A system apparatus and an oil phase hydrogenation method for oil phase hydrogenation

Abstract

The present application relates to a kind of system device and oil phase hydrogenation method for oil phase hydrogenation, including hydrogen delivery unit, raw oil delivery unit, heating unit, hydrogenation unit, hydrogenation reaction unit and separation unit;Hydrogenation reaction unit includes the first hydrogenation subunit and the second hydrogenation subunit connected in sequence, and hydrogenation internal member is arranged between the adjacent catalyst bed of first hydrogenation subunit;Hydrogenation internal member is double-layer pipe component, and the hole with the diameter of 0.0001-1mm is set on inner layer pipe, the hole with the diameter of 1-100mm is set on outer layer pipe, and the top of outer layer pipe is provided with gas-liquid dispersion guide vane, by using hydrogenation internal member, hydrogen is efficiently dispersed and dissolved in oil phase with micro-bubble form, reach hydrogen, oil phase, catalyst gas-liquid-solid three-phase interface efficient contact, further substantially strengthen hydrogenation reaction and improve oil phase hydrogenation reaction rate, reduce reaction pressure, improve hydrogenation product sulfur, nitrogen, metal and the removal efficiency of impurities such as residual carbon.

Description

Technical Field

[0001] This invention relates to the field of oil refining and chemical technology, specifically to a system and method for oil-phase hydrogenation. Background Technology

[0002] Currently, oil-phase hydrogenation mainly includes hydrogenation of residue oil, gasoline and diesel oil, wax oil, and lubricating oil. Among these, residue oil processing technology is an indispensable process in all petroleum refining processes. Residue oil processing mainly includes solvent deasphalting, viscosity-reducing cracking, coking, catalytic cracking, and hydrogenation. Residue oil hydrogenation technology, with its strong adaptability to feedstocks and operational flexibility, is an important technical means to achieve the clean and efficient utilization of residue oil resources.

[0003] For example, CN103131470A discloses a method for hydrotreating residual oil; the residual oil feedstock is mixed with catalytic cracking recycle oil that has undergone hydrotreating pretreatment, and optionally with catalytic cracking slurry from which solid dust has been separated, and enters an upflow reactor from the bottom of the reactor to contact the upflow hydrotreating catalyst for hydrotreating reaction. The reactants I sequentially enter 3-6 trickle bed reactors arranged in series. Reactants II undergo gas-liquid separation in a hot high-pressure separator. The liquid phase material is fractionated to obtain hydrotreating residual oil, which is used as feed for the catalytic cracking unit. The gas phase material is mixed with the recycle oil from the catalytic cracking unit and enters the catalytic cracking recycle oil hydrotreating pretreatment reactor. Material III undergoes gas-liquid separation. The gas phase is removed from hydrocarbons, hydrogen sulfide, and ammonia impurities and then enters an upflow reactor. The liquid phase is hydrotreating pretreated and then mixed with the residual oil feedstock.

[0004] Compared to other residue hydrotreating technologies, fixed-bed hydrotreating technology has lower investment and operating costs, and is safer and simpler to operate. It is the most widely used and technologically mature residue hydrotreating technology in industry to date. In fixed-bed hydrotreating, the gaseous phase of hydrogen and the liquid phase of residue oil mix and flow through the catalyst bed. The hydrogen, residue oil, and catalyst need to undergo a hydrogenation reaction at the gas-liquid-solid three-phase interface. However, due to the low solubility of hydrogen in residue oil and its poor fluidity, it is difficult to mix hydrogen and residue oil uniformly, leading to uneven gas-liquid phase distribution in the catalyst bed. Consequently, the mass transfer rate in the residue hydrotreating reaction is much slower than the intrinsic reaction rate. The mass transfer process is the rate-controlling step of the hydrogenation reaction, resulting in a low catalytic reaction rate. Therefore, the residue hydrotreating process must be carried out under harsh conditions such as high temperature and high pressure, resulting in huge energy and material consumption.

[0005] In summary, current fixed-bed catalytic hydrogenation processes for residual oil still suffer from problems such as low hydrogenation reaction rate, high reaction pressure, and poor impurity removal efficiency. Summary of the Invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to provide a system device and method for oil phase hydrogenation, so as to solve the problems that existing fixed-bed catalytic hydrogenation processes for oil phase still have low hydrogenation reaction rate, high reaction pressure and poor impurity removal effect.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a system apparatus for oil-phase hydrogenation, the system apparatus for oil-phase hydrogenation comprising a hydrogen delivery unit, a feedstock oil delivery unit, a heating unit, a hydrogen mixing unit, a hydrogenation reaction unit, and a separation unit;

[0009] The hydrogenation reaction unit includes a first hydrogenation subunit and a second hydrogenation subunit connected in sequence, and a hydrogen mixing internal component is provided between adjacent catalyst beds of the first hydrogenation subunit.

[0010] The hydrogen mixing internal component is a double-layer tube component. The inner tube is provided with holes with a diameter of 0.0001-1 mm, and the outer tube is provided with holes with a diameter of 1-100 mm. A gas-liquid dispersion guide plate is provided at the top of the outer tube.

[0011] The first outlet of the hydrogen delivery unit is connected to the heating unit;

[0012] The material outlet of the raw oil conveying unit is connected to the heating unit;

[0013] The second outlet of the hydrogen delivery unit is connected to the inlet of the hydrogen mixing unit;

[0014] The third outlet of the hydrogen delivery unit is connected to the inlet of the hydrogen mixing internal component.

[0015] The heating unit, hydrogen mixing unit, hydrogenation reaction unit, and separation unit are connected in sequence.

[0016] The first flow port of the separation unit is connected to the main hydrogen pipe of the hydrogen delivery unit.

[0017] The system device for oil-phase hydrogenation provided by this invention utilizes specific hydrogen mixing internal components to efficiently disperse and dissolve hydrogen in the oil phase in the form of microbubbles, achieving efficient contact at the gas-liquid-solid three-phase interface of hydrogen, residual oil, and catalyst. This significantly enhances the hydrogenation reaction process. Compared to traditional oil-phase trickle bed hydrogenation technology, this hydrogenation scheme can increase the oil-phase hydrogenation reaction rate, reduce reaction pressure, and improve the removal efficiency of impurities such as sulfur, nitrogen, metals, and residual carbon in the hydrogenation products. This is of great significance for refineries to save energy, reduce emissions, and improve quality and efficiency.

[0018] As a preferred technical solution of the present invention, the hydrogen delivery unit includes a hydrogen supply device, a compression device and a first filtration device connected in sequence;

[0019] Preferably, the first flow port of the separation unit is connected to the main hydrogen pipe after the first filtration device.

[0020] As a preferred technical solution of the present invention, the raw material oil conveying unit includes a raw material liquid supply device, a conveying buffer device, a second filtration device and a first pump connected in sequence;

[0021] Preferably, the material outlet of the first pump is connected to the heating unit.

[0022] As a preferred technical solution of the present invention, the second hydrogenation subunit includes at least three sets of hydrogen mixing devices and hydrogenation reaction devices connected in sequence.

