Slurry bed reaction device and residual oil slurry bed hydrocracking method and system

Abstract

The invention discloses a slurry bed reaction device and a residual oil slurry bed hydrocracking method and system. The slurry bed reaction device comprises multiple stages of slurry bed reactors which are arranged step by step from a reaction inlet to a reaction outlet; a spiral reaction channel is arranged in each stage of slurry bed reactor; the spiral diameter of the spiral reaction channel is gradually reduced, and the height-diameter ratio of the spiral reaction channel is gradually increased. The inferior oil raw material is cracked step by step, the cracking reaction depth is improved, and the effect of improving the residual oil conversion rate is achieved; and the flowing speed of reactants in the step-by-step cracking process along the spiral reaction channel of the multi-stage slurry bed reactor is also increased step by step, and the reactants are not easy to backmix to the previous stage of slurry bed for reaction, so that the excessive cracking of light components caused by the deposition of reaction green coke and the backmixing of materials is finally inhibited. According to the invention, the intermediate product is fractionated from the extracted cracking product and is circularly returned to the slurry bed reactor of the corresponding level, so that step-by-step cracking and staged cracking are realized, and finally, the target of increasing the yield of chemical raw materials is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of inferior oil processing, and in particular to a slurry bed reaction device and a residual oil slurry bed hydrocracking method and system. Background Art

[0002] This section is intended to provide a background or context to the embodiments of the invention recited in the claims. No admission is made that the description herein is prior art by inclusion in this section.

[0003] In view of the increasing amount of low-quality crude oil resources such as high sulfur, high metal, and high residual carbon in the crude oil pool and the pressure of "transforming from refining to chemical industry", oil refining enterprises are facing great processing pressure and technical difficulties. For the above-mentioned low-quality oil, heavy oil catalytic cracking and heavy oil fixed bed hydrotreatment are used. The catalyst surface is deactivated very quickly due to coking and metal deposition; the delayed coking process has a high coke output and poor coke quality; although the boiling bed hydrogenation technology can process low-quality oil, its process flow and equipment are complex, and the light oil yield is low. Compared with the above technologies, the heavy oil slurry bed hydrocracking technology can process more inferior raw materials, and its product quality is better and the light oil yield is also higher. It is a process technology that is more in line with the trend of efficient resource utilization and helps the goal of "transforming from refining to chemical industry". Among them, the slurry bed hydrocracking reaction system and catalyst, as the core technology of the process, have always been the focus of attention and patent protection points of technicians in this field. Major oil refining companies in the world have invested huge resources and manpower in concentrated development.

[0004] At present, the world's mainstream heavy oil slurry bed hydrocracking processes mainly include: the EST process of Italy's ENI, the HDHPLUS-SHP process jointly developed by Venezuela's PDVSA and France's Axens, Chevron's VRSH process, KBR and BP's VCC process, UOP's Uniflex process and other processes. The above processes each have their own advantages and characteristics, but there are great differences in reactor type, catalyst type, operating process and other aspects.

[0005] The EST process uses an oil-soluble residue oil slurry bed hydrocracking catalyst, which is converted into a nano-thin layer of unsupported MoS2 in the slurry bed reactor and adopts complex in-reactor process control technology. The main features of the process are: ① The unconverted oil is circulated multiple times, the total conversion rate of the crude oil is high, and there is no fuel oil or coke product; ② The product quality is relatively good, and gasoline and diesel meet the Euro IV standard; ③ The metals in the crude oil are basically removed; ④ The consumption of the higher-cost catalyst is low.

[0006] The HDHPLUS-SHP process sets up two slurry bed reactors with complex internal components to operate in series. It uses solid particle catalysts and requires the addition of a certain amount of additives. The catalyst system has insufficient dispersibility in the crude oil and uses harsher reaction process conditions. It requires the disposal of about 10% of unconverted tail oil, and the economic efficiency of the device is insufficient.

