Slurry bed reaction apparatus and residue slurry bed hydrocracking process and system

Abstract

The application discloses a slurry bed reaction device and a residual oil slurry bed hydrocracking method and system, which comprises a plurality of slurry bed reactors arranged step by step from a reaction inlet to a reaction outlet; each slurry bed reactor is provided with a spiral reaction channel; the spiral diameter of the spiral reaction channel gradually decreases step by step, and the height-diameter ratio of the spiral reaction channel gradually increases step by step. The application improves the cracking reaction depth by cracking poor oil raw materials step by step, realizes the effect of improving the residual oil conversion rate, and makes the flow speed of the reactants also gradually increase in the process of gradually cracking along the spiral reaction channel of the multi-stage slurry bed reactor, and is not easy to backmix to the slurry bed reaction of the previous stage, so as to finally realize the inhibition of the deposition of reaction coke and the excessive cracking of light components caused by backmixing of materials. The application realizes step-by-step cracking and segmented cracking by fractionating the extracted cracking products into intermediate products and recycling them back to the corresponding slurry bed reactor, and finally realizes the goal of producing more chemical raw materials.

Description

Technical Field

[0001] This invention relates to the field of inferior oil processing technology, and in particular, to a slurry bed reactor and a method and system for slurry bed hydrocracking of residue oil. Background Technology

[0002] This section is intended to provide background or context for the embodiments of the invention set forth in the claims. The description herein is not an admission that it is prior art simply because it is included in this section.

[0003] Faced with the increasing prevalence of high-sulfur, high-metal, and high-carbon-residue crude oil resources in crude oil pools, and the pressure of "refining transforming into chemical processing," refining enterprises are experiencing immense processing pressure and technical challenges. For these inferior oils, processes such as heavy oil catalytic cracking and heavy oil fixed-bed hydrocracking suffer from rapid catalyst deactivation due to coking and metal deposition. Delayed coking processes yield high coke output, but the quality of the coke is poor. While fluidized bed hydrocracking can process inferior oils, its process flow and equipment are complex, resulting in low light oil yields. In contrast, heavy oil slurry-bed hydrocracking technology can process even lower-quality feedstocks, producing higher-quality products and achieving higher light oil yields. This technology is more aligned with the trend of efficient resource utilization and supports the goal of "refining transforming into chemical processing." The slurry-bed hydrocracking reaction system and catalyst are the core technologies of this process, consistently a focus of attention and patent protection for engineers in this field. Major refining companies worldwide have invested significant resources and manpower in their concentrated development.

[0004] Currently, the world's mainstream heavy oil slurry bed hydrocracking processes mainly include: ENI's EST process in Italy, the HDHPLUS-SHP process jointly developed by PDVSA in Venezuela and Axens in France, Chevron's VRSH process, KBR and BP's VCC process, and UOP's Uniflex process. Each of these processes has its own advantages and characteristics, but there are significant differences in reactor type, catalyst type, and operating process.

[0005] The EST process uses an oil-soluble residue slurry bed hydrocracking catalyst, which is converted into a nano-scale thin-layer form of carrier-free MoS2 in a slurry bed reactor. It employs complex in-reactor process control technology. Its main characteristics are: ① multiple recycling of unconverted oil, high total feedstock conversion rate, and no fuel oil or coke products; ② superior product quality, with gasoline and diesel meeting Euro IV standards; ③ near-complete removal of metals from the feedstock; ④ lower consumption of the relatively expensive catalyst.

[0006] The HDHPLUS-SHP process involves two slurry bed reactors with complex internal components operating in series. It uses a solid particulate catalyst and requires the addition of a certain amount of additives. The catalyst system has insufficient dispersibility in the feedstock and adopts relatively harsh reaction process conditions. It requires the removal of about 10% of unconverted tail oil, resulting in insufficient economic efficiency of the unit.

[0007] The VCC process employs a non-metallic slurry-bed hydrocracking catalyst and multiple reactors operating in series to reduce the impact of reactant backmixing. The operating pressure is 18 MPa to 20 MPa; increasing the reaction severity can achieve a single-pass conversion rate of 95% for the residue oil. In the thermal separator, light components are separated from the unconverted tail oil. The unconverted tail oil is completely discharged from the bottom of the thermal separator without recirculation. This external discharge of tail oil aims to control coking and maintain stable operation of the unit, but its economic efficiency is relatively poor.

[0008] Currently, slurry bed reactors are mainly divided into two categories: one is an empty tank form with no internal components or simple internal components, such as the EST process of ENI in Italy. This requires multiple reactors in series or a single reactor in series with an external circulation device. It uses highly active, oil-soluble catalysts and a complex control system to circulate and convert inferior heavy oil to achieve deep cracking of heavy oil. The other category is slurry bed reactors with complex internal components. This type of technology has been developed in recent years to achieve goals such as enhanced in-vessel backmixing of the reaction stream and suppression of coke deposition, enhanced heat and mass transfer, and timely separation of light components from the system while cracking heavy oil. Although it can significantly improve the depth of reaction, it has problems such as complex design and operation, and high difficulty in manufacturing and maintenance.

[0009] The aforementioned slurry bed reactors, reaction systems, and processes each have their own advantages, but they still have certain shortcomings that require continuous optimization and improvement by researchers. Summary of the Invention

[0010] The purpose of this invention is to provide a slurry bed reactor and a method and system for slurry bed hydrocracking of residue oil, in order to solve the technical problems of the easy deposition and clogging of reactant coke in current slurry bed reactor equipment, and the easy backmixing of reactants leading to over-cracking of light components.