[0023] Preferably, the fourth outlet of the hydrogen delivery unit is connected to a hydrogen mixing device.

[0024] As a preferred technical solution of the present invention, the hydrogenation reaction unit and the separation unit are connected by a bubble coalescence device.

[0025] As a preferred embodiment of the present invention, the separation unit includes a first separator, a second separator, and a third separator;

[0026] Preferably, the material outlet of the bubble coalescence device is connected to the material inlet of the first separator;

[0027] Preferably, the first material outlet of the first separator is connected to the material inlet of the second separator;

[0028] Preferably, the first material outlet of the second separator is connected to the main hydrogen pipe of the hydrogen conveying unit;

[0029] Preferably, the second material outlet of the first separator and the second material outlet of the second separator are both connected to the material inlet of the third separator;

[0030] Preferably, the first material outlet of the third separator is connected to the fractionation system;

[0031] Preferably, the second material outlet of the third separator is connected to the gas recovery system.

[0032] In a second aspect, the present invention provides an oil-phase hydrogenation method, the oil-phase hydrogenation method comprising performing a hydrogenation reaction of an oil phase and hydrogen gas using a system apparatus as described in the first aspect for oil-phase hydrogenation.

[0033] As a preferred technical solution of the present invention, the oil phase hydrogenation method includes: mixing preheated hydrogen and preheated oil phase and then performing catalytic hydrogenation to obtain hydrogenated heavy oil.

[0034] As a preferred technical solution of the present invention, the oil phase targeted by the oil phase hydrogenation method includes one or a combination of at least two of diesel oil, wax oil, lubricating oil, kerosene, residual oil or reformed oil.

[0035] Preferably, the oil phase hydrogenation method is applied to heavy oil and / or residue oil.

[0036] As a preferred embodiment of the present invention, the temperature of the preheated hydrogen is 300-350°C;

[0037] Preferably, the temperature of the preheated oil phase is 300-350℃;

[0038] Preferably, the volume ratio of hydrogen to oil phase in the catalytic hydrogenation is (10-1000):1;

[0039] Preferably, the volume hourly space velocity (VHSV) for the catalytic hydrogenation is 0.1-2.5 h⁻¹. -1 ;

[0040] Preferably, the reaction pressure for catalytic hydrogenation is 10-20 MPa;

[0041] Preferably, the reaction temperature for catalytic hydrogenation is 320-450°C.

[0042] Compared with existing technical solutions, the present invention has the following beneficial effects:

[0043] The hydrogen-oil interphase hybridization enhanced oil-phase hydrogenation system method provided by this invention can significantly enhance the hydrogenation reaction characteristics of the gas-liquid-solid three-phase interface of hydrogen, residue oil, and catalyst, improve catalyst utilization, reduce reaction temperature, pressure, and hydrogen-oil ratio, and significantly reduce energy and material consumption of the equipment. It has the advantages of high equipment safety performance and low investment cost. The obtained residue oil product has a sulfur mass percentage of ≤0.382%, a total nitrogen content of ≤756μg / g, a residual carbon mass percentage of ≤4.1%, and a metal (Ni+V) content of ≤7.2μg / g. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of a system apparatus for oil-phase hydrogenation provided in an embodiment of the present invention;

[0045] Figure 2 This is a schematic diagram of the double-layer tube component of the hydrogen mixing internal component in an embodiment of the present invention.

[0046] In the diagram: 1-Hydrogen supply equipment, 2-Compression equipment, 3-First filtration equipment, 4-Raw material supply equipment, 5-Transportation and buffer equipment, 6-Second filtration equipment, 7-First pump, 8-Heating unit, 9-Hydrogen mixing unit, 10-First hydrogenation subunit, 11-Hydrogen mixing internal components, 12-First hydrogen mixing equipment, 13-First hydrogenation reaction equipment, 14-Second hydrogen mixing equipment, 15-Second hydrogenation reaction equipment, 16-Third hydrogen mixing equipment, 17-Third hydrogenation reaction equipment, 18-Fourth hydrogen mixing equipment, 19-Fourth hydrogenation reaction equipment, 20-Bubble coalescence equipment, 21-First separator, 22-Second separator, 23-Second pump, 24-Third separator, 25-Fractioning system, 26-Gas recovery system.

[0047] The present invention will now be described in further detail. However, the examples described below are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims. Detailed Implementation

[0048] To better illustrate the present invention and facilitate understanding of its technical solutions, typical but non-limiting embodiments of the present invention are as follows:

[0049] This embodiment provides a system apparatus for oil-phase hydrogenation, such as... Figure 1 As shown, the system for oil-phase hydrogenation includes a hydrogen delivery unit, a feedstock oil delivery unit, a heating unit 8, a hydrogen mixing unit 9, a hydrogenation reaction unit, and a separation unit.

[0050] The hydrogenation reaction unit includes a first hydrogenation subunit 10 and a second hydrogenation subunit connected in sequence, and a hydrogen mixing internal component 11 is provided between adjacent catalyst beds of the first hydrogenation subunit 10.

[0051] The hydrogen mixing inner component 11 is a double-layer tube component. The inner tube is provided with holes with a diameter of 0.0001-1 mm, and the outer tube is provided with holes with a diameter of 1-100 mm. A gas-liquid dispersion guide plate is provided at the top of the outer tube.

[0052] The first outlet of the hydrogen delivery unit is connected to the heating unit 8;

[0053] The material outlet of the raw oil conveying unit is connected to the heating unit 8;

[0054] The second outlet of the hydrogen delivery unit is connected to the inlet of the hydrogen mixing unit 9;

[0055] The third outlet of the hydrogen delivery unit is connected to the inlet of the hydrogen mixing internal component 11.

[0056] The heating unit 8, the hydrogen mixing unit 9, the hydrogenation reaction unit, and the separation unit are connected in sequence.

[0057] The first flow port of the separation unit is connected to the main hydrogen pipe of the hydrogen delivery unit.

[0058] In this invention, the hydrogen mixing inner component 11 is a double-layer tube component. The inner tube is provided with holes of 0.0001-1 mm in diameter, for example, holes of 0.0001 mm, 0.0002 mm, 0.0003 mm, 0.0004 mm, 0.0005 mm, 0.0006 mm, 0.0007 mm, 0.0008 mm, 0.0009 mm, 0.001 mm, 0.002 mm, 0.003 mm, 0.004 mm, 0.005 mm, and 0.006 mm in diameter. The values ​​may be m, 0.007mm, 0.008mm, 0.009mm, 0.01mm, 0.02mm, 0.03mm, 0.04mm, 0.05mm, 0.06mm, 0.07mm, 0.08mm, 0.09mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, or 1mm, but are not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0059] In this invention, the hydrogen mixing inner component 11 is a double-layer tube component, with holes of diameter 1-100 mm provided on the outer tube, for example, holes of diameters of 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 12 mm, 14 mm, 16 mm, 18 mm, 20 mm, 22 mm, 24 mm, 26 mm, 28 mm, 30 mm, 32 mm, 34 mm, 36 mm, 38 mm, 40 mm, 42 mm, and 44 mm. The following values ​​are acceptable: 46mm, 48mm, 50mm, 52mm, 54mm, 56mm, 58mm, 60mm, 62mm, 64mm, 66mm, 68mm, 70mm, 72mm, 74mm, 76mm, 78mm, 80mm, 82mm, 84mm, 86mm, 88mm, 90mm, 92mm, 94mm, 96mm, 98mm, or 100mm, but are not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0060] In this invention, the distribution of holes on the inner and outer tubes of the double-layer tube component in the hydrogen mixing internal component 11 can be equidistant or non-equidistant, with a specific spacing range of 0.001-10mm; at the same time, the diameter of the holes distributed on the inner and outer tubes can be uniform, i.e., equal, or it can be a combination of holes formed by multiple hole diameters within the range.