[0007] The VCC process uses a non-metallic slurry bed hydrocracking catalyst and a process in which multiple reactors are operated in series, thereby reducing the impact of back-mixing of the reaction materials. The operating pressure is 18MPa to 20MPa. Increasing the severity of the reaction can achieve a single-pass conversion rate of 95% for the residual oil. In the hot separator, the light components are separated from the unconverted tail oil, and the unconverted tail oil is completely discharged from the bottom of the hot separator without recycling. The purpose of controlling coking and maintaining stable operation of the device is achieved by discharging the tail oil externally, and the economic efficiency of the device is poor.

[0008] At present, slurry bed reactors are mainly divided into two categories: one is the empty barrel form with no internal components or simple internal components, such as the EST process of ENI in Italy, which requires connecting multiple reactors in series or using a single reactor in series with external circulation equipment, using highly active, oil-soluble catalysts, and setting up a complex control system to circulate and transform inferior heavy oil to achieve deep cracking of heavy oil; the other is a slurry bed reactor with complex internal components. This type of technology is basically newly developed in recent years, and it can achieve the goals of enhancing the in-vessel backmixing of the reaction flow and inhibiting the deposition of coke, enhancing heat transfer and mass transfer, and separating the light components from the system in time while cracking the heavy oil. Although it can significantly improve the reaction depth, it has problems such as complex design and operation, and difficulty in manufacturing and maintenance.

[0009] The above-mentioned slurry bed reactor, reaction system and process method each have their own advantages, but there are still certain shortcomings, which require researchers to continuously optimize and improve. Summary of the invention

[0010] The purpose of the present invention is to provide a slurry bed reaction device and a residue oil slurry bed hydrocracking method and system to solve the technical problems that reaction coke products in the current slurry bed reaction equipment are easy to deposit and block the equipment, and the reaction materials are easy to backmix and cause excessive cracking of the light components.

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

[0012] The present invention provides a slurry bed reaction device, comprising a multi-stage slurry bed reactor arranged in stages from a reaction inlet to a reaction outlet; a spiral reaction channel is arranged in each stage of the slurry bed reactor, the spiral reaction channel is spirally arranged around the axis of the slurry bed reactor, and the spiral reaction channels of the slurry bed reactors at each stage are connected; wherein the spiral diameter of the spiral reaction channels of the multi-stage slurry bed reactors decreases step by step, and the aspect ratio of the spiral height to the spiral diameter of the spiral reaction channels of the multi-stage slurry bed reactors increases step by step; wherein each stage of the slurry bed reactor below the highest stage slurry bed reactor is provided with an extraction port connected to the output end of the spiral reaction channel, and at least one stage of the slurry bed reactor above the lowest stage slurry bed reactor is provided with a circulation inlet connected to the input end of the spiral reaction channel.

[0013] In an embodiment of the present invention, the number of stages of the slurry bed reactor is three to six.

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

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

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

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

[0018] In an embodiment of the present invention, the slurry bed reaction device also includes an online monitoring mechanism. At least one density meter is provided in the spiral reaction channel of each stage of the slurry bed reactor. The density meter is electrically connected to the online analysis mechanism to monitor the cracking reaction depth in the spiral reaction channel according to the density of the cracking products in the spiral reaction channel.

[0019] In an embodiment of the present invention, a plurality of temperature measuring elements are provided in the spiral reaction channel of each stage of the slurry bed reactor, 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 comprises an outer cylinder, an inner cylinder and a spiral blade, wherein the spiral blade is spirally arranged around the axis of the slurry bed reactor, the inner cylinder is placed in the outer cylinder and connected through the spiral blade, and the annulus between the inner cylinder and the outer cylinder is separated by the spiral blade to form the spiral reaction channel; wherein the density meter and the temperature measuring element are installed on the outer wall surface 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.