[0011] The above-mentioned objectives of the present invention can be achieved by the following technical solutions:

[0012] This invention provides a slurry bed reactor apparatus, comprising a multi-stage slurry bed reactor arranged sequentially from its reaction inlet to its reaction outlet; each stage of the slurry bed reactor is provided with a spiral reaction channel, the spiral reaction channel being spirally arranged around the axis of the slurry bed reactor, and the spiral reaction channels of each stage of the slurry bed reactor are interconnected; wherein, the spiral diameter of the spiral reaction channel of the multi-stage slurry bed reactor decreases progressively, and the ratio of the spiral height to the spiral diameter of the spiral reaction channel of the multi-stage slurry bed reactor increases progressively; wherein each stage of the slurry bed reactor below the highest stage is provided with an exhaust port connected to the output end of its spiral reaction channel, and at least one stage of the slurry bed reactor above the lowest stage is provided with a circulation inlet connected to the input end of its spiral reaction channel.

[0013] In embodiments of the present invention, the slurry bed reactor has three to six stages.

[0014] In an embodiment of the present invention, the height-to-diameter ratio of the spiral reaction channel of the subsequent slurry bed reactor is 1 to 3 times that of the spiral reaction channel of the preceding slurry bed reactor.

[0015] In embodiments of the present invention, the spiral diameter and cross-sectional area of ​​the spiral reaction channel of each stage of the slurry bed reactor are set according to their preset flow rate; wherein, the preset flow rate of the spiral reaction channel of the preceding stage of the slurry bed reactor is 1.5 to 3 times the preset flow rate of the spiral reaction channel of the following stage of the slurry bed reactor.

[0016] In embodiments of the present invention, each stage of the slurry bed reactor above the lowest stage is provided with a circulation inlet connected to the input end of its spiral reaction channel; or only the second stage of the slurry bed reactor is provided with a circulation inlet connected to the input end of its spiral reaction channel.

[0017] In embodiments of the present invention, the multi-stage slurry bed reactors are arranged coaxially from bottom to top, with the reaction inlet located at the bottom of the first-stage slurry bed reactor, the reaction outlet located at the top of the highest-stage slurry bed reactor, the extraction outlet located at the top of its corresponding slurry bed reactor, and the circulation inlet located at the bottom of its corresponding slurry bed reactor.

[0018] In embodiments of the present invention, the slurry bed reactor further includes an online monitoring mechanism. At least one densitometer is provided in the spiral reaction channel of each stage of the slurry bed reactor. The densitometer is electrically connected to the online monitoring mechanism to monitor the cracking reaction depth in the spiral reaction channel based on the density of the cracking products in the spiral reaction channel.

[0019] In embodiments of the present invention, each stage of the slurry bed reactor is provided with a plurality of temperature measuring elements in the spiral reaction channel, and the plurality of temperature measuring elements are electrically connected to the online monitoring mechanism to monitor the reaction temperature in the spiral reaction channel.

[0020] In an embodiment of the present invention, the slurry bed reactor includes an outer cylinder, an inner cylinder, and helical blades. The helical blades are arranged spirally around the axis of the slurry bed reactor. The inner cylinder is placed inside the outer cylinder and connected to it by the helical blades. The annular space between the inner cylinder and the outer cylinder is separated by the helical blades to form the helical reaction channel. The densitometer and the temperature measuring element are installed on the outer wall of the inner cylinder. An auxiliary heating mechanism is installed in the inner cylinder. The online monitoring mechanism is electrically connected to the auxiliary heating mechanism.

[0021] This invention also provides a method for slurry bed hydrocracking of residue oil, comprising the following steps: mixing feedstock oil with a catalyst and heating with hydrogen to form a reaction feedstock; conveying the reaction feedstock to a first-stage slurry bed reactor of a slurry bed reactor for cracking reaction; wherein, a portion of the cracking products generated by each stage of the slurry bed reactor below the highest stage enters the next stage of the slurry bed reactor for stage-by-stage cracking reaction; extracting another portion of the cracking products generated by each stage of the slurry bed reactor below the highest stage and the cracking products generated by the highest-stage slurry bed reactor; separating and processing the extracted cracking products to obtain a final product and an intermediate product; recycling the intermediate product to the corresponding stage of the slurry bed reactor for cracking reaction, and repeating this cycle until the intermediate product is converted into the final product.

[0022] In an embodiment of the present invention, the step of mixing the feedstock oil with the catalyst and heating it with hydrogen to form a reaction feedstock includes the following steps: uniformly dispersing the catalyst into the carrier oil in a catalyst preparation tank to form a first mixture; injecting the first mixture into a feedstock oil preparation tank to mix it thoroughly with the feedstock oil, and then injecting it into a heat exchanger to exchange heat and form a second mixture; conveying the second mixture to a static heavy oil hydrogen mixer to mix it thoroughly with hydrogen, and then conveying it to a feedstock heating furnace for heating and processing to form the reaction feedstock.

[0023] In embodiments of the present invention, the reaction conditions for the cracking reaction in the slurry bed reactor include: a reaction temperature of 380℃~450℃, a reaction pressure of 10.0 MPa~20.0 MPa, and a volume hourly space velocity of 0.5~1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300-1000.

[0024] In an embodiment of the present invention, the extraction of another portion of the cracking products generated by the slurry bed reactors of each stage below the highest level, as well as the cracking products generated by the highest-level slurry bed reactor, includes the following steps: monitoring the density of the cracking products at the output end of the spiral reaction channel of each stage of the slurry bed reactor; when the density of the cracking products in the slurry bed reactor decreases by 0.5% to 5%, extracting 10% to 30% of the material stock in the slurry bed reactor from the slurry bed reactor.