[0061] In this invention, the top of the outer tube is provided with a gas-liquid dispersion guide plate, the upper side of which refers to the direction perpendicular to the horizontal plane with the horizontal plane as the reference.

[0062] In this invention, the hydrogen mixing internal component 11 can disperse hydrogen material into micro-nano-scale bubbles with a bubble diameter ranging from 0.0001 to 1 mm. The dispersed bubbles are uniformly dispersed in the liquid phase to form a pseudo-homogeneous material stream.

[0063] In this invention, the gas-liquid dispersion guide plate provided at the top of the outer tube of the hydrogen mixing internal component 11 can improve the radial dispersion uniformity of microbubbles in the reactor, and at the same time block the catalyst particles deposited in the upper bed.

[0064] In this invention, the gas-liquid dispersion guide plate is exemplarily a Y-shaped gas-liquid dispersion guide plate, such as... Figure 2 As shown.

[0065] In this invention, the hydrogen mixing internal component 11 is disposed between adjacent catalyst beds of the first hydrogenation subunit 10. For example, it is a U-structure with the open end connected to hydrogen gas. It is then built into the gap between the catalyst beds of the hydrogenation reactor to supplement hydrogen gas to the reactor bed in a multi-stage feeding manner, control the bed temperature, and cold hydrogen comes out from the distributor in the form of micro-nano bubbles and is efficiently and uniformly dispersed in the oil phase of the bed. The hydrogen bubble size is 0.0001-1mm, or it is a semi-closed structure of other structures.

[0066] In this invention, the catalyst loading form in the first hydrogenation subunit 10 is as follows: the reactor is loaded with protective agent and demetallizing agent alternately in layers from bottom to top. The protective agent is preferably loaded in descending order of size, and 4-5 types of demetallizing agent are loaded in ascending order of activity. The volume of protective agent accounts for 20-30% of the total volume of the reactor, and the volume of demetallizing agent accounts for 70%-80% of the total volume of the reactor, totaling 100%.

[0067] In this invention, the protective agent packed in the first hydrogenation subunit 10 can be selected from protective agents commonly used in oil-phase hydrogenation in the art. For example, taking residue hydrogenation as an example, the protective agent used is mainly composed of alumina and is prepared into irregular structures such as porous spheres, honeycomb cylinders, porous foams, and Raschig rings. The protective agent can be selected from the CG series residue hydrogenation protective agents developed by CNOOC Chemical and New Materials Science Research Institute, or it can be prepared according to the knowledge in the art as needed.

[0068] In this invention, the demetallizing agent packed in the first hydrogenation subunit 10 can be selected from commonly used demetallizing agents in oil-phase hydrogenation. Taking residue hydrogenation as an example, the demetallizing agent uses alumina as a carrier and can add relevant additives such as P, Si, B, F, etc., with one or more elements selected from Co, Ni, Mo, and W as the active component of the demetallizing agent. The demetallizing agent can be selected from the CDM series residue hydrogenation demetallizing agents developed by CNOOC Chemical and New Materials Science Research Institute, or it can be prepared according to the knowledge in this field as needed.

[0069] In the first hydrogenation subunit 10, the volume of the protective agent accounts for 20-30% of the total volume of the reactor. For example, it can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%, but is not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0070] The proportion of the demetallizing agent filling volume in the first hydrogenation subunit 10 to the total reactor volume can be 80%, 79%, 78%, 77%, 76%, 75%, 74%, 73%, 72%, 71%, or 70%, but is not limited to the listed values. Other unlisted values ​​within this range also meet the requirements.

[0071] For example, the average particle size range of the protective agent from bottom to top is 30.0-40.0 mm, 15.0-20 mm, 10.0-14.0 mm, 5.0-9.0 mm, and 2.0-4.0 mm, and the mass content of active metal MoO3 in the demetallizing agent ranges from 0.0-0.3%, 0.4-0.8%, 1.0-2.0%, 2.5-4.0%, and 5.0-8.0%.

[0072] Specifically, the reactor is filled with protective agent and demetallizing agent from bottom to top as follows: starting from the bottom of the reactor, a layer of protective agent with an average particle size range of 30.0-40.0 mm is sequentially loaded, followed by a layer of demetallizing agent with a MoO3 mass content of 0.0-0.3%, a layer of protective agent with an average particle size range of 15.0-20 mm, a layer of demetallizing agent with a MoO3 mass content of 0.4-0.8%, a layer of protective agent with an average particle size range of 10.0-14.0 mm, and so on. The composition consists of a layer of demetallizing agent with a MoO3 mass content of 1.0-2.0%, a layer of protective agent with an average particle size range of 5.0-9.0 mm, a layer of demetallizing agent with a MoO3 mass content of 2.5-4.0%, a layer of protective agent with an average particle size range of 2.0-4.0 mm, and a layer of demetallizing agent with a MoO3 mass content of 5.0-8.0%. Other cases follow the same pattern. The specific filling volume of the corresponding protective agent and demetallizing agent can be adjusted by the thickness of the corresponding layer.

[0073] In this invention, the purpose of the heating unit is to heat a portion of the pre-mixed oil phase and hydrogen gas, thereby improving the subsequent processing. The heating equipment can be any commonly used heating equipment in the art.

[0074] Specifically, the hydrogen delivery unit includes a hydrogen supply device 1, a compression device 2, and a first filtration device 3 connected in sequence.

[0075] In this invention, the first filtration device 3 is capable of filtering particulate impurities in hydrogen gas, with the particle size range being 1-10 μm.

[0076] In this invention, the particle size range of particulate impurities is any particle size value within the range, that is, it can be particulate impurities with uniform particle size, or it can be a composition of particles with multiple particle size values.

[0077] The first flow port of the separation unit is connected to the main hydrogen pipe after the first filtration device 3;

[0078] The hydrogen separated from the first flow port of the separation unit is supplied as hydrogen raw material through the main hydrogen pipe. That is, in this invention, the end of the main hydrogen pipe is divided into 4 outlets through sub-pipes and fed into the corresponding equipment in the system.

[0079] Specifically, the raw material oil conveying unit includes a raw material liquid supply device 4, a conveying buffer device 5, a second filtration device 6, and a first pump 7 connected in sequence;

[0080] In this invention, the second filtration device 6 can filter particulate impurities in the oil phase, and the particle size range of the particulate impurities is 10-1000μm.

