center and different radii, and the surface corresponding to the large pore passage on the spherical surface is the cross section.
Further, the macropores of the surface of the carrier extend from the outer surface to the direction of the center of the sphere.
Further, the bottom surface of the large pore channel in the carrier is at least one of round, oval, polygonal and irregular on the outer surface of the sphere.
Furthermore, the large pore channels of the carrier are conical pore channels or pyramid pore channels, and preferably, the angle of the vertex angle of the conical pore channels or the pyramid pore channels is 5-50 degrees.
Wherein the calculation formula of the sphere surface area is S = π D, D being the diameter of the sphere.
The sectional area of the large pore channels is gradually reduced from outside to inside along the radial direction, namely the sectional area of each large pore channel is gradually reduced along the whole interval range from outside to inside along the radial direction, but is allowed to be kept constant in one or more intervals. The interval refers to the distance between any two sections in the whole interval of the large pore passage, wherein the interval length of any interval does not exceed 1/4 of the longest depth of the large pore passage.
Further, the cross-sectional area of the large pore passage of the carrier is gradually reduced from the outside to the inside in the radial direction, and the minimum cross-sectional area accounts for 10% or less, preferably 5% or less, and more preferably 2% or less of the area of the bottom surface of the large pore passage.
Furthermore, the sectional area of the large pore channel of the carrier is gradually reduced from outside to inside along the radial direction, and the sectional area from the bottom to the position with the longest depth of 1/2 accounts for 20-70% of the area of the bottom of the large pore, preferably 25-65%.
Further, the sectional area of the large pore passage is gradually reduced from outside to inside along the radial direction, and the sectional area from the bottom surface to the position with the longest depth 1/2 accounts for 30% -80%, preferably 45% -75% of the sectional area from the bottom surface to the position with the longest depth 1/4.
Further, the sectional area of the large pore passage is gradually reduced from outside to inside along the radial direction, and the sectional area from the bottom surface to the position with the longest depth 3/4 accounts for 40% -80%, preferably 55% -75% of the sectional area from the bottom surface to the position with the longest depth 1/2.
Further, the width of the minimum cross section of the large pore channel is not more than 30 μm.
The macroporous channels are distributed on the surface of the carrier, wherein the minimum wall thickness between any two adjacent macroporous channels accounts for 1/8-1/5 of the diameter of the sphere. Wherein, the macropores on the surface of the carrier are preferably the same, i.e. the shape and size are substantially the same, and can be made into the same macropores by the same guide mold, and further preferably, the macropores of the carrier are uniformly distributed on the surface of the sphere.
In the hydrotreatment method of the residual oil, in the hydrotreatment catalyst M, the carrier is spherical, and is provided with conical large channels with the vertexes pointing to the center of the sphere and the bottom surfaces on the surface of the sphere, the diameter of the spherical carrier is 3.5-10.0 mm, wherein the area of the bottom surface of each conical large channel is 0.05-4.5% of the surface area of the sphere, the area of the total bottom surface of each conical large channel is 5-50% of the surface area of the sphere, the height of each conical large channel is 50-99% of the radius of the spherical carrier, preferably 55-96%, the angle of the vertex angle of each conical large channel is 5-50%, and the conical channels of the carrier are uniformly distributed on the surface of the sphere.
Furthermore, 4-40 conical large channels, preferably 8-40 conical large channels are arranged in the carrier of the hydrotreating catalyst M.
The hydrotreating catalyst M of the invention is composed of Al2O3-SiO2Is a carrier, wherein SiO is based on the weight of the carrier2The weight content is 20-50%, preferably 30-40%.
In the method for hydrotreating residuum according to the present invention, the carrier of the hydrotreating catalyst M preferably further contains a first metal component oxide, and the first metal component oxide is NiO. The first metal component oxide NiO and Al2O3Is 0.001: 1-0.13: 1, preferably 0.005: 1-0.05: 1.
in the residue oil hydrotreating method of the present invention, the carrier of the hydrotreating catalyst M has the following properties: the specific surface area is 100-200 m2The pore volume is more than 0.70mL/g, preferably 0.75-1.15 mL/g, the pore volume occupied by the pore diameter of 20-100 nm is 35-60% of the total pore volume, and the average pore diameter is more than 15nm, preferably 17-30 nm.
In the method for hydrotreating residuum according to the present invention, in the hydrotreating catalyst M, the active metal component includes a second metal component, i.e., a group vib metal, and a third metal element, i.e., a group viii metal element, where the group vib metal is preferably Mo, and the group viii metal is preferably Ni and/or Co.
In the residual oil hydrotreating method, the content of the second metal component in terms of oxide in the hydrotreating catalyst M is 0.10-10.0%, preferably 0.5-7.5%, the total content of the first metal component and the third metal component in terms of oxide is 0.03-5.0%, preferably 0.05-3.0%, the content of silicon oxide is 25.0-35.0%, and the content of aluminum oxide is 55.0-65.0%, based on the weight of the catalyst.
In the present invention, the catalyst M may be loaded in a random packing manner. The catalyst M can be packed in a separate fouling vessel or in the entire filter distribution plate. If there are a plurality of reactors, the catalyst M may be loaded in one or more of the reactors, the catalyst M loaded in each reactor may be the same or different, and the loading height and loading amount of the catalyst M in each reactor may be the same or different.