[0025] In an embodiment of the present invention, the step of separating and processing the extracted cracking products to obtain at least one final product and one intermediate product includes the following steps: conveying the cracking products to a high-pressure separator for gas-liquid separation; conveying the liquid phase product in the high-pressure separator to a low-pressure separator via a pressure reducing valve for deep gas-liquid separation; and after removing large particulate solid impurities from the liquid phase product in the low-pressure separator via a filter group, the product is heated in a fractionation furnace and then fed into a fractionation tower for separation to obtain the final product and the intermediate product.

[0026] In embodiments of the present invention, the following steps are also included: a hydrogen source is transported to the static heavy oil hydrogen mixer via a circulating hydrogen compressor; the gaseous products in the high-pressure separator are circulated to the circulating hydrogen compressor via a hydrogen compressor deliquescence buffer tank, and then transported to the static heavy oil hydrogen mixer.

[0027] In embodiments of the present invention, the feedstock oil is a low-quality oil composed of at least one or more of high-sulfur residue oil, high-metal residue oil, atmospheric residue oil, vacuum residue oil, extra-heavy crude oil, catalytic slurry oil, and oil sands bitumen; the carrier oil is a mixed oil composed of at least one or more of catalytic diesel oil, coking diesel oil, hydrocracking diesel oil, coal-to-oil fractions, and biodiesel; the intermediate products include diesel oil, wax oil, and hydrotreated tailings; the final products include target products and non-target products, the target product being naphtha, and the by-products including light hydrocarbons and coke.

[0028] In embodiments of the present invention, the step of recycling the intermediate products to the corresponding stage of the slurry bed reactor for cracking reaction includes the following steps: the diesel oil is recycled to the third stage of the slurry bed reactor for cracking reaction, the wax oil is recycled to the second stage of the slurry bed reactor for cracking reaction, and the hydrotreated tailings are treated by hydrogen mixing and heating in the static heavy oil hydrogen mixer and the feedstock heater and then mixed with the reaction feedstock before being recycled to the first stage of the slurry bed reactor for cracking reaction; or all intermediate products are recycled to the second stage of the slurry bed reactor for cracking reaction.

[0029] The present invention also provides a residue oil slurry bed hydrocracking system for implementing the above-mentioned residue oil slurry bed hydrocracking method.

[0030] The features and advantages of this invention are:

[0031] The slurry bed reactor of the present invention, by setting up a multi-stage slurry bed reactor, cracks inferior oil feedstock step by step, thereby increasing the depth of cracking reaction and achieving the effect of improving residue oil conversion rate.

[0032] The slurry bed reactor of the present invention, by setting a spiral reaction channel for spiral conveying, and by progressively decreasing the spiral diameter and increasing the height-to-diameter ratio of the spiral reaction channel in the multi-stage slurry bed reactor, causes the flow velocity (i.e., linear velocity) of the reactants to progressively increase during the progressive cracking process along the spiral reaction channel of the multi-stage slurry bed reactor, and makes it less likely for the reactants to backmix to the previous stage of the slurry bed reaction, thereby ultimately suppressing the deposition of reactant coke and the excessive cracking of light components caused by material backmixing.

[0033] The slurry bed reactor of the present invention can effectively save the footprint of the device by arranging the multi-stage slurry bed reactors from bottom to top and coaxially.

[0034] The slurry bed reactor of the present invention monitors the cracking reaction depth based on the cracking products by setting multiple densitometers in each stage of the slurry bed reactor, and then fractionates some of the cracking products generated by each stage of the slurry bed reactor according to the feedback from the densitometers, thereby effectively controlling the cracking reaction depth.

[0035] The residue oil slurry bed hydrocracking method and system of the present invention achieves step-by-step cracking and segmented cracking by recycling the intermediate products from fractionation back to the corresponding level of slurry bed reactor, and ultimately achieves the goal of producing more chemical feedstocks. Attached Figure Description

[0036] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0037] Figure 1 This is a schematic diagram of the structure of a slurry bed reactor in one embodiment of the present invention.

[0038] Figure 2 This is a schematic diagram of the process flow for slurry bed hydrocracking of residue oil in one embodiment of the present invention.

[0039] In the picture:

[0040] 1. Catalyst preparation tank; 2. Feedstock preparation tank; 3. Feedstock pump; 4. Heat exchanger; 5. Static heavy oil hydrogen mixer; 6. Feedstock heater; 7. Slurry bed reactor; 8. High-pressure separator; 9. Pressure reducing valve; 10. Low-pressure separator; 11. Filter assembly; 12. Fractionating heater; 13. Fractionating tower; 14. Circulating hydrogen compressor; 15. Hydrogen compressor desliming buffer tank;

[0041] 71. Reaction inlet;

[0042] 72. First-stage slurry bed reactor; 73. Inner cylinder of the first-stage slurry bed reactor; 74. Spiral reaction channel of the first-stage slurry bed reactor;

[0043] 75. Second-stage slurry bed reactor; 76. Inner cylinder of the second-stage slurry bed reactor; 77. Spiral reaction channel of the second-stage slurry bed reactor;

[0044] 78. The third-stage slurry bed reactor; 79. The inner cylinder of the third-stage slurry bed reactor; 710. The spiral reaction channel of the third-stage slurry bed reactor;

[0045] 711. Reaction outlet. Detailed Implementation

[0046] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0047] Implementation Method 1

[0048] like Figure 1 As shown, the present invention provides a slurry bed reactor 7, comprising a multi-stage slurry bed reactor arranged in stages from its reaction inlet 71 to its reaction outlet 711; each stage of the slurry bed reactor is provided with a spiral reaction channel, the spiral reaction channel being spirally arranged around the axis of the slurry bed reactor, and the spiral reaction channels of each stage of the slurry bed reactor are interconnected; wherein, the spiral diameter of the spiral reaction channel of the multi-stage slurry bed reactor decreases progressively, and the height-to-diameter ratio of the spiral reaction channel of the multi-stage slurry bed reactor increases progressively; wherein each stage of the slurry bed reactor below the highest stage is provided with an exhaust port connected to the output end of its spiral reaction channel, and at least one stage of the slurry bed reactor above the lowest stage is provided with a circulation inlet connected to the input end of its spiral reaction channel.