[0081] The material outlet of the first pump 7 is connected to the heating unit 8;

[0082] Specifically, the second hydrogenation subunit includes at least three sets of hydrogen mixing devices and hydrogenation reaction devices connected in sequence;

[0083] In this invention, exemplarily, at least three sets of hydrogen mixing devices and hydrogenation reaction devices are connected in sequence, including at least a first hydrogen mixing device 12, a first hydrogenation reaction device 13, a second hydrogen mixing device 14, a second hydrogenation reaction device 15, a third hydrogen mixing device 16, a third hydrogenation reaction device 17, a fourth hydrogen mixing device 18, and a fourth hydrogenation reaction device 19 connected in sequence. When there are more than three sets, the same principle applies. That is, one set of the second hydrogenation subunit in this invention is a hydrogen mixing device and a hydrogenation reaction device connected in sequence. When there are multiple sets, the sets can be connected in series. The catalyst setting is reasonably set according to actual needs.

[0084] For example, when four sets of connected hydrogen mixing equipment and hydrogenation reaction equipment are set up, at least one type of demetallizing agent is loaded sequentially from top to bottom in the first hydrogenation reaction equipment 13 of the second hydrogenation subunit. Preferably, 3-4 types of demetallizing agents are loaded in order of decreasing size and increasing activity. At least one type of demetallizing and desulfurization transition catalyst is loaded in the second hydrogenation reaction equipment 15. At least one type of desulfurization catalyst is loaded in the third hydrogenation reaction equipment 17. At least one type of desulfurization catalyst is loaded in the fourth hydrogenation reaction equipment 19. At least one type of residual carbon removal catalyst is loaded in the fourth hydrogenation reaction equipment 19.

[0085] In this invention, the demetallizing agent used in the first hydrogenation reaction device 13 can be selected as a demetallizing agent of the same series as the demetallizing agent loaded in the first hydrogenation subunit 10.

[0086] In this invention, the demetallization and desulfurization transition catalyst used in the second hydrogenation reaction unit 15 can be selected from commonly used demetallization and desulfurization transition catalysts in oil-phase hydrogenation in the art, such as those using alumina as a support, which have certain demetallization and desulfurization performance, further removing metals that are difficult to remove after demetallization, and using Ni and Mo as the active components of the demetallization agent. The demetallization and desulfurization transition agent can be selected from the CDM-410 series residue oil hydrogenation demetallization and desulfurization transition agent developed by CNOOC Chemical and New Materials Science Research Institute, or can be prepared according to the knowledge in the art as needed.

[0087] In this invention, the desulfurization catalyst used in the third hydrogenation reaction unit 17 can be selected from commonly used desulfurization catalysts in oil-phase hydrogenation in this field. For example, taking residue oil hydrogenation as an example, the desulfurization catalyst uses alumina as a support and one or more elements selected from Co, Ni, Mo, and W as the active component of the demetallizing agent. The demetallizing agent can be selected from the CDS series residue oil hydrogenation desulfurizing agent developed by CNOOC Chemical and New Materials Science Research Institute, or it can be prepared according to the knowledge in this field as needed.

[0088] In this invention, the decarbonization catalyst used in the fourth hydrogenation reaction unit 19 can be selected from commonly used decarbonization catalysts in oil-phase hydrogenation processes in this field. For example, taking residue oil hydrogenation as an example, the decarbonization catalyst uses alumina as a support and can add relevant additives such as P, Si, B, F, etc., with one or more elements selected from Co, Ni, Mo, and W as the active component of the decarbonization catalyst. The demetallizing agent can be selected from the CDC series residue oil hydrogenation decarbonization catalyst developed by CNOOC Chemical and New Materials Science Research Institute, or it can be prepared according to the knowledge in this field as needed.

[0089] Among them, at least one demetallizing agent, preferably 3-4 types of demetallizing agents are filled in order of decreasing size and increasing activity, with corresponding size ranges of 3.1-5.0 mm, 2.1-3.0 mm, 1.6-2.0 mm, and 1.0-1.5 mm, and the mass percentage content of active metal MoO3 ranges of 5.0-6.5%, 6.6-7.5%, 7.6-8.5%, and 8.6-10.0%.

[0090] For example, the top-to-bottom assembly is based on the top of the reactor, and sequentially fills a layer of demetallizing agent with a thickness of 3.1-5.0 mm, a layer of demetallizing agent with a MoO3 mass percentage of 5.0-6.5%, a layer of demetallizing agent with a thickness of 2.1-3.0 mm, a layer of demetallizing agent with a MoO3 mass percentage of 6.6-7.5%, a layer of demetallizing agent with a MoO3 mass percentage of 1.6-2.0 mm, a layer of demetallizing agent with a MoO3 mass percentage of 7.6-8.5%, a layer of demetallizing agent with a MoO3 mass percentage of 1.0-1.5 mm, and a layer of demetallizing agent with a MoO3 mass percentage of 8.6-10.0%.

[0091] In this invention, the hydrogen mixing device in the hydrogen mixing unit 9 and the hydrogen mixing device in the second hydrogenation subunit efficiently and uniformly disperse the fed hydrogen in the feed oil in the form of micro-nano-scale bubbles. The hydrogen oil flows out from the mixer outlet in a pseudo-homogeneous phase. The bubble size of the hydrogen in the outlet material is between 0.0001-1 mm and is dispersed in the oil phase with a uniform bubble size.

[0092] In this invention, the hydrogen mixing device in the hydrogen mixing unit 9 and the hydrogen mixing device in the second hydrogenation subunit are hydrogen-oil mixing devices commonly used in the art, such as the hydrogen-oil mixing device disclosed in CN113368594A or other commercially available hydrogen-oil mixing devices.

[0093] Specifically, the fourth outlet of the hydrogen delivery unit is connected to the hydrogen mixing equipment;

[0094] Specifically, the hydrogenation reaction unit and the separation unit are connected by a bubble coalescence device 20;

[0095] In this invention, the bubble coalescence device 20 adopts a cyclone flow method, which causes the hydrogen and oil phases to coalesce into a continuous phase under the action of centrifugal force, which is then separated from the oil phase and enters the separation unit for separation.

[0096] Specifically, the separation unit includes a first separator 21, a second separator 22, and a third separator 24;

[0097] The material outlet of the bubble coalescence device 20 is connected to the material inlet of the first separator 21.

[0098] The first material outlet of the first separator 21 is connected to the material inlet of the second separator 22.

[0099] The first material outlet of the second separator 22 is connected to the main hydrogen pipe of the hydrogen conveying unit.

[0100] In this invention, the first material outlet of the second separator 22 is connected to the main hydrogen pipe of the hydrogen delivery unit via the second pump 23, so as to complete the secondary utilization of the recovered hydrogen.

[0101] The second material outlet of the first separator 21 and the second material outlet of the second separator 22 are both connected to the material inlet of the third separator 24.