In the method for hydrotreating the residual oil, under the hydrotreating reaction condition, the residual oil raw material and hydrogen sequentially pass through one or more serially connected hydrogenation reactors, and the catalyst is contacted for reaction.
In the residue oil hydrotreating method of the present invention, the operating conditions of each reactor are, independently: the reaction pressure is 5-25 MPa, the reaction temperature is 300-430 ℃, and the liquid hourly space velocity is 0.05-5.0 h-1The volume ratio of hydrogen to oil is 150: 1-1000: 1.
Compared with the prior art, the invention has the advantages that:
1. the inventor of the invention finds that iron and calcium in the residual oil can be divided into two main types of organic and inorganic, wherein inorganic iron and calcium are easy to remove, but organic iron and calcium are not easy to remove, even ferrous sulfide and calcium sulfide are generated, the iron and calcium sulfide are attached to the surface of the catalyst and are easy to fall off to penetrate through the catalyst bed along with material flow, and fragments and particles of the fallen ferrous sulfide and calcium sulfide can enter the downstream catalyst bed, so that the void ratio of the downstream catalyst bed is reduced, the pressure drop of the bed is increased, even partial material flow of the bed is uneven, radial temperature difference is generated, and the operation of downstream devices (such as catalytic cracking devices) is influenced. In addition, because the residual oil hydrogenation device raw material filter can only filter out mechanical impurities with the particle size of more than 25 mu m generally, the mechanical impurities with the particle size of less than 25 mu m can enter the reactor and are attached to the outer surface and the orifice part of the catalyst, so that the activity of the catalyst can not be exerted to the greatest extent, and meanwhile, the mechanical impurities can also become coke nuclei for coke deposition, the existence of the mechanical impurities can also increase the carbon deposit amount, and the carbon deposits occupy gaps among catalyst particles, so that the logistics throughput is reduced, and the bed pressure drop can be continuously increased along with the accumulation of the mechanical impurities. For this reason, the inventors have invented a method for grading the catalyst M and have made reasonable use thereof, thereby solving the problem.
2. The top of the conventional downflow fixed bed residual oil hydrogenation reactor is provided with an inlet diffuser and a distribution disc, a large space is arranged between the diffuser and the distribution disc, and the reactor is not filled with a catalyst and is in an idle state. The method of the invention fills the hydrotreating catalyst M in the idle space, and because the hydrotreating catalyst M has proper granularity, pore channel structure and unique channel structure, the method can remove iron and calcium impurities in residual oil, and effectively deposit and attach in the large pore channel on the outer surface of the catalyst, thereby reducing the influence of the iron and calcium impurities on downstream high-activity desulfurization and denitrification carbon residue removal catalyst bed layers and downstream devices, simultaneously having higher demetallization activity, further deeply removing metal impurities Ni and V, and having certain desulfurization and carbon residue removal activity. In addition, because the space of the container has enough gaps, the residual oil flow can flow through the gaps among the catalyst M particles in the initial operation stage of the device, and the residual oil flow can pass through the gaps around the container after the catalyst M particles are fully accumulated with dirt and carbon deposits in the later operation stage of the device, so that the filling of the catalyst M can not cause the bed pressure drop to rise.
3. The surface of the hydrotreating catalyst M adopted by the invention is provided with a certain number of large channels with certain sizes, the large channels are not communicated and do not penetrate, the sectional area of the large channels is gradually reduced from outside to inside along the radial direction, and the shape of the large channels is preferably conical (conical or pyramidal). The large pore channels on the catalyst particles can greatly reduce the diffusion distance and resistance of residual oil molecules to the interior of the catalyst particles. The non-communicated and non-penetrated pore canal prevents the residual oil material flow from directly flowing out of the pore canal, thereby improving the retention time of the residual oil material flow in the pore canal and increasing the deposition probability of particulate matters and dirt. The inventor creatively discovers through a large number of experiments that the pore channel of the catalyst carrier has a conical structure, the front end of the conical pore channel is an acute angle, and the reacted particles and scales are easy to bridge within a distance of 20-30 mu m of the pore channel to form a micron-sized grid and gradually expand from inside to outside in the large pore channel, so that the deposition and adhesion efficiency of the scales such as iron is greatly improved. The general prepared through-channels are more than 0.1mm, bridging space with the distance of 20-30 mu m is not easy to provide, and simultaneously, due to the through-channels, material flow scouring exists, the difficulty of deposit of the dirt is increased, and the deposit and adhesion efficiency of the dirt is reduced. Meanwhile, in the method, a small amount of nickel salt is preferably added into the catalyst carrier, so that a proper amount of nickel-aluminum spinel structure is generated in the roasting process, the strength and the water resistance of the catalyst are further improved, and the catalytic performance is not influenced.
4. The method is especially suitable for the hydrotreatment of the residual oil containing iron, the content of organic iron and inorganic iron in the residual oil can be more than 5 mu g/g or more than 20 mu g/g in terms of iron, and the content of calcium can be more than 5 mu g/g or more than 20 mu g/g. The catalyst filling method of the invention not only can effectively remove and attach iron and/or calcium impurities, has high overall activity of the catalyst, but also can prolong the running period of the device.