[0049] In other words, the slurry bed reactor closest to the reaction inlet 71, with the largest spiral diameter in the spiral reaction channel 74 and the smallest height-to-diameter ratio in the spiral reaction channel 74, is the first-stage slurry bed reactor 72, i.e., the lowest-stage slurry bed reactor, where the reactants first enter; then, in sequence, the second-stage slurry bed reactor 75, the third-stage slurry bed reactor 78, and so on; among them, the slurry bed reactor 78 closest to the reaction outlet, with the smallest spiral diameter in the spiral reaction channel 710 and the largest height-to-diameter ratio in the spiral reaction channel 710, is the highest-stage slurry bed reactor, i.e., the last slurry bed reactor to enter. For example... Figure 1 In one embodiment of the present invention shown, the slurry bed reactor has three stages, with the third-stage slurry bed reactor 78 being the highest-level slurry bed reactor.

[0050] The slurry bed reactor 7 of the present invention, by setting up a multi-stage slurry bed reactor, progressively cracks inferior oil feedstock, thereby increasing the depth of the cracking reaction and achieving the effect of improving residue-to-oil conversion rate. Furthermore, by setting up a spiral reaction channel with a spiral conveyor, and by progressively decreasing spiral diameter and increasing height-to-diameter ratio of the spiral reaction channel in the multi-stage slurry bed reactor, the flow velocity (i.e., linear velocity) of the reactants during progressive cracking along the spiral reaction channel of the multi-stage slurry bed reactor also progressively increases, and backmixing to the previous stage of the slurry bed reaction is less likely. This ultimately suppresses the deposition of reactive coke and the excessive cracking of light components caused by material backmixing.

[0051] Furthermore, the reaction outlet 711 can serve as the extraction outlet of the highest-level slurry bed reactor 78, and the reaction inlet 71 can serve as the circulation inlet of the first-stage slurry bed reactor 72. The cracking products generated by the cracking reaction in each stage of the slurry bed reactor can be extracted from their corresponding extraction outlets, thereby separating the final product and intermediate product. The intermediate product can be recycled back to the corresponding stage of the slurry bed reactor from the corresponding circulation inlet to undergo cracking reaction again, thereby realizing staged cracking and cyclic cracking, achieving deep conversion, and improving the conversion rate and the yield of the target product.

[0052] The spiral diameter of the spiral reaction channel is twice the radial distance between the spiral channel and the axis of the slurry bed reactor 7. The spiral height of the spiral reaction channel is the axial distance between the input and output ends of the spiral reaction channel. Specifically, the slurry bed reactor includes an outer cylinder, an inner cylinder, and spiral blades. The spiral blades are spirally arranged around the axis of the slurry bed reactor 7. The inner cylinder is placed inside the outer cylinder and connected by the spiral blades. The annular space between the inner and outer cylinders is separated by the spiral blades to form a spiral reaction channel. The structure is simple and easy to manufacture. That is to say, the outer diameter of the spiral reaction channel is equal to the diameter of the outer cylinder, which is also the diameter of the slurry bed reactor; the inner diameter of the spiral reaction channel is equal to the diameter of the inner cylinder; and the height (i.e., axial length) of the slurry bed reactor is similar to the spiral height of the spiral reaction channel. Therefore, the diameter of the multi-stage slurry bed reactor decreases progressively, and the height-to-diameter ratio of the multi-stage slurry bed reactor to its diameter increases progressively.

[0053] Specifically, such as Figure 1 In one embodiment of the present invention shown, the diameter of the inner cylinder 73 of the first-stage slurry bed reactor 72 is the same as the spiral inner diameter of its spiral reaction channel 74; the diameter of the inner cylinder 76 of the second-stage slurry bed reactor 75 is the same as the spiral inner diameter of its spiral reaction channel 77; and the diameter of the inner cylinder 79 of the third-stage slurry bed reactor 78 is the same as the spiral inner diameter of its spiral reaction channel 710.

[0054] like Figure 1 As shown, in this embodiment of the invention, the multi-stage slurry bed reactors are arranged coaxially from bottom to top. The reaction inlet 71 is located at the bottom of the first-stage slurry bed reactor 72, the reaction outlet 711 is located at the top of the highest-stage slurry bed reactor 78, the extraction outlet is located at the top of its corresponding slurry bed reactor, and the circulation inlet is located at the bottom of its corresponding slurry bed reactor. By arranging the multi-stage slurry bed reactors coaxially in the vertical direction, the footprint of the entire device can be effectively reduced, and it is also beneficial to suppress excessive cracking caused by backmixing of light components.

[0055] This invention discovers that the number of stages in a slurry bed reactor, i.e., the number of slurry bed reactors, affects the overall design cost, manufacturing cost, and final product yield of the apparatus. Therefore, in the embodiments of this invention, the number of stages in the slurry bed reactor is three to six, which achieves a relatively ideal final product yield while keeping design and manufacturing costs low. Furthermore, considering the overall design cost, manufacturing cost, and final product yield, the preferred number of stages in the slurry bed reactor is three to four. When the number of stages in the slurry bed reactor is less than three, the final product yield is not ideal; when the number of stages in the slurry bed reactor is more than six, it increases the overall design and manufacturing cost of the apparatus without achieving a more ideal final product yield.