[0021] The present invention also provides a residue oil slurry bed hydrocracking method, comprising the following steps: mixing raw oil with a catalyst and heating with hydrogen to obtain a reaction raw material; conveying the reaction raw material to a first-stage slurry bed reactor of a slurry bed reaction device for cracking reaction; wherein a portion of the cracking products produced by each stage of the slurry bed reactor below the highest stage enters the next stage of the slurry bed reactor and undergoes cracking reaction step by step; another portion of the cracking products produced by each stage of the slurry bed reactor below the highest stage and the cracking products produced by the highest stage of the slurry bed reactor are extracted; the extracted cracking products are separated and processed to obtain final products and intermediate products; the intermediate products are circulated to the slurry bed reactor of the corresponding stage for cracking reaction, and the cycle is repeated until the intermediate products are converted into the final products.

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

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

[0024] In an embodiment of the present invention, extracting another part of the cracked products produced by the slurry bed reactors at each level lower than the highest level and the cracked products produced by the highest level slurry bed reactor includes the following steps: monitoring the density of the cracked products at the output end of the spiral reaction channel of the slurry bed reactors at each level; when the density of the cracked products of the slurry bed reactor decreases by 0.5% to 5%, extracting 10% to 30% of the cracked products accounting for the material reserves of the slurry bed reactor from the slurry bed reactor.

[0025] In an embodiment of the present invention, the extraction of the cracked product is separated and processed to obtain at least one final product and an intermediate product, comprising the following steps: conveying the cracked product to a high-pressure separator for gas-liquid separation; conveying the liquid product in the high-pressure separator to a low-pressure separator via a pressure reducing valve for deep gas-liquid separation; passing the liquid product in the low-pressure separator through a filter group to remove large particles of solid impurities, then entering a fractionation heating furnace for heating, and then entering a distillation tower for separation to obtain the final product and the intermediate product.

[0026] In an embodiment of the present invention, the following steps are also included: the hydrogen source is transported to the static heavy oil hydrogen mixer via a circulating hydrogen compressor; the gaseous product in the high-pressure separator is 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 an embodiment of the present invention, the feedstock oil is an inferior oil mixed with at least one or more of high-sulfur residue oil, high-metal residue oil, atmospheric residue oil, vacuum residue oil, extra-thick crude oil, catalytic oil slurry and oil sand asphalt; the carrier oil is a mixed oil mixed with at least one or more of catalytic diesel, coker diesel, hydrocracking diesel, coal-to-liquid fraction and biodiesel; the intermediate products include diesel, wax oil and hydrogenation tails; the final products include target products and non-target products, the target product is naphtha, and the by-products include light hydrocarbons and coke.

[0028] In an embodiment of the present invention, the recycling of the intermediate products to the slurry bed reactor of the corresponding level for cracking reaction comprises the following steps: the diesel is circulated to the slurry bed reactor of the third level for cracking reaction, the wax oil is circulated to the slurry bed reactor of the second level for cracking reaction, the hydrogenation tailings are treated by hydrogen mixing and heating in the static heavy oil hydrogen mixer and the raw material heating furnace and then mixed with the reaction raw materials and recycled to the slurry bed reactor of the first level for cracking reaction; or the intermediate products are all circulated to the slurry bed reactor of the second level for cracking reaction.

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

[0030] The characteristics and advantages of the present invention are:

[0031] The slurry bed reaction device of the present invention, by arranging a multi-stage slurry bed reactor, cracks the inferior oil raw material step by step, improves the cracking reaction depth, and achieves the effect of improving the residual oil conversion rate.

[0032] The slurry bed reaction device of the present invention is provided with a spiral reaction channel for spiral conveying, and the spiral diameter of the spiral reaction channel of the multi-stage slurry bed reactor is gradually reduced and the height-to-diameter ratio of the spiral reaction channel is gradually increased, so that the flow velocity (i.e., linear velocity) of the reactants is gradually increased during the step-by-step cracking along the spiral reaction channel of the multi-stage slurry bed reactor, and it is not easy to be back-mixed to the previous stage of slurry bed reaction, thereby ultimately achieving the goal of suppressing the deposition of reaction coke products and excessive cracking of light components caused by material back-mixing.