Drawings
FIG. 1 is a schematic sectional view of a process for preparing a support of a residual oil hydrotreating catalyst M of the present invention;
FIG. 2 is a schematic view of a hemispherical cavity mold for forming a mold shell;
FIG. 3 is a schematic sectional view of a support of the catalyst M prepared;
FIG. 4 is a schematic perspective view of a support for the catalyst M prepared;
FIG. 5 is a schematic of a fixed bed residuum hydrogenation reactor equipped with a scale;
FIG. 6 is a schematic diagram of a fixed bed residuum hydrogenation reactor equipped with a filtration distribution tray;
the reference numerals are explained below:
1. a mold housing; 2. a pasty material; 3. a guide die capable of forming a conical large pore channel; 4. a cavity; 5. conical shaped prickles; 6. a conical bore; 7. an inlet diffuser; 8. a distribution tray; 9. a scale deposit; 10. a filter distribution tray.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, which are not intended to limit the scope of the present invention. In the present invention, wt% is a mass fraction.
In the invention, the specific surface area, the pore volume, the pore diameter and the pore distribution are measured by adopting a low-temperature liquid nitrogen adsorption method.
The hydrotreating catalyst M of the present invention can be prepared by a process comprising:
(1) adding an acidic peptizing agent into a silicon source for acidification treatment;
(2) adding pseudo-boehmite and a curing agent into the step (1) to prepare a paste material;
(3) adding the paste material obtained in the step (2) into a mould, and heating the mould containing the paste material for a certain time to solidify and form the paste material;
(4) removing the material in the step (3) from the mold, washing, drying and roasting to obtain a catalyst carrier;
(5) and (4) impregnating the carrier obtained in the step (4) with active metal components of the supported catalyst, and drying and roasting to obtain the hydrotreating catalyst M.
In the preparation method of the hydrotreating catalyst M of the present invention, the first metal oxide is preferably introduced into the support, and the first metal source (nickel source) may be introduced in step (1) and/or step (2), and the preferred introduction method is as follows: adding a nickel source into the material obtained in the step (1), and dissolving the nickel source into the material. The nickel source can adopt soluble nickel salt, wherein the soluble nickel salt can be one or more of nickel nitrate, nickel sulfate and nickel chloride, and nickel nitrate is preferred.
In the preparation method of the hydrotreating catalyst M, the silicon source in the step (1) is one or more of water glass and silica sol, wherein the mass content of silicon in terms of silicon oxide is 20-40%, preferably 25-35%; the acid peptizing agent is one or more of nitric acid, formic acid, acetic acid and citric acid, preferably nitric acid, and the mass concentration of the acid peptizing agent is 55-75%, preferably 60-65%; the adding amount of the acidic peptizing agent is that the molar ratio of hydrogen ions to silicon dioxide is 1: 1.0-1: 1.5; the pH value of the silicon source after acidification treatment is 1.0-4.0, preferably 1.5-2.5.
In the preparation method of the hydrotreating catalyst M, the dry weight of the pseudo-boehmite in the step (2) is more than 70 percent, and the pseudo-boehmite is converted into gamma-Al by high-temperature roasting2O3The latter properties are as follows: the pore volume is more than 0.95mL/g, the preferable pore volume is 0.95-1.2 mL/g, and the specific surface area is 270m2More than g, preferably the specific surface area is 270-330 m2(ii) in terms of/g. The curing agent is one or more of urea and organic ammonium salt. The organic ammonium salt is hexamethinetetrammonium. The addition amount of the curing agent is 1: 1.5-1: 2.0 in terms of the molar ratio of nitrogen atoms to silicon dioxide; the solid content of the prepared paste material is 25-45% by weight of silicon dioxide and aluminum oxide, preferably 28-40%, and the paste material is a plastic body with certain fluidity.
In the preparation method of the hydrotreating catalyst M of the present invention, the mold in the step (3) includes a shell with a spherical cavity and a guide mold capable of matching with the shape of the pore passage required by the present invention, the shell is made of a rigid material, and the external shape may be any shape, preferably a symmetrical geometric shape such as a sphere. The invention takes the mould with the spherical external shape and the membrane guiding structure capable of forming the conical pore as an example for explanation, and the spherical shell can be composed of two identical hemispheroids or four quarter spheres. The diameter of the spherical cavity can be adjusted according to the size of catalyst particles, so that the diameter of the final spherical carrier is 3.5-10.0 mm. The material of the guide mould is selected from substances which can be removed by heating or burning, such as graphite, wood, paper, paraffin or petroleum resin. The structure of the guide film is matched with a three-dimensional conical pore channel in the carrier, conical barbs are arranged towards the center of the sphere, the bottom surface of the guide film is connected with the surface of a quarter sphere, the thickness d of the guide film except the conical barbs is 0-2 mm, and the conical barbs in the guide film are centrosymmetric. Thereby forming a guided mode capable of producing a conical bore.
The structure of the guide die is matched with the pore channel in the carrier, and the conical pore channel is generated after the guide die is removed.
In the preparation method of the hydrotreating catalyst M, in the step (3), spherical shells of all parts are fixed with each other to form two complete hemispheroid cavities, four guide molds are spliced into two hemispheroids and are respectively placed in the two complete hemispheroid cavities, at the moment, a paste material is injected or pressed into the two hemispheroid cavities, and the two hemispheroids are combined together to form a complete sphere and are fixed after the whole cavities are filled.
In the preparation method of the hydrotreating catalyst M, in the step (3), the heating temperature of the die for containing the paste material is 70-200 ℃, preferably 100-150 ℃, and the constant temperature time is 30-240 minutes, preferably 50-120 minutes, so that the material is cured.