[0056] The present invention also discovered that the depth of the reaction of reactants in a slurry bed reactor is related to the height-to-diameter ratio of the spiral reaction channels of each stage of the slurry bed reactor and the material flow rate, which in turn influences the depth of the cracking reaction. Therefore, in embodiments of the present invention, the height-to-diameter ratio of the multi-stage slurry bed reactor is controlled, with the height-to-diameter ratio of the spiral reaction channel of the subsequent stage slurry bed reactor being 1 to 3 times, preferably 1 to 2 times, that of the spiral reaction channel of the preceding stage slurry bed reactor. Furthermore, the preset flow rate of the spiral reaction channel of the preceding stage slurry bed reactor is controlled to be 1.5 to 3 times, preferably 1.5 to 2 times, that of the spiral reaction channel of the subsequent stage slurry bed reactor. Based on this, the spiral height, spiral diameter, and channel cross-sectional area of ​​the spiral reaction channels of each stage of the slurry bed reactor are set.

[0057] In embodiments of the present invention, the slurry bed reactor 7 further includes an online monitoring mechanism. At least one densitometer is installed in the spiral reaction channel of each stage of the slurry bed reactor. The densitometer is electrically connected to the online monitoring mechanism to monitor the cracking reaction depth within the spiral reaction channel based on the density of the cracking products within the spiral reaction channel. Specifically, one or more densitometers can be provided. In this embodiment, the densitometer is located at or near the output end of the spiral reaction channel, that is, the densitometer of each stage of the slurry bed reactor is located near the reaction inlet or outlet at the top of its corresponding slurry bed reactor. In other embodiments, each stage of the slurry bed reactor has multiple outlets, which are spaced apart along the conveying direction of the spiral reaction channel and connected to it. Correspondingly, multiple densitometers are installed in the spiral reaction channel of each stage of the slurry bed reactor, and each densitometer is located near multiple outlets. Therefore, cracking products within the spiral reaction channel can be selectively extracted from different outlets based on the density of cracking products at different locations monitored by different densitometers within the same spiral reaction channel.

[0058] In addition, multiple temperature sensing elements are installed within the spiral reaction channels of each stage of the slurry bed reactor. These elements are electrically connected to an online monitoring mechanism to monitor the reaction temperature within the spiral reaction channels. Specifically, the number of temperature sensing elements can be three to six, seven to ten, or more. The multiple temperature sensing elements of each stage of the slurry bed reactor are mounted on the outer wall of the inner cylinder. An auxiliary heating mechanism is installed within the inner cylinder and is electrically connected to the online monitoring mechanism. The online monitoring mechanism receives temperature signals from the temperature sensing elements and controls the auxiliary heating mechanism to heat the spiral reaction channels based on these signals, thereby adjusting the reaction temperature. In an embodiment of the invention, the auxiliary heating mechanism is an electrically heated salt bath module, which can increase the temperature of the spiral reaction channels by 50°C to 100°C.

[0059] Implementation Method 2

[0060] Combination Figure 1 and Figure 2 As shown, the present invention also provides a method for hydrocracking of residue oil in a slurry bed, comprising the following steps:

[0061] Step S1: Mix the raw oil with the catalyst and heat it with hydrogen to produce the reaction raw material.

[0062] Specifically, mixing the feedstock oil with the catalyst and heating it with hydrogen to form a reaction feedstock includes the following steps: uniformly dispersing the catalyst into the carrier oil in the catalyst preparation tank 1 to form a first mixture; injecting the first mixture into the feedstock oil preparation tank 2 to mix it thoroughly with the feedstock oil, and then injecting it into the heat exchanger 4 to exchange heat and form a second mixture; conveying the second mixture to the static heavy oil hydrogen mixer 5 to mix it thoroughly with hydrogen, and then conveying it to the feedstock heating furnace 6 to heat and process it into a reaction feedstock.

[0063] The feedstock oil is a low-quality oil composed of at least one or more of the following: high-sulfur residue oil, high-metal residue oil, atmospheric residue oil, vacuum residue oil, extra-heavy crude oil, catalytic slurry oil, and oil sands bitumen. The carrier oil is a mixed oil composed of at least one or more of the following: catalytic diesel oil, coking diesel oil, hydrocracking diesel oil, coal-to-oil fractions, and biodiesel. After being mixed with the feedstock oil and carrying the catalyst, the carrier oil is injected into the heat exchanger 4 by the feedstock pump 3 for heat exchange.

[0064] Step S2: The reactants are fed from the reaction inlet 71 of the first-stage slurry bed reactor 72 to the slurry bed reactor 7 for stage-by-stage cracking reaction; wherein, a portion of the cracking products generated in each stage of the slurry bed reactor below the highest stage enters the next stage of the slurry bed reactor for stage-by-stage cracking reaction. The slurry bed reactor 7 has the same specific structure, working principle and beneficial effects as the slurry bed reactor 7 in Embodiment 1, and will not be described again here.

[0065] Specifically, the reaction conditions for the cracking reaction of the reactants in the slurry bed reactor 7 include: a reaction temperature of 380℃~450℃, a reaction pressure of 10.0 MPa~20.0 MPa, and a volume hourly space velocity of 0.5 h⁻¹. -1 ~1.5 h -1 The hydrogen-to-oil volume ratio is 300-1000. Preferably, the reaction temperature is 400℃-430℃, the reaction pressure is 14.0 MPa-16.0 MPa, and the volume hourly space velocity is 0.5 h⁻¹. -1 ~1.0 h -1 The hydrogen-to-oil volume ratio is 500-800.