[0102] The first material outlet of the third separator 24 is connected to the fractionation system 25;

[0103] The second material outlet of the third separator 24 is connected to the gas recovery system 26;

[0104] In this invention, the first separator 21 is a hot high-pressure separator, the second separator 22 is a cold high-pressure separator, and the third separator 24 is a cold low-pressure separator.

[0105] In this invention, the hydrogen oil obtained from the hydrogenation reaction is separated into light components by a hot high-pressure separator, and then enters a cold high-pressure separator to separate light hydrogen components. The hydrogen is then fed into the hydrogenation system via a circulating hydrogen compressor. The heavy components from the hot and cold high-pressure separators enter a cold low-pressure separator. The top gas enters the gas recovery system 26, and the bottom liquid phase enters the fractionation system 25.

[0106] Furthermore, the present invention provides an oil-phase hydrogenation method based on the aforementioned system apparatus for oil-phase hydrogenation, the oil-phase hydrogenation method comprising:

[0107] Preheated hydrogen and preheated oil phase are mixed and then subjected to catalytic hydrogenation to obtain hydrogenated heavy oil.

[0108] Specifically, the oil phase targeted by the oil phase hydrogenation method includes one or a combination of at least two of the following: diesel oil, wax oil, lubricating oil, kerosene, residual oil, or reformed oil.

[0109] Specifically, the oil phase hydrogenation method is applied to heavy oil and / or residue oil.

[0110] Specifically, the temperature of the preheated hydrogen is 300-350℃, for example, it can be 300℃, 310℃, 320℃, 330℃, 340℃ or 350℃, etc., but is not limited to the listed values. Other unlisted values ​​within this range also meet the requirements.

[0111] Specifically, the temperature of the preheated oil phase is 300-350℃, for example, it can be 300℃, 310℃, 320℃, 330℃, 340℃ or 350℃, etc., but is not limited to the listed values. Other unlisted values ​​within this range also meet the requirements.

[0112] Specifically, the volume ratio of hydrogen to oil phase in the catalytic hydrogenation is (10-1000):1, for example, it can be 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1 or 1000:1, but is not limited to the listed values. Other unlisted values ​​within this range also meet the requirements.

[0113] Specifically, the volume hourly space velocity (VHSV) for the catalytic hydrogenation is 0.1-2.5 h⁻¹. -1 For example, it could be 0.1h -1 0.2h -1 0.4h -1 0.6h -1 0.8h -1 1h -1 1.2h -1 1.4h -1 1.6h -1 1.8h -1 2.2h -1 2.4h -1 Or 2.5h -1 The values ​​may include, but are not limited to, the listed values; other unlisted values ​​within this range also meet the requirements.

[0114] Specifically, the reaction pressure for catalytic hydrogenation is 10-20 MPa, for example, it can be 10 MPa, 11 MPa, 12 MPa, 13 MPa, 14 MPa, 15 MPa, 16 MPa, 17 MPa, 18 MPa, 19 MPa or 20 MPa, but is not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0115] Specifically, the reaction temperature for catalytic hydrogenation is 320-450℃, for example, it can be 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃ or 450℃, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also acceptable.

[0116] In this invention, hydrogen and oil phases can be separated by gas-liquid separation after catalytic hydrogenation. The separated hydrogen is returned to the hydrogen supply end as a raw material for use, while other gases enter the gas recovery system 26. The heavy oil obtained from hydrogenation is further processed by subsequent fractionation.

[0117] In the gas-liquid separation process, the first separation involves separating the material after the bubbles have coalesced to obtain a first light component and a first heavy component.

[0118] The temperature for the first separation is 320-450℃, for example, it can be 320℃, 340℃, 360℃, 380℃, 400℃, 420℃, 440℃ or 450℃, etc., but is not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0119] The pressure of the first separation is 10-20 MPa, for example, it can be 10 MPa, 12 MPa, 14 MPa, 16 MPa, 18 MPa or 20 MPa, but is not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0120] The first light component is then subjected to a second separation to obtain a second heavy component and a second light component, namely hydrogen, which is returned to the feed gas inlet as a hydrogen source.

[0121] The second separation temperature is 25-150℃, for example, it can be 25℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃ or 150℃, but is not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0122] The pressure of the second separation is 10-20 MPa, for example, it can be 10 MPa, 12 MPa, 14 MPa, 16 MPa, 18 MPa or 20 MPa, but is not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0123] The first and second heavy components are mixed and then separated in the third separation. The light component obtained from the third separation enters the gas recovery system 26, and the heavy component obtained is the heavy oil obtained after hydrogenation.

[0124] The third separation temperature is 25-150℃, for example, it can be 25℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃ or 150℃, but is not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0125] The pressure of the third separation is 1-10 MPa, for example, it can be 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa or 10 MPa, but is not limited to the listed values. Other unlisted values ​​within this range are also acceptable.

[0126] In this embodiment, any combination of parameters in the corresponding steps described above can achieve the technical effect of the present invention, and is not limited to the examples shown in the following specific embodiments.

[0127] In this invention, the selection of protective agent, demetallizing agent, demetallizing and desulfurizing transition agent, desulfurizing agent and decarbonizing agent can be made reasonably according to the hydrogenation target, and the types of related reagents do not affect the hydrogenation treatment effect of the device provided by this invention.

[0128] To further illustrate the superior hydrogenation performance of the system for oil-phase hydrogenation provided by the present invention, specific embodiments are described below:

[0129] Example 1

[0130] This embodiment provides a system device for oil-phase hydrogenation, which includes a hydrogen conveying unit, a feedstock oil conveying unit, a heating unit 8, a hydrogen mixing unit 9, a hydrogenation reaction unit, and a separation unit;

[0131] The hydrogenation reaction unit includes a first hydrogenation subunit 10 and a second hydrogenation subunit connected in sequence, and a hydrogen mixing internal component 11 is provided between adjacent catalyst beds of the first hydrogenation subunit 10.

[0132] The hydrogen mixing inner component 11 is a double-layer tube component. The inner tube is provided with holes with a diameter of 0.0001-1 mm, and the outer tube is provided with holes with a diameter of 1-100 mm. A gas-liquid dispersion guide plate is provided at the top of the outer tube.

[0133] The first outlet of the hydrogen delivery unit is connected to the heating unit 8;

[0134] The material outlet of the raw oil conveying unit is connected to the heating unit 8;

[0135] The second outlet of the hydrogen delivery unit is connected to the inlet of the hydrogen mixing unit 9;

[0136] The third outlet of the hydrogen delivery unit is connected to the inlet of the hydrogen mixing internal component 11.

[0137] The heating unit 8, the hydrogen mixing unit 9, the hydrogenation reaction unit, and the separation unit are connected in sequence.

[0138] The first flow port of the separation unit is connected to the main hydrogen pipe of the hydrogen delivery unit.