In the preparation method of the hydrotreating catalyst M, the mold is removed in the step (4), namely the lower shell is taken, and the pasty material in the mold releases alkaline gas after being heated, so that the pasty material is solidified and contracted to automatically remove the spherical shell. In the step (4), the spherical material after the spherical shell is removed is washed to be neutral by deionized water, and the quarter sphere is used as a guide die, so that the guide die and the sphere can be automatically separated due to the washing, disturbance and soaking of the deionized water in the washing process, and the sphere is provided with a needed large pore channel. The drying temperature is 100-150 ℃, and the drying time is 4-10 hours. The roasting temperature is 500-900 ℃, preferably 550-800 ℃, and the roasting time is 2-8 hours.
In the preparation method of the hydrotreating catalyst M of the present invention, the drying and calcining conditions after the carrier is impregnated with the catalyst active metal component in the step (5) are as follows: drying at 100-150 ℃ for 4-10 hours, and roasting at 400-600 ℃ for 2-6 hours.
The method for hydrotreating residual oil is suitable for hydrotreating residual oil containing iron and/or calcium. Preferably, the content of organic iron and inorganic iron in the residual oil raw material is more than 5 mu g/g, more preferably more than 20 mu g/g, and the content of calcium is more than 5 mu g/g, more preferably more than 20 mu g/g in terms of iron. 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 heavy oil and the like. The residual feedstock may contain various conventional impurities such as sulfur, nitrogen, asphaltenes, metallic impurities, carbon residue, and the like. The properties of the resid feedstock can be: the sulfur content is not more than 4wt%, the nitrogen content is not more than 0.7wt%, the metal content (Ni + V) is not more than 140 mug/g, the carbon residue value is not more than 17wt%, and the asphaltene content is not more than 5 wt%. The residual oil raw material 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 refining oil and the like.
The process of the present invention employs a downflow fed hydrogenation reactor, the material first contacting catalyst M after entering the reactor.
In the invention, the number of the hydrogenation reactors is 1-7, preferably 2-5.
The hydrotreating catalyst M of the present invention will be described in detail below with reference to the drawings.
The present invention is described by taking the example that the external shape is spherical and the guide film is capable of forming a conical pore channel, as shown in fig. 1-4, when the present invention is used for preparing a residual oil hydrotreating catalyst carrier, the mold comprises a shell 1 with a spherical cavity (see fig. 1) and a guide film 3 capable of forming a conical pore channel (see fig. 1). The invention is illustrated by the outer shape being spherical, the spherical shell may be composed of two identical hemispheres. The spherical cavity has a diameter D (see fig. 1). The guide mold is made of heat or combustion removable material, such as graphite, wood, paper, paraffin or petroleum resin. The structure of the guide die is matched with a three-dimensional conical pore channel in the carrier, a conical burr 5 is arranged towards the center of the sphere, the bottom surface of the guide film is connected with the surface of a quarter sphere, the thickness of the part of the guide film, except the conical burr 5, is d, and the conical burr in the guide film is in central symmetry. See in particular fig. 1 and 3. The conical bore 6 created after the guide die is removed.
In the method, firstly, spherical shells of all parts are fixed with each other to form two complete hemispheroid cavities 4 (see figure 2), a guide die capable of forming a three-dimensional conical pore passage is placed into one hemispheroid cavity 4, the pasty material 2 is pressed into the two hemispheroid cavities 4, and the two hemispheroids are combined to form a complete sphere and fixed after the whole cavity is filled. The guide film forms conical cells 6 as shown in fig. 3. The catalyst carrier prepared by the invention is shown in a schematic perspective view in figure 4.
The catalyst M of the present invention may be packed in a scale or in a filter distribution plate. The catalyst M of the present invention can be packed in the fouling device or the filter distribution plate in a volume equal to the effective volume of the upper space occupied by the packed volume of the catalyst M.
Example 1
Weighing 400g of water glass with the silicon oxide content of 30wt%, adding the water glass into a beaker, starting a stirring device, slowly adding 150g of nitric acid solution with the mass concentration of 62% into the beaker, adding nickel nitrate, stirring and dissolving the mixture until the pH value of the water glass solution in the beaker is 2.0, and adding 385.3g of pseudo-boehmite (with the properties of the pore volume of 1.05mL/g and the specific surface area of 306 m) into the solution2The dry basis is 70 wt%), the molar ratio of nickel oxide to aluminum oxide in the carrier is controlled to be 0.06:1, 35g of curing agent urea is added after uniform stirring, deionized water is added after the urea is completely dissolved, so that the material in the beaker is in a paste state with certain fluidity, and the solid content is 33% in terms of silicon dioxide and aluminum oxide.
The pasty material is pressed into two identical hemispheres with spherical cavities. Wherein, a hemisphere is put into a guide die, and the guide die is made of wood. The guide film of the spherical carrier is matched with the carrier, a conical pore channel structure can be formed, the guide film is divided into a quarter sphere, and the guide film is provided with 6 conical prickles towards the center of the sphere. The vertex of the conical prickle points to the center of the sphere, and the bottom surface of the conical prickle is connected with the surface of a quarter of the sphere. The conical pore channels of the carrier are uniformly distributed on the surface of the sphere.
The pasty material is pressed into the two hemispheroidal cavities, and the two hemispheroids are combined together to form a complete sphere and fixed after the whole cavity is filled with the pasty material.