[0066] Step S3: Extract another portion of the cracking products generated by each level of slurry bed reactor below the highest level, as well as the cracking products generated by the highest level slurry bed reactor.

[0067] Specifically, the cracking products from each stage of the slurry bed reactor below the highest level, as well as the cracking products from the highest-level slurry bed reactor, are extracted. This includes the following steps: monitoring the density of the cracking products at the output end of the spiral reaction channel of each stage of the slurry bed reactor; when the density of the cracking products in the slurry bed reactor decreases by 0.5% to 5%, 10% to 30% of the material stock in the slurry bed reactor is extracted from the slurry bed reactor. Preferably, when the density of the cracking products in the slurry bed reactor decreases by 1% to 2.5%, 10% to 20% of the material stock in the slurry bed reactor is extracted from the slurry bed reactor. The remaining cracking products in each stage of the slurry bed reactor below the highest level can then enter the next stage of the slurry bed reactor for further cracking.

[0068] Step S4: Separate and process the extracted cracking products to obtain at least one final product and one intermediate product.

[0069] Specifically, the extracted cracking products are separated and processed to obtain at least one final product and an intermediate product, including the following steps: the cracking products are fed to a high-pressure separator 8 for gas-liquid separation; the liquid phase product in the high-pressure separator 8 is fed to a low-pressure separator 10 via a pressure reducing valve 9 for deep gas-liquid separation; the liquid phase product in the low-pressure separator 10 is filtered through a filter group 11 to remove large particulate solid impurities and then fed into a fractionation furnace 12 for heating and then into a fractionation tower 13 for separation to obtain the final product and the intermediate product.

[0070] The final products include naphtha, light hydrocarbons, and coke. Naphtha is the target product, while light hydrocarbons (i.e., C1-C4 components) and coke are byproducts of over-cracking. The intermediate products include diesel, wax oil, and hydrotreated tailings. The intermediate products can be converted into the final products, namely naphtha, light hydrocarbons, and coke, through further cracking.

[0071] Step S5: The intermediate products are recycled to the corresponding level of slurry bed reactor for cracking reaction. This cycle is repeated until all intermediate products are converted into at least one final product. By recycling the intermediate products to the corresponding level of slurry bed reactor for cracking reaction again, it is beneficial to control the depth of the cracking reaction, thereby improving the conversion rate to the target product and reducing the conversion rate to by-products.

[0072] Combination Figure 1 and Figure 2As shown, in some embodiments of the present invention, the intermediate products are recycled to the corresponding level of slurry bed reactor for cracking reaction, including the following steps: diesel oil is recycled to the third-level slurry bed reactor 78 for cracking reaction; wax oil is recycled to the second-level slurry bed reactor 75 for cracking reaction; hydrotreated tailings are mixed with hydrogen and heated by a static heavy oil hydrogen mixer 5 and a feedstock heater 6 and then recycled to the first-level slurry bed reactor 72 for cracking reaction after being mixed with the reaction feedstock.

[0073] In other embodiments of the present invention, the intermediate products are recycled to the second-stage slurry bed reactor 75 for cracking reaction.

[0074] In addition, the present invention includes the following steps: the hydrogen source is transported to the static heavy oil hydrogen mixer 5 via the circulating hydrogen compressor 14; the gaseous products in the high-pressure separator 8 are circulated to the circulating hydrogen compressor 14 via the hydrogen compressor deliquescence buffer tank 15, and then transported to the static heavy oil hydrogen mixer 5, thereby realizing the recycling of hydrogen.

[0075] In some embodiments of the present invention, each stage of the slurry bed reactor is provided with multiple extraction ports. The multiple extraction ports are spaced apart along the conveying direction of the spiral reaction channel and are connected to the spiral reaction channel. Correspondingly, multiple densitometers are provided in the spiral reaction channel of each stage of the slurry bed reactor, and the multiple densitometers are respectively located near the multiple extraction ports. Therefore, when the densitometer near any extraction port in the same spiral reaction channel detects a decrease in the density of the cracking products by 0.5% to 5%, 10% to 20% of the cracking products are extracted from the slurry bed reactor from its corresponding extraction port.

[0076] Implementation Method 3

[0077] The present invention also provides a residue oil slurry bed hydrocracking system for implementing the above-mentioned residue oil slurry bed hydrocracking method.

[0078] To better understand and implement the slurry bed reactor and residue oil slurry bed hydrocracking method and system of the present invention, some specific embodiments are provided below for illustration:

[0079] The slurry reaction bed devices of the residue oil slurry bed hydrocracking system in Preferred Embodiment 1, Preferred Embodiment 2, Preferred Embodiment 3, Preferred Embodiment 4, and Superior Embodiment 1 and Superior Embodiment 2 are slurry reaction bed devices of some embodiments of the present invention.

[0080] The difference between the slurry-bed hydrocracking system of the residual oil in the comparative example and the slurry-bed hydrocracking system of the present invention is that the slurry-bed reactor does not have a spiral reaction channel, that is, it is an empty cylinder structure.

[0081] However, the process methods used in each preferred embodiment, each superior embodiment, and the comparative examples are all the residue oil slurry bed hydrocracking method of the present invention.

[0082] The feedstock oil used in all preferred embodiments, superior embodiments and comparative examples is the same, and the catalyst used is an oil-soluble, highly dispersed molybdenum-based catalyst. It does not require pre-sulfurization and can be used directly after heating to the activation temperature.

[0083] The specific process conditions are shown in the table below:

[0084]

[0085] Information on the crude oil is shown in the table below.