[0139] In this embodiment, the hydrogen mixing inner component 11 is a double-layer tube component. The inner tube has holes with a diameter of 0.0001-1 mm, and the diameters of these holes are 0.0001 mm, 0.0002 mm, 0.0003 mm, 0.0004 mm, 0.0005 mm, 0.0006 mm, 0.0007 mm, 0.0008 mm, 0.0009 mm, 0.001 mm, 0.002 mm, 0.003 mm, 0.004 mm, 0.005 mm, and 0.006 mm, respectively. The diameters are m, 0.007mm, 0.008mm, 0.009mm, 0.01mm, 0.02mm, 0.03mm, 0.04mm, 0.05mm, 0.06mm, 0.07mm, 0.08mm, 0.09mm, 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, and 1mm, respectively. This means the holes on the inner tube are not of equal diameter, but are evenly spaced with a spacing of 1mm.

[0140] In this invention, the hydrogen mixing inner component 11 is a double-layer tube component. The outer tube is provided with holes of diameter 1-100mm, with hole diameters of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 12mm, 14mm, 16mm, 18mm, 20mm, 22mm, 24mm, 26mm, 28mm, 30mm, 32mm, 34mm, 36mm, 38mm, 40mm, 42mm, and 4mm respectively. 4mm, 46mm, 48mm, 50mm, 52mm, 54mm, 56mm, 58mm, 60mm, 62mm, 64mm, 66mm, 68mm, 70mm, 72mm, 74mm, 76mm, 78mm, 80mm, 82mm, 84mm, 86mm, 88mm, 90mm, 92mm, 94mm, 96mm, 98mm, 100mm, meaning the holes on the outer tube are not of equal diameter, and the holes are evenly spaced.

[0141] In this embodiment, the gas-liquid dispersion guide plate is a Y-shaped gas-liquid dispersion guide plate.

[0142] In this embodiment, the catalyst loading method in the first hydrogenation subunit 10 is as follows: the reactor is loaded with protective agent and demetallizing agent alternately in layers from bottom to top. Five types of protective agent and demetallizing agent are loaded according to size from large to small and activity from weak to strong. Among them, the size of the protective agent is selected as 30.0 mm, 16.0 mm, 12.0 mm, 6.0 mm and 3.0 mm, and the mass percentage of active metal MoO3 in the demetallizing agent is in the range of 0.3%, 0.8%, 1.5%, 3.5% and 6.5%. The protective agent accounts for 25% of the total reactor volume, and the demetallizing agent accounts for 75% of the total reactor volume. The specific filling configuration is as follows: starting from the bottom of the reactor, a layer of protective agent with an average particle size range of 30 mm, a layer of demetallizing agent with a MoO3 mass content of 0.3%, a layer of protective agent with an average particle size range of 16 mm, a layer of demetallizing agent with a MoO3 mass content of 0.8%, a layer of protective agent with an average particle size range of 12 mm, a layer of demetallizing agent with a MoO3 mass content of 1.5%, a layer of protective agent with an average particle size range of 6 mm, a layer of demetallizing agent with a MoO3 mass content of 3.5%, a layer of protective agent with an average particle size range of 3 mm, and a layer of demetallizing agent with a MoO3 mass content of 6.5%.

[0143] The hydrogen delivery unit includes a hydrogen supply device 1, a compression device 2, and a first filtration device 3 connected in sequence.

[0144] The first flow port of the separation unit is connected to the main hydrogen pipe after the first filtration device 3;

[0145] The hydrogen separated from the first flow port of the separation unit is supplied as hydrogen raw material through the main hydrogen pipe. That is, in this invention, the end of the main hydrogen pipe is divided into 4 outlets through sub-pipes and fed into the corresponding equipment in the system.

[0146] The raw material oil conveying unit includes a raw material liquid supply device 4, a conveying buffer device 5, a second filtration device 6, and a first pump 7 connected in sequence.

[0147] The material outlet of the first pump 7 is connected to the heating unit 8;

[0148] The second hydrogenation subunit includes four sets of hydrogen mixing equipment and hydrogenation reaction equipment connected in sequence.

[0149] In this embodiment, the four sets of hydrogen mixing devices and hydrogenation reaction devices connected in sequence include the first hydrogen mixing device 12, the first hydrogenation reaction device 13, the second hydrogen mixing device 14, the second hydrogenation reaction device 15, the third hydrogen mixing device 16, the third hydrogenation reaction device 17, the fourth hydrogen mixing device 18, and the fourth hydrogenation reaction device 19 connected in sequence.

[0150] In this embodiment, the protective agent, demetallizing agent, demetallizing and desulfurizing transition agent, desulfurizing agent, and carbon residue removal agent used in the hydrogenation process are selected from the CG series protective agent, CDM series demetallizing agent, CDM-410-12 demetallizing and desulfurizing transition agent, CDS series desulfurizing agent, and CDC series carbon residue removal agent developed by CNOOC Chemical and New Materials Research Institute. All of these are commercially available reagents.

[0151] In the second hydrogenation subunit, the first hydrogenation reaction device 13 is loaded with at least one demetallizing agent from top to bottom. Preferably, four types of demetallizing agents are loaded in descending order of size and ascending order of activity. Specifically, the top-to-bottom assembly is as follows, with the top of the reactor as the reference: a layer of demetallizing agent with an average particle size of 3 mm, a layer of demetallizing agent with a MoO3 mass percentage of 6.5%, a layer of demetallizing agent with a particle size of 1.8 mm, a layer of demetallizing agent with a MoO3 mass percentage of 7.5%, a layer of demetallizing agent with a MoO3 mass percentage of 1.6 mm, a layer of demetallizing agent with a MoO3 mass percentage of 8.5%, a layer of demetallizing agent with a MoO3 mass percentage of 1.3 mm, and a layer of demetallizing agent with a MoO3 mass percentage of 10.0%. The second hydrogenation reaction device 15 is loaded with a demetallization and desulfurization transition catalyst. The third hydrogenation reaction device 17 is loaded with a desulfurization catalyst. The fourth hydrogenation reaction device is loaded with a carbon removal catalyst.

[0152] In this invention, the hydrogen mixing device in the hydrogen mixing unit 9 and the hydrogen mixing device in the second hydrogenation subunit are hydrogen-oil mixing devices commonly used in the art, such as the hydrogen-oil mixing device disclosed in CN113368594A or other commercially available hydrogen-oil mixing devices. In this embodiment, the hydrogen-oil mixing device disclosed in CN113368594A is used.

[0153] The fourth outlet of the hydrogen delivery unit is connected to the hydrogen mixing equipment.

[0154] The hydrogenation reaction unit and the separation unit are connected by a bubble coalescence device 20.

[0155] The separation unit includes a first separator 21, a second separator 22, and a third separator 24.

[0156] The material outlet of the bubble coalescence device 20 is connected to the material inlet of the first separator 21.

[0157] The first material outlet of the first separator 21 is connected to the material inlet of the second separator 22.

[0158] The first material outlet of the second separator 22 is connected to the main hydrogen pipe of the hydrogen conveying unit.

[0159] In this invention, the first material outlet of the second separator 22 is connected to the main hydrogen pipe of the hydrogen delivery unit via the second pump 23, so as to complete the secondary utilization of the recovered hydrogen.