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

[0034] The slurry bed reaction device of the present invention is equipped with multiple density meters in each stage of the slurry bed reactor, so as to monitor the cracking reaction depth according to the cracking products, and then according to the feedback results of the density meters, part of the cracking products produced by each stage of the slurry bed reactor are fractionated, so as to effectively control the cracking reaction depth.

[0035] The residue oil slurry bed hydrocracking method and system of the present invention realizes step-by-step cracking and staged cracking by recycling the fractionated intermediate products back to the slurry bed reactor of the corresponding level, thereby ultimately achieving the goal of producing more chemical raw materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0037] Figure 1 It is a schematic structural diagram of a slurry bed reaction device in one embodiment of the present invention.

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

[0039] In the figure:

[0040] 1. Catalyst preparation tank; 2. Raw oil preparation tank; 3. Raw material pump; 4. Heat exchanger; 5. Static heavy oil hydrogen mixer; 6. Raw material heating furnace; 7. Slurry bed reaction device; 8. High-pressure separator; 9. Pressure reducing valve; 10. Low-pressure separator; 11. Filter group; 12. Fractionation heating furnace; 13. Fractionation tower; 14. Circulating hydrogen compressor; 15. Hydrogen compressor deliquation buffer tank;

[0041] 71. Reaction inlet;

[0042] 72. The first-stage slurry bed reactor; 73. The inner cylinder of the first-stage slurry bed reactor; 74. The spiral reaction channel of the first-stage slurry bed reactor;

[0043] 75. The second-stage slurry bed reactor; 76. The inner cylinder of the second-stage slurry bed reactor; 77. The 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 exit. DETAILED DESCRIPTION

[0046] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work 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 reaction device 7, comprising a multi-stage slurry bed reactor arranged in stages from a reaction inlet 71 to a reaction outlet 711; a spiral reaction channel is provided in each stage of the slurry bed reactor, the spiral reaction channel is spirally arranged around the axis of the slurry bed reactor, and the spiral reaction channels of the slurry bed reactors of each stage are connected; wherein the spiral diameter of the spiral reaction channels of the multi-stage slurry bed reactor decreases step by step, and the aspect ratio of the spiral height to the spiral diameter of the spiral reaction channels of the multi-stage slurry bed reactor increases step by step; wherein each stage of the slurry bed reactor lower than the highest stage slurry bed reactor is provided with an extraction outlet connected to the output end of its spiral reaction channel, and at least one stage of the slurry bed reactor higher than the lowest stage slurry bed reactor is provided with a circulation inlet connected to the input end of its spiral reaction channel.

[0049] That is to say, the slurry bed reactor closest to the reaction inlet 71, with the largest spiral diameter of the spiral reaction channel 74 and the smallest aspect ratio of the spiral height to the spiral diameter of the spiral reaction channel 74 is the first-stage slurry bed reactor 72, i.e., the lowest-stage slurry bed reactor, i.e., the slurry bed reactor into which the reaction raw materials first enter; followed by the second-stage slurry bed reactor 75, the third-stage slurry bed reactor 78, ...; among them, the slurry bed reactor 78 closest to the reaction outlet, with the smallest spiral diameter of the spiral reaction channel 710 and the largest aspect ratio of the spiral height to the spiral diameter of the spiral reaction channel 710 is the highest-stage slurry bed reactor, i.e., the slurry bed reactor into which the reactants enter last. Figure 1 In the illustrated embodiment of the present invention, the number of stages of slurry bed reactors is three, and the third stage slurry bed reactor 78 is the highest stage slurry bed reactor.