[0086]

[0087] The properties of the crude oil are shown in the table below:

[0088]

[0089] The evaluation and analysis methods are shown in the table below:

[0090]

[0091] The evaluation and analysis results are shown in the table below:

[0092]

[0093] Comparative analysis:

[0094] First, comparing the preferred embodiment 2 and the comparative example, it can be seen that, under the same reaction conditions and the same number of slurry bed reactors, when using the slurry bed reactor of the present invention, its single-pass conversion rate (conversion rate of feedstock oil to light hydrocarbons, naphtha, diesel oil, and vacuum gas oil) is 87.7%, the total conversion rate (conversion rate of feedstock oil to light hydrocarbons and naphtha after recycling reaction) is 90.03%, the single-pass coking rate is 2.1%, the total coking rate is 9.97%, and the total naphtha yield is 85.5%. However, when using a multi-stage hollow cylinder slurry bed reactor, its single-pass conversion rate is 81.8%, the total conversion rate is 84.63%, the single-pass coking rate is 5.3%, the total coking rate is 15.37%, and the total naphtha yield is 73.18%. Therefore, the slurry bed reactor of the present invention has significant advantages, and in terms of the removal rate of impurities such as sulfur, nitrogen, residual carbon, and metals, the experimental results of the present invention are also superior to those of the hollow cylinder slurry bed reactor.

[0095] Secondly, a comparison of the preferred embodiments, superior embodiments, and comparative examples reveals that within the range of process conditions in all preferred embodiments, superior embodiments, and comparative examples, as the number of stages of the slurry bed reactor, the height-to-diameter ratio of two adjacent stages of the slurry bed reactor, the severity of the reaction conditions, and the decrease in the amount of material stored in the slurry bed reactor (i.e., the increase in the amount extracted from the top of each stage of the slurry bed reactor) increase, the density (i.e., specific gravity) of the reaction products gradually decreases, the impurity removal rate increases, the total naphtha yield first increases and then decreases, while the yields of light hydrocarbons (i.e., C1-C4 components) and coke first decrease and then increase.

[0096] It is important to note that the above-mentioned patterns were obtained within the optimal operating range of this invention. When key factors such as the number of reactor stages, the height-to-diameter ratio of adjacent slurry bed reactors, the material reserves in the slurry bed reactor, and the severity of reaction conditions deviate from this range, the design cost, manufacturing cost, complexity, functional integration, and operating cost of the equipment will increase, but a more ideal total naphtha yield will not be achieved. Instead, the yields of light hydrocarbons and coke will increase.

[0097] In summary, this invention effectively suppresses the deposition and blockage of reaction equipment by reactive coke and the excessive cracking of light components caused by backmixing of reactants by optimizing the flow pattern of materials inside the slurry bed reactor. By adopting the approach of "staged reaction", "precise circulation reaction" and "gradual residence time", this method can produce chemical raw materials from inferior oil in the largest possible quantity while ensuring continuous and stable operation of the equipment, with no tailings discharge, thus achieving a highly efficient and deep conversion process for inferior oil.

[0098] The above descriptions are merely a few embodiments of the present invention. Those skilled in the art can make various modifications or variations to the embodiments of the present invention based on the content disclosed in the application documents without departing from the spirit and scope of the present invention.

Claims

1. A slurry bed reactor, characterized in that, The system includes a multi-stage slurry bed reactor arranged in stages from its reaction inlet to its reaction outlet; each stage of the slurry bed reactor is provided with a spiral reaction channel, which is spirally arranged around the axis of the slurry bed reactor, and the spiral reaction channels of each stage of the slurry bed reactor are connected to each other; In the multi-stage slurry bed reactor, the spiral diameter of the spiral reaction channel decreases progressively, and the ratio of the spiral height to the spiral diameter of the spiral reaction channel increases progressively. Each of the slurry bed reactors below the highest level is provided with an exhaust port connected to the output end of its spiral reaction channel, and at least one of the slurry bed reactors above the lowest level is provided with a circulation inlet connected to the input end of its spiral reaction channel. The multi-stage slurry bed reactors are arranged coaxially from bottom to top, with the reaction inlet located at the bottom of the first-stage slurry bed reactor, the reaction outlet located at the top of the highest-stage slurry bed reactor, the extraction outlet located at the top of its corresponding slurry bed reactor, and the circulation inlet located at the bottom of its corresponding slurry bed reactor. The slurry bed reactor includes an outer cylinder, an inner cylinder, and helical blades. The helical blades are arranged spirally around the axis of the slurry bed reactor. The inner cylinder is placed inside the outer cylinder and connected to it through the helical blades. The annular space between the inner cylinder and the outer cylinder is separated by the helical blades to form the helical reaction channel.

2. The slurry bed reactor according to claim 1, characterized in that, The slurry bed reactor has three to six stages.

3. The slurry bed reactor according to claim 1, characterized in that, The height-to-diameter ratio of the spiral reaction channel in the subsequent slurry bed reactor is 1 to 3 times that of the spiral reaction channel in the preceding slurry bed reactor.

4. The slurry bed reactor according to claim 1, characterized in that, The spiral diameter and cross-sectional area of ​​the spiral reaction channel of each stage of the slurry bed reactor are set according to their preset flow rate; wherein, the preset flow rate of the spiral reaction channel of the preceding stage of the slurry bed reactor is 1.5 to 3 times the preset flow rate of the spiral reaction channel of the following stage of the slurry bed reactor.

5. The slurry bed reactor according to claim 1, characterized in that, Each stage of the slurry bed reactor above the lowest stage is provided with a circulation inlet connected to the input end of its spiral reaction channel; or only the second stage of the slurry bed reactor is provided with a circulation inlet connected to the input end of its spiral reaction channel.