[0160] The second material outlet of the first separator 21 and the second material outlet of the second separator 22 are both connected to the material inlet of the third separator 24.

[0161] The first material outlet of the third separator 24 is connected to the fractionation system 25;

[0162] The second material outlet of the third separator 24 is connected to the gas recovery system 26;

[0163] In this embodiment, the first separator 21 is a hot high-pressure separator, the second separator 22 is a cold high-pressure separator, and the third separator 24 is a cold low-pressure separator.

[0164] In this embodiment, the hydrogen oil two-phase mixture obtained from the hydrogenation reaction is separated into light components by a hot high-pressure separator, and then enters a cold high-pressure separator to separate light hydrogen components. The hydrogen is then fed into the hydrogenation system via a circulating hydrogen compressor. The heavy components from the hot high-pressure separator and the cold high-pressure separator enter the cold low-pressure separator. The top gas enters the gas recovery system 26, and the bottom liquid phase enters the fractionation system 25.

[0165] Application Example 1

[0166] This application example provides an oil-phase hydrogenation method, performed using the system apparatus provided in Example 1, specifically including:

[0167] Preheated hydrogen and preheated oil phase are mixed and then subjected to catalytic hydrogenation to obtain hydrotreated heavy oil;

[0168] The preheated oil phase is residual oil;

[0169] The temperature of the preheated hydrogen is 300°C; the temperature of the preheated oil phase is 300°C.

[0170] The volume ratio of hydrogen to oil phase in the catalytic hydrogenation is 800:1; the volume hourly space velocity (VHSV) of the catalytic hydrogenation is 0.5 h⁻¹. -1 The reaction pressure for the catalytic hydrogenation is 12 MPa; the reaction temperature for the catalytic hydrogenation is 360 °C.

[0171] The temperature of the first separation is 400℃; the pressure of the first separation is 15MPa;

[0172] The temperature for the second separation is 100℃; the pressure for the second separation is 16MPa.

[0173] The temperature for the third separation is 90℃; the pressure for the third separation is 5MPa.

[0174] Application Example 2

[0175] This application example provides an oil-phase hydrogenation method, performed using the system apparatus provided in Example 1, specifically including:

[0176] Preheated hydrogen and preheated oil phase are mixed and then subjected to catalytic hydrogenation to obtain hydrotreated heavy oil;

[0177] The preheated oil phase is residual oil;

[0178] The temperature of the preheated hydrogen is 350°C; the temperature of the preheated oil phase is 350°C.

[0179] The volume ratio of hydrogen to oil phase in the catalytic hydrogenation is 10:1; the volume hourly space velocity (VHSV) of the catalytic hydrogenation is 0.1 h⁻¹. -1 The reaction pressure for catalytic hydrogenation is 15 MPa; the reaction temperature for catalytic hydrogenation is 370 °C.

[0180] The temperature of the first separation is 450℃; the pressure of the first separation is 20MPa;

[0181] The temperature for the second separation is 25℃; the pressure for the second separation is 10MPa.

[0182] The temperature of the third separation is 12℃; the pressure of the third separation is 1MPa.

[0183] Application Example 3

[0184] This application example provides an oil-phase hydrogenation method, performed using the system apparatus provided in Example 1, specifically including:

[0185] Preheated hydrogen and preheated oil phase are mixed and then subjected to catalytic hydrogenation to obtain hydrotreated heavy oil;

[0186] The preheated oil phase is residual oil;

[0187] The temperature of the preheated hydrogen is 325°C; the temperature of the preheated oil phase is 325°C.

[0188] The volume ratio of hydrogen to oil phase in the catalytic hydrogenation is 1000:1; the volume hourly space velocity (VHSV) of the catalytic hydrogenation is 2.5 h⁻¹. -1 The reaction pressure for catalytic hydrogenation is 10 MPa; the reaction temperature for catalytic hydrogenation is 380 °C.

[0189] The temperature of the first separation is 320℃; the pressure of the first separation is 10MPa;

[0190] The temperature for the second separation is 150℃; the pressure for the second separation is 20MPa.

[0191] The temperature for the third separation is 150℃; the pressure for the third separation is 10MPa.

[0192] Application Example 4

[0193] The only difference from Application Example 1 is that the catalyst loading method in the first hydrogenation subunit is changed from bottom to top to top, that is, the order of catalyst bed arrangement is reversed.

[0194] Comparative Application Example 1

[0195] The only difference from Application Example 1 is that there is no hydrogen mixing internal component between adjacent catalyst beds in the first hydrogenation subunit.

[0196] Comparative Application Example 2

[0197] The only difference from Application Example 1 is that the positions of the heating unit and the hydrogen mixing unit are switched, that is, the hydrogen and oil phase are mixed before heating.

[0198] Comparative Application Example 3

[0199] The only difference from Application Example 4 is that the residual oil is hydrogenated using a trickle bed hydrogenation method. The reactor series connection method, catalyst loading method and product separation method are the same. The hydrogen pressure is 10 MPa and the reaction temperature is 380℃.

[0200] Comparative Application Example 4

[0201] The only difference from Application Example 1 is that the mixed hydrogen internal component does not have an inner tube, which is a separate outer tube component.

[0202] Comparative Application Example 5

[0203] The only difference from Application Example 1 is that the mixed hydrogen internal component does not have an outer tube, which means it is a separate inner tube component.

[0204] Comparative Application Example 6

[0205] The only difference from Application Example 1 is the replacement of the apertures of the inner and outer tubes in the hydrogen mixing internal component, that is, the aperture of the inner tube becomes larger and the aperture of the outer tube becomes smaller.

[0206] The heavy oil obtained from the application examples and comparative application examples was subjected to component analysis as follows: Sulfur content test method: GB / T17040 Determination of Sulfur Content in Petroleum Products (Energy Dispersive X-ray Fluorescence Spectrometry); Carbon Residue Test Method: GB / T268 Determination of Carbon Residue in Petroleum Products (Kondratiev Method); Nitrogen Content Test Method: SH / T0657 Determination of Trace Nitrogen in Liquid Petroleum Hydrocarbons (Oxidative Combustion and Chemiluminescence Method); Metal Content Analysis Method: SH / T0715 Determination of Nickel, Vanadium and Iron Content in Crude Oil and Residual Fuel Oil (ICP).

[0207] The component contents of the residual oil feedstock used in the above application examples and comparative application examples are as follows: sulfur content is 4.33 wt%, total nitrogen content is 2700 μg / g, residual carbon content is 13.84%, and metal (Ni+V) content is 85.5 μg / g.

[0208] Table 1

[0209]

[0210]

[0211] The results from the above application examples show that in the hydrogenation reaction system device provided by the present invention, the hydrogen-oil mixing equipment and hydrogen mixing internal components in the system device can efficiently generate microbubbles of uniform size, so that the solubility of hydrogen in the liquid phase reaches saturation, forming a pseudo-homogeneous flow containing microbubbles of uniform size; in the hydrogenation system method, hydrogen participates efficiently in the hydrogenation reaction of feedstock oil, reducing reaction pressure and temperature.