Heating a mould containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material in the mould is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 750 ℃ to obtain the spherical catalyst carrier A. Wherein, the diameter of the obtained catalyst carrier A is 3.5mm, the number of the conical pore canals is 24, the height of the conical pore canals is 1.6mm, the angle of the apex angle of the conical pore canal is 20 degrees, the area of the bottom surface of the conical pore canal is 0.754 percent of the surface area of the sphere, and the total area of the conical bottom surfaces is 18 percent of the surface area of the sphere.
The carrier A was impregnated with Mo-Ni-P solution, dried at 120 ℃ for 6 hours, and calcined at 500 ℃ for 3 hours to obtain the catalyst M1 of the present invention, the catalyst properties are shown in Table 1.
Example 2
The preparation was carried out as in example 1, except that the amount of nickel nitrate was increased to control the molar ratio of nickel oxide to alumina in the carrier to be 0.10:1, and the properties of the prepared catalyst carrier B and the prepared catalyst M2 were as shown in Table 1.
The diameter of the obtained catalyst carrier B is 8mm, the number of the conical pore channels is 40, the height of the conical pore channels is 3.5mm, the angle of the vertex angle of the conical pore channel is 15 degrees, the area of the bottom surface of the conical pore channel is 0.43 percent of the surface area of the sphere, and the total area of the conical bottom surfaces is 17 percent of the surface area of the sphere.
Example 3
The procedure is as in example 1 except that the curing agent urea was changed to 46.6g hexamethylenetetramine and catalyst support C and catalyst M3 were prepared having the properties shown in Table 1.
Wherein, the diameter of the obtained catalyst carrier C is 6mm, the number of the conical pore canals is 40, the height of the conical pore canals is 2.5mm, the angle of the apex angle of the conical pore canal is 25 degrees, the area of the bottom surface of the conical pore canal is 1.17 percent of the surface area of the sphere, and the total area of the conical bottom surfaces is 46.85 percent of the surface area of the sphere.
Example 4
The procedure is as in example 1 except that no nickel nitrate is added and catalyst support D and catalyst M4 are prepared having the properties shown in Table 1.
Example 5
Weighing 800g of water glass with the silicon oxide content of 30wt%, adding the water glass into a beaker, starting a stirring device, slowly adding 299g of nitric acid solution with the mass concentration of 62% into the beaker, adding nickel nitrate, stirring and dissolving the water glass solution, then keeping the pH value of the water glass solution in the beaker to be 2.0, and then adding 575g of pseudo-boehmite (the property is as follows: the pore volume is 1.05mL/g, the specific surface area is 306 m)2The dry basis is 70 wt%), the molar ratio of nickel oxide to aluminum oxide in the carrier is controlled to be 0.06:1, 75g of curing agent urea is added after uniform stirring, deionized water is added after the urea is completely dissolved, so that the material in the beaker is in a paste shape with certain fluidity, and the solid content is 35% in terms of silicon dioxide and aluminum oxide.
The guide film of the spherical carrier is matched with the carrier, a conical pore channel structure can be formed, the guide film is divided into a quarter sphere and is provided with 2 conical prickles towards the center of the sphere. The vertex of the conical prickle points to the center of the sphere, and the bottom surface of the conical prickle is connected with the surface of a quarter of the sphere. The conical pore channels of the carrier are uniformly distributed on the surface of the sphere.
The pasty material is pressed into the two hemispheroidal cavities, and the two hemispheroids are combined together to form a complete sphere and fixed after the whole cavity is filled with the pasty material.
Heating a mould containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material in the mould is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 800 ℃ to obtain the spherical catalyst carrier E. The diameter of the obtained catalyst carrier F is 5mm, the number of the conical pore channels is 8, the height of the conical pore channels is 1.8mm, the angle of the vertex angle of the conical pore channel is 45 degrees, the area of the bottom surface of the conical pore channel is 3.66 percent of the surface area of the sphere, and the total area of the conical bottom surfaces is 29.29 percent of the surface area of the sphere.
The carrier E was impregnated with Mo-Ni-P solution, dried at 120 ℃ for 6 hours, and calcined at 550 ℃ for 3 hours to obtain the catalyst M5 of the present invention, the catalyst properties are shown in Table 1.
Comparative example 1
Weighing 400g of water glass with the silicon oxide content of 30wt%, adding the water glass into a beaker, starting a stirring device, slowly adding 150g of nitric acid solution with the mass concentration of 62% into the beaker, then adding 42.9g of nickel nitrate, stirring and dissolving the mixture until the pH value of the water glass solution in the beaker is 2.0, and then adding 385.3g of pseudo-boehmite (with the properties as follows: the pore volume is 1.05mL/g, and the specific surface area is 306 m) into the solution270wt% of dry basis), adding 35g of curing agent urea after uniformly stirring, adding deionized water after the urea is completely dissolved, and enabling the materials in the beaker to be in a paste shape with certain fluidity and the solid content of the materials calculated by silicon dioxide and aluminum oxide to be 33%.
The paste material was pressed into two identical hemispherical hollow rigid molds, the diameter of the spherical cavity being the same as in example 1 without a conductive film. After the whole cavity is filled, the two hemispheres are combined together to form a complete sphere and fixed.
Heating a mould containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material in the mould is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 750 ℃ to obtain the spherical catalyst carrier F of the comparative example, wherein the diameter of the obtained catalyst carrier G is 3.5 mm.