6. The slurry bed reactor according to claim 1, characterized in that, The slurry bed reactor also includes an online monitoring mechanism. At least one densitometer is provided in the spiral reaction channel of each stage of the slurry bed reactor. The densitometer is electrically connected to the online monitoring mechanism to monitor the cracking reaction depth in the spiral reaction channel based on the density of the cracking products in the spiral reaction channel.

7. The slurry bed reactor according to claim 6, characterized in that, Each of the various stages of the slurry bed reactor is equipped with multiple temperature sensing elements in the spiral reaction channel. These multiple temperature sensing elements are electrically connected to the online monitoring mechanism to monitor the reaction temperature in the spiral reaction channel.

8. The slurry bed reactor according to claim 7, characterized in that, The densitometer and the temperature measuring element are mounted on the outer wall of the inner cylinder. An auxiliary heating mechanism is installed in the inner cylinder, and the online monitoring mechanism is electrically connected to the auxiliary heating mechanism.

9. A method for slurry-bed hydrocracking of residue oil in a slurry-bed reactor according to any one of claims 1-8, characterized in that, Includes the following steps: The feedstock oil is mixed with the catalyst and then heated with hydrogen to produce the reaction feedstock. The reactants are fed into the first-stage slurry bed reactor of the slurry bed reactor for cracking; wherein, a portion of the cracking products generated in each stage of the slurry bed reactor below the highest stage enters the next stage of the slurry bed reactor for cracking in stages. Another portion of the cracking products generated by the slurry bed reactors of each level below the highest level, as well as the cracking products generated by the slurry bed reactor of the highest level, are extracted. The extracted cracking products are separated and processed to obtain the final product and intermediate products; The intermediate product is recycled to the corresponding stage of the slurry bed reactor for cracking reaction, and this cycle is repeated until the intermediate product is converted into the final product.

10. The residue slurry bed hydrocracking method according to claim 9, characterized in that, The process of mixing the feedstock oil with the catalyst and then heating it with hydrogen to produce the reaction feedstock includes the following steps: The catalyst is uniformly dispersed into the carrier oil in a catalyst preparation tank to form a first mixture; The first mixture is injected into the raw oil preparation tank and thoroughly mixed with the raw oil, and then injected into the heat exchanger for heat exchange to form the second mixture; The second mixture is fed into a static heavy oil hydrogen mixer to be fully mixed with hydrogen, and then fed into a raw material heating furnace for heating and processing into the reaction raw material.

11. The residue oil slurry bed hydrocracking method according to claim 9, characterized in that, The reaction conditions for the cracking reaction in the slurry bed reactor include: a reaction temperature of 380℃~450℃, a reaction pressure of 10.0 MPa~20.0 MPa, and a volume hourly space velocity of 0.5~1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300-1000.

12. The residue slurry bed hydrocracking method according to claim 9, characterized in that, The extraction of another portion of the cracking products from the slurry bed reactors below the highest level, as well as the cracking products from the highest level slurry bed reactor, includes the following steps: Monitor the density of the cracking products at the output end of the spiral reaction channel of each stage of the slurry bed reactor; When the density of the cracking products in the slurry bed reactor decreases by 0.5% to 5%, 10% to 30% of the cracking products, which account for 10% to 30% of the material stock in the slurry bed reactor, are extracted from the slurry bed reactor.

13. The residue oil slurry bed hydrocracking method according to claim 10, characterized in that, The process of separating and processing the extracted cracking products to obtain the final product and intermediate products includes the following steps: The cracking products are fed into a high-pressure separator for gas-liquid separation. The liquid phase product in the high-pressure separator is transported to the low-pressure separator via a pressure reducing valve for deep gas-liquid separation. After large solid particles are removed from the liquid phase product in the low-pressure separator by the filter group, it enters the fractionation furnace for heating and then enters the fractionation tower for separation to obtain the final product and the intermediate product.

14. The residue slurry bed hydrocracking method according to claim 13, characterized in that, It also includes the following steps: The hydrogen source is delivered to the static heavy oil hydrogen mixer via a circulating hydrogen compressor; The gaseous products in the high-pressure separator are circulated to the circulating hydrogen compressor via the hydrogen compressor dehydration buffer tank, and then transported to the static heavy oil hydrogen mixer.

15. The residue oil slurry bed hydrocracking method according to claim 10, characterized in that, The feedstock oil is a low-quality oil composed of one or more of the following: high-sulfur residue oil, high-metal residue oil, atmospheric residue oil, vacuum residue oil, extra-heavy crude oil, catalytic slurry oil, and oil sands asphalt. The carrier oil is a mixture of one or more of the following: catalytic diesel, coking diesel, hydrocracking diesel, coal-to-oil fractions, and biodiesel. The intermediate products include diesel oil, wax oil, and hydrotreated tailings. The final product includes a target product and by-products, wherein the target product is naphtha and the by-products include light hydrocarbons and coke.

16. The residue slurry bed hydrocracking method according to claim 15, characterized in that, The intermediate product is recycled to the corresponding stage of the slurry bed reactor for cracking reaction, including the following steps: The diesel fuel is recycled to the third-stage slurry bed reactor for cracking, the wax oil is recycled to the second-stage slurry bed reactor for cracking, and the hydrotreated tailings are treated with hydrogen by the static heavy oil mixer and the feedstock heater, mixed with the reactants, and then recycled to the first-stage slurry bed reactor for cracking; or The intermediate products are all recycled to the second-stage slurry bed reactor for cracking.

17. A residue oil slurry bed hydrocracking system, characterized in that, Used for implementing the residue oil slurry bed hydrocracking method according to any one of claims 9 to 16.

Images