[0212] Combining the results of Application Example 1 and Comparative Application Example 1, it can be seen that, compared to Comparative Application Example 1 which did not have a hydrogen mixing internal component, the hydrogen mixing internal component of this invention can enhance the hydrogenation reaction process, reduce the sulfur and nitrogen content of the hydrogenated products, and improve the removal rate of metals and residual carbon. Combining Application Example 1 and Comparative Application Example 2, it can be seen that, in Application Example 1, the hydrogen mixing equipment is placed after the feedstock oil heater. Compared to Comparative Application Example 2 where the hydrogen mixing equipment is placed before the feedstock oil heater, the hydrogen mixing equipment of this invention, placed after the feedstock oil heater, can enhance the hydrogenation reaction process, reduce the sulfur and nitrogen content of the hydrogenated products, and improve the removal rate of metals and residual carbon. Combining Application Example 1 and Application Example 4, it can be seen that, in Application Example 1, a hydrogen-oil mixer and hydrogen mixing internal component are provided. Compared to the conventional trickle bed in Application Example 4, at lower pressure and the same temperature, this invention can achieve higher removal rates of sulfur, nitrogen, residual carbon, and heavy metals at lower pressure. Combining Application Example 3 and Comparative Application Example 3, it can be seen that Application Example 3 is equipped with a hydrogen-oil mixer and a cold hydrogen medium scale distributor. Compared with the conventional trickle bed in Comparative Application Example 3, under the same pressure and temperature, the present invention can achieve higher removal of sulfur, nitrogen, residual carbon and heavy metals.

[0213] Furthermore, based on the results of Application Example 1, Comparative Application Example 4, Comparative Application Example 5, and Comparative Application Example 6, it can be seen that changing the structure and related parameters of the hydrogen mixing internal components will significantly reduce the hydrogenation effect and significantly increase the impurity content of the oil phase obtained after hydrogenation, which is not conducive to obtaining high-quality hydrogenated oil products.

[0214] The present invention is described in detail through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the components used in the present invention, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0215] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0216] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0217] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A system arrangement for the hydrogenation of an oil phase, characterized in that The system device for oil phase hydrogenation comprises a hydrogen delivery unit, a raw oil delivery unit, a heating unit, a hydrogen mixing unit, a hydrogenation reaction unit and a separation unit; The hydrogenation reaction unit comprises a first hydrogenation subunit and a second hydrogenation subunit connected in sequence, and a hydrogen mixing internal component is arranged between adjacent catalyst beds of the first hydrogenation subunit; The hydrogen mixing internal component is a double-layer pipe component, holes with a diameter of 0.0001-1mm are arranged on the inner layer pipe, holes with a diameter of 1-100mm are arranged on the outer layer pipe, and a gas-liquid dispersion guide vane is arranged on the top of the outer layer pipe; The first discharge port of the hydrogen delivery unit is connected with the heating unit; The material outlet of the raw oil delivery unit is connected with the heating unit; The second discharge port of the hydrogen delivery unit is connected with the gas inlet of the hydrogen mixing unit; The third discharge port of the hydrogen delivery unit is connected with the gas inlet of the hydrogen mixing internal component; The heating unit, the hydrogen mixing unit, the hydrogenation reaction unit and the separation unit are connected in sequence; The first material flow port of the separation unit is connected with the total hydrogen pipe of the hydrogen delivery unit; The second hydrogenation subunit comprises at least three groups of hydrogen mixing equipment and hydrogenation reaction equipment connected in sequence; The fourth discharge port of the hydrogen delivery unit is connected with the hydrogen mixing equipment.

2. The system for the hydroprocessing of an oil phase according to claim 1, wherein, The hydrogen delivery unit comprises hydrogen supply equipment, compression equipment and first filter equipment connected in sequence.

3. The system for the hydroprocessing of an oil phase according to claim 2, wherein, The first material flow port of the separation unit is connected with the total hydrogen pipe after the first filter equipment.

4. The system for the hydroprocessing of an oil phase of claim 1, wherein, The raw oil delivery unit comprises raw liquid supply equipment, delivery buffer equipment, second filter equipment and first pump connected in sequence.

5. The system for the hydroprocessing of an oil phase according to claim 4, wherein, The material outlet of the first pump is connected with the heating unit.

6. The system for the hydroprocessing of an oil phase of claim 1 wherein, The hydrogenation reaction unit and the separation unit are connected through a bubble coalescence equipment.

7. The system for the hydroprocessing of an oil phase according to claim 6, wherein, The separation unit comprises a first separator, a second separator and a third separator.

8. The system for the hydroprocessing of an oil phase according to claim 7, wherein, The material outlet of the bubble coalescence equipment is connected with the material inlet of the first separator.

9. The system for the hydroprocessing of an oil phase of claim 7, wherein, The first material outlet of the first separator is connected with the material inlet of the second separator.

10. The system for the hydroprocessing of an oil phase of claim 7, wherein, The first material outlet of the second separator is connected with the total hydrogen pipe of the hydrogen delivery unit.

11. The system for the hydroprocessing of an oil phase of claim 7, wherein, The second material outlet of the first separator and the second material outlet of the second separator are both connected with the material inlet of the third separator.

12. The system for the hydroprocessing of an oil phase of claim 7, wherein, The first material outlet of the third separator is connected with a fractionation system.

13. The system for the hydroprocessing of an oil phase of claim 7, wherein, The second material outlet of the third separator is connected with a gas recovery system.

14. An oil phase hydrogenation process characterized by, The oil phase hydrogenation method comprises hydrogenation reaction of an oil phase and hydrogen by using the system device for oil phase hydrogenation according to any one of claims 1-13.

15. The process of claim 14 wherein the oil phase is hydrogenated. The oil phase hydrogenation method comprises mixing preheated hydrogen and preheated oil phase and then performing catalytic hydrogenation to obtain hydrogenated heavy oil.

16. The process of claim 14 wherein the oil phase is hydrogenated. The oil phase for the oil phase hydrogenation method comprises one or a combination of at least two of diesel oil, wax oil, lubricating oil, kerosene, residual oil or reforming generated oil.

17. The process of claim 16 wherein the oil phase is hydrogenated. The oil phase for the oil phase hydrogenation method is residual oil.

18. The process of claim 15 wherein the oil phase is hydrogenated. The temperature of the preheated hydrogen is 300-350℃.

19. The process of claim 15 wherein the oil phase is hydrogenated. The temperature of the preheated oil phase is 300-350℃.

20. The process of claim 15 wherein the oil phase is hydrogenated. The volume ratio of hydrogen to oil phase in the catalytic hydrogenation is (10-1000):

1.

21. The oil phase hydroalkylation process of claim 15 wherein, The volume space velocity of the catalytic hydrogenation is 0.1-2.5h -1 .

22. The oil phase hydroalkylation process of claim 15 wherein, The reaction pressure of the catalytic hydrogenation is 10-20 MPa.

23. The oil phase hydroalkylation process of claim 15 wherein, The reaction temperature of the catalytic hydrogenation is 320-450℃.

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