The carrier F was impregnated with Mo-Ni-P solution, dried at 120 ℃ for 6 hours, and calcined at 500 ℃ for 3 hours to obtain the catalyst F of this comparative exampleCThe catalyst properties are shown in Table 1.
Comparative example 2
Weighing 400g of water glass with the silicon oxide content of 30wt%, adding the water glass into a beaker, starting a stirring device, slowly adding 150g of nitric acid solution with the mass concentration of 62% into the beaker, then adding 42.9g of nickel nitrate, stirring and dissolving the mixture until the pH value of the water glass solution in the beaker is 2.0, and then adding 385.3g of pseudo-boehmite (with the properties as follows: the pore volume is 1.05mL/g, and the specific surface area is 306 m) into the solution270wt% of dry basis), evenly stirring, adding 35g of curing agent urea, adding deionized water after the urea is completely dissolved, and enabling the materials in the beaker to be pasty with certain fluidityAnd a solid content based on silica and alumina was 33%.
And pressing the pasty material into two rigid body molds with the same hemispherical hollow structure, and adjusting the diameter of the spherical cavity to enable the diameter of the final catalyst carrier to be 8mm without a guide film. After the whole cavity is filled, the two hemispheres are combined together to form a complete sphere and fixed.
Heating a mould containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material in the mould is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 750 ℃ to obtain the spherical catalyst carrier G of the comparative example, wherein the diameter of the obtained catalyst carrier G is 8 mm.
The carrier G was impregnated with a Mo-Ni-P solution, dried at 120 ℃ for 6 hours, and calcined at 500 ℃ for 3 hours to obtain the catalyst G of this comparative exampleCThe catalyst properties are shown in Table 1.
TABLE 1 Properties of catalyst supports and catalysts prepared in inventive and comparative examples
Catalyst support numbering
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, m2/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
Hole distribution,%
<8.0nm
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
20-100nm
36.7
36.9
36.9
36.6
36.9
35.6
35.3
Catalyst numbering
M1
M2
M3
M4
M5
FC
GC
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 pressureStrength, N/grain
41
43
36
38
49
86
92
Examples 6 to 10 (Scale deposit)
The present embodiment is divided into a conventional catalyst loading section and a loading section of the catalyst M in the upper space.
Conventional catalyst loading: four conventional downflow fixed bed hydrogenation reactors are adopted, the first reactor (R1) is provided with a hydrogenation protective agent bed layer in which hydrogenation protective agent is filled, the second reactor (R2) is provided with a hydrogenation demetalization catalyst bed layer in which hydrogenation demetalization catalyst is filled, the third reactor (R3) is provided with a hydrogenation desulfurization catalyst bed layer in which hydrogenation desulfurization catalyst is filled, the fourth reactor (R4) is provided with a hydrogenation denitrification catalyst bed layer in which hydrogenation desulfurization catalyst and hydrogenation denitrification catalyst are filled, and the volume ratio of the catalyst filled in R1, R2, R3 to R4 is 20:25:25: 25: 30. Examples 6-10 were loaded in the same manner as the conventional catalyst, as shown in Table 3.
Loading of catalyst M in the upper space: in the top of the conventionally packed R1, R2, R3 and R4 reactors, as shown in fig. 5, an inlet diffuser 7 and a distribution tray 8 are arranged in the hydrogenation reactor, wherein an upper space is formed by the inlet diffuser 7 and the distribution tray 8; the head space is filled with a hydrotreating catalyst M. A plurality of fouling devices 9 are used for filling the catalyst M, the bottoms and the peripheries of the fouling devices are made of grid nets with the space or the hole diameter smaller than 3.5mm, and gaps are reserved among the fouling devices, so that raw oil overflowing from the side wall gaps and/or the tops of the fouling devices can be allowed to pass through. In examples 6 to 10, the hydrotreating catalysts M1 to M5 prepared in examples 1 to 5 were loaded, respectively, and the specific catalyst types and the loading amounts in the respective reactors are shown in Table 4.
The properties of the resid feedstock processed in this example are shown in Table 2, the operating conditions employed are shown in Table 6, and the specific reaction results are shown in Table 7.
Comparative examples 3 to 4
The difference from example 6 is that: catalyst M employs catalysts Fc and Gc, respectively, in place of catalyst M1. Specific catalyst types and loadings in each reactor are shown in table 4. The operating conditions employed are shown in Table 6, and the specific reaction results are shown in Table 7.
Comparative example 5
The difference from example 6 is that: the catalyst in the catalyst M is replaced by a conventional hydrodemetallization catalyst FZC-204A. The properties of the specific catalysts are shown in Table 5, and the loading of the catalysts in the respective reactors is shown in Table 4. The operating conditions employed are shown in Table 6, and the specific reaction results are shown in Table 7.
Comparative example 6
The difference from example 6 is that: the catalyst M is not provided, and is in an idle state at the top of the conventional reactor. The operating conditions employed are shown in Table 6, and the specific reaction results are shown in Table 7.
Examples 11 to 15 (Filter distributor plate)
The present embodiment is divided into a conventional catalyst loading section and a loading section of the catalyst M in the upper space.
The conventional catalyst loading was the same as in examples 6-10.
Loading of catalyst M in the upper space: in the top of the conventionally packed R1, R2, R3 and R4 reactors, as shown in fig. 5, an inlet diffuser 7 and a distribution tray 8 are arranged in the hydrogenation reactor, wherein an upper space is formed by the inlet diffuser 7 and the distribution tray 8; the head space is filled with a hydrotreating catalyst M. A layer of filtering distribution disk 10 is used to fill catalyst M, the bottom and periphery of the filtering distribution disk are made of grid net with the distance or hole diameter less than 3.5mm, and a certain gap is arranged between the periphery of the filtering distribution disk and the wall of the reactor. In examples 11 to 15, the hydrotreating catalysts M1 to M5 prepared in examples 1 to 5 were loaded, respectively, and the specific catalyst types and the loading amounts in the respective reactors are shown in Table 8.
The properties of the resid feedstock processed in this example are shown in Table 2, the operating conditions employed are shown in Table 6, and the specific reaction results are shown in Table 9.
Comparative examples 7 to 8
The difference from example 11 is that: catalysts Fc and Gc were used instead of catalyst M1, respectively. Specific catalyst types and loadings in each reactor are shown in table 8. The operating conditions employed are shown in Table 6, and the specific reaction results are shown in Table 9.
Comparative example 9
The difference from example 11 is that: the conventional hydrodemetallization catalyst FZC-204A is adopted to replace the catalyst M1. The properties of the specific catalysts are shown in Table 5, and the loading of the catalysts in the respective reactors is shown in Table 8. The operating conditions employed are shown in Table 6, and the specific reaction results are shown in Table 9.
TABLE 2 Properties of the raw materials
Item
Starting materials A
S， wt%
3.25
N，μg/g
3982
Carbon Residue (CCR), wt%
13.63
Density (20 ℃), kg/m3
991.8
Viscosity (100 ℃ C.), mm2/s
136.0
Ni+V，μg/g
118. 0
Fe，μg/g
25
Ca，μg/g
22
TABLE 3 catalyst loading in examples 6-10 and comparative examples 3-6
R1
R2
R3
R4
Examples 6 to 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
TABLE 4 catalyst loading in examples 6-10 and comparative examples 3-6
Examples of the embodiments
Number (C)
R1
R2
R3
R4
Example 6
The M1 packing volume was 50% of the volume of the head space of R1
The M1 packing volume was 50% of the volume of the head space of R2
The M1 packing volume was 50% of the volume of the head space of R3
The M1 packing volume was 50% of the volume of the head space of R4
Example 7
The M2 packing volume was 50% of the volume of the head space of R1
The M2 packing volume was 50% of the volume of the head space of R2
The M2 packing volume was 50% of the volume of the head space of R3
The M2 packing volume was 50% of the volume of the head space of R4
Example 8
The M3 packing volume was 50% of the volume of the head space of R1
The M3 packing volume was 50% of the volume of the head space of R2
The M3 packing volume was 50% of the volume of the head space of R3
The M3 packing volume was 50% of the volume of the head space of R4
Example 9
The M4 packing volume was 50% of the volume of the head space of R1
The M4 packing volume was 50% of the volume of the head space of R2
The M4 packing volume was 50% of the volume of the head space of R3
The M4 packing volume was 50% of the volume of the head space of R4
Example 10
The M5 packing volume was 50% of the volume of the head space of R1
The M5 packing volume was 50% of the volume of the head space of R2
The M5 packing volume was 50% of the volume of the head space of R3
The M5 packing volume was 50% of the volume of the head space of R4
Comparative example 3
The Fc loading volume was 50% of the headspace volume of R1
The Fc loading volume was 50% of the headspace volume of R2
The Fc loading volume was 50% of the headspace volume of R3
The Fc loading volume was 50% of the headspace volume of R4
Comparative example 4
The Gc filling volume accounts for 50 percent of the volume of the upper space of the R1
The Gc filling volume accounts for 50 percent of the volume of the upper space of the R2
The Gc filling volume accounts for 50 percent of the volume of the upper space of the R3
The Gc filling volume accounts for 50 percent of the volume of the upper space of the R4
Comparative example 5
FZC-204A deviceFilling volume of R1 upper space body
50% of the product
FZC-204A filling volume occupying R2 upper space body
50% of the product
FZC-204A filling volume occupying R3 upper space body
50% of the product
FZC-204A filling volume occupying R4 upper space body
50% of the product
Comparative example 6
No catalyst loading on top
No catalyst loading on top
No catalyst loading on top
No catalyst loading on top
TABLE 5 Properties of catalysts used in comparative examples 5 and 9 of the present invention
Catalyst type
FZC-204A
Particle shape
All-grass of Tetrastigma
Particle diameter/mm
1.2
Length of particles/mm
9.0
Strength/N. (mm)-1
20
Specific surface area/m2.g-1
171
Pore volume/cm3.g-1
0.63
Wear rate/wt%
0.5
Chemical composition/wt%
MoO3
11.5
NiO
2.5
TABLE 6 operating conditions for examples 6 to 15 and comparative examples 3 to 9
Residual oil feedstock
Starting materials A
Reaction pressure, MPa
15.7
Liquid hourly volume space velocity, h-1
0.31
Volume ratio of hydrogen to oil
650
Reaction temperature of
R1
385
R2
385
R3
385
R4
385
TABLE 7 Properties of the oils formed by hydrogenation of the residues
Example 6
Example 7
Example 8
Example 9
Example 10
Running time, h
5000
5000
5000
5000
5000
Density (20 ℃ C.), g/cm3
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，μg.g-1
10.4
9.4
10.7
12.4
10.7
Fe，μg.g-1
2.2
2.0
2.3
3.0
2.1
Ca，μg.g-1
1.5
1.4
1.3
2.1
1.3
Total pressure drop of bed layer, MPa
1.53
1.46
1.51
1.55
1.52
TABLE 7 Properties of the oils formed by hydrogenating the residues
Comparative example 3
Comparative example 4
Comparative example 5
Comparative example 6
Running time, h
5000
5000
5000
5000
Density (20 ℃ C.), g/cm3
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，μg.g-1
13.4
13.5
13.3
14.6
Fe，μg.g-1
6.5
6.6
6.4
8.6
Ca，μg.g-1
5.6
5.8
5.4
7.6
Total pressure drop of bed layer, MPa
1.70
1.72
1.75
1.86
TABLE 8 catalyst loading in examples 11-15 and comparative examples 7-9
Examples of the embodiments
Number (C)
R1
R2
R3
R4
Example 11
The M1 packing volume was 50% of the volume of the head space of R1
The M1 packing volume was 50% of the volume of the head space of R2
The M1 packing volume was 50% of the volume of the head space of R3
The M1 packing volume was 50% of the volume of the head space of R4
Example 12
The M2 packing volume was 50% of the volume of the head space of R1
The M2 packing volume was 50% of the volume of the head space of R2
The M2 packing volume was 50% of the volume of the head space of R3
The M2 packing volume was 50% of the volume of the head space of R4
Example 13
The M3 packing volume was 50% of the volume of the head space of R1
The M3 packing volume was 50% of the volume of the head space of R2
The M3 packing volume was 50% of the volume of the head space of R3
The M3 packing volume was 50% of the volume of the head space of R4
Example 14
The M4 packing volume was 50% of the volume of the head space of R1
The M4 packing volume was 50% of the volume of the head space of R2
The M4 packing volume was 50% of the volume of the head space of R3
The M4 packing volume was 50% of the volume of the head space of R4
Example 15
The M5 packing volume was 50% of the volume of the head space of R1
The M5 packing volume was 50% of the volume of the head space of R2
The M5 packing volume was 50% of the volume of the head space of R3
The M5 packing volume was 50% of the volume of the head space of R4
Comparative example 7
The Fc loading volume was 50% of the headspace volume of R1
The Fc loading volume was 50% of the headspace volume of R2
The Fc loading volume was 50% of the headspace volume of R3
The Fc loading volume was 50% of the headspace volume of R4
Comparative example 8
The Gc filling volume accounts for 50 percent of the volume of the upper space of the R1
The Gc filling volume accounts for 50 percent of the volume of the upper space of the R2
The Gc filling volume accounts for 50 percent of the volume of the upper space of the R3
The Gc filling volume accounts for 50 percent of the volume of the upper space of the R4
Comparative example 9
FZC-204A filling volume occupying R1 upper space body
50% of the product
FZC-204A filling volume occupying R2 upper space body
50% of the product
FZC-204A filling volume occupying R3 upper space body
Product 50%
FZC-204A filling volume occupying R4 upper space body
50% of the product
TABLE 9 Properties of the oils formed by hydrogenation of the residues
Example 11
Example 12
Example 13
Example 14
Example 15
Running time, h
5000
5000
5000
5000
5000
Density (20 ℃ C.), g/cm3
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，μg.g-1
10.3
9.3
10.6
12.3
10.6
Fe，μg.g-1
2.1
1.9
2.2
2.9
2
Ca，μg.g-1
1.4
1.3
1.2
2
1.2
Total pressure drop of bed layer, MPa
1.52
1.45
1.5
1.54
1.51
TABLE 9 Properties of the oils formed by hydrogenation of the residues
Comparative example 7
Comparative example 8
Comparative example 9
Running time, h
5000
5000
5000
Density (20 ℃ C.), g/cm3
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，μg.g-1
13.3
13.4
13.2
Fe，μg.g-1
6.4
6.5
6.3
Ca，μg.g-1
5.5
5.7
5.3
Total pressure drop of bed layer, MPa
1.69
1.71
1.74
As can be seen from tables 7 and 9, the residue hydrotreating process of the present invention has a high impurity removal rate and a small bed pressure drop, and particularly, iron and calcium are effectively removed. When the catalyst M adopts the catalyst Fc or Gc, the hydrotreating catalyst has no channel, so that the residual oil diffusion path is prolonged, the activity is influenced, and simultaneously, impurities such as deposited carbon deposit occupy more inter-particle spaces due to the lack of impurity-containing volume carbon spaces of tapered pore channels, so that the bed layer void ratio is reduced, the pressure drop is increased, and the activity and the service life of the catalyst are influenced. And when the catalyst M adopts the demetallization or desulfurization catalyst which is conventional in the field, the iron and calcium impurities in the residual oil raw material cannot be effectively removed. Compared with the conventional filling mode of filling the catalyst M at the top, the filling of the catalyst M can enhance the impurity removal performance of the volume carbon and delay the rise of pressure drop. It is fully demonstrated that the method of the present invention is particularly suitable for treating residual oil with high content of iron and calcium impurities, not only can effectively remove and attach iron and/or calcium impurities, but also can prolong the operation period of the device, and the overall activity of the catalyst is high.