[0050] The slurry bed reaction device 7 of the present invention, by setting up a multi-stage slurry bed reactor, cracks the inferior oil raw material step by step, improves the cracking reaction depth, and achieves the effect of improving the residual oil conversion rate. And by setting up a spiral reaction channel for spiral transportation, and the spiral diameter of the spiral reaction channel of the multi-stage slurry bed reactor is gradually reduced and the height-to-diameter ratio of the spiral reaction channel is gradually increased, so that the flow speed (that is, the linear speed) of the reactants in the process of step-by-step cracking along the spiral reaction channel of the multi-stage slurry bed reactor is also gradually increased, and it is not easy to be mixed back to the previous stage of the slurry bed reaction, so as to finally achieve the suppression of the deposition of reaction coke and the excessive cracking of light components caused by the material backmixing.

[0051] In addition, the reaction outlet 711 can be used as the extraction outlet of the highest-level slurry bed reactor 78, and the reaction inlet 71 can be used as the circulation inlet of the first-level slurry bed reactor 72. The cracking products produced by the cracking reactions in each level of the slurry bed reactor can be extracted from the corresponding extraction outlets, and then separated to obtain the final product and the intermediate product, while the intermediate product can be circulated back from the corresponding circulation inlet to the slurry bed reactor of the corresponding level for cracking reaction again, thereby realizing graded cracking and circulating cracking, achieving deep conversion, and being beneficial to improving the conversion rate and the yield of the target product.

[0052] Among them, the spiral diameter of the spiral reaction channel is twice the radial distance between the spiral channel and the axis of the slurry bed reaction device 7. The spiral height of the spiral reaction channel is the axial distance between the input end of the spiral reaction channel and the output end of the spiral reaction channel. Specifically, the slurry bed reactor includes an outer cylinder, an inner cylinder and a spiral blade, the spiral blade is spirally arranged around the axis of the slurry bed reaction device 7, the inner cylinder is placed in the outer cylinder and connected by the spiral blade, and the annulus between the inner cylinder and the outer cylinder is separated by the spiral blade to form a spiral reaction channel, which has a simple structure and is easy to process. In other words, the spiral outer diameter of the spiral reaction channel is equal to the diameter of the outer cylinder, that is, the diameter of the slurry bed reactor; the spiral inner diameter of the spiral reaction channel is equal to the diameter of the inner cylinder, and the height (that is, the 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 also decreases step by step, and the height-to-diameter ratio of the height of the multi-stage slurry bed reactor to its diameter also increases step by step.

[0053] Specifically, 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 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 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 spiral inner diameter of its spiral reaction channel 710.

[0054] like Figure 1 As shown, in the embodiment of the present invention, the multi-stage slurry bed reactor is coaxially arranged 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 port is located at the top of the corresponding slurry bed reactor, and the circulation inlet is located at the bottom of the corresponding slurry bed reactor. By arranging the multi-stage slurry bed reactor coaxially in the vertical direction, the floor space of the entire device can be effectively reduced, and it is also beneficial to suppress the back mixing of light components and excessive cracking.

[0055] The present invention finds that the number of stages of the slurry bed reactor, that is, the number of slurry bed reactors, will affect the design cost, manufacturing cost and yield of the final product of the entire device. Therefore, in the embodiment of the present invention, the number of stages of the slurry bed reactor is three to six, which can obtain a more ideal yield of the final product, and the design cost and manufacturing cost are also low. Further, the number of stages of the slurry bed reactor is preferably three to four, after comprehensively evaluating the design cost, manufacturing cost and yield of the final product. When the number of stages of the slurry bed reactor is lower than three, the yield of the final product is not ideal. When the number of stages of the slurry bed reactor is higher than six, the design cost and manufacturing cost of the entire device will be increased, but a more ideal yield of the final product will not be obtained.

[0056] The present invention also discovered that the depth of the cracking reaction is related to the relationship between the depth of the step-by-step reaction of the reactants in the slurry bed reaction device and the height-to-diameter ratio of the spiral reaction channels of the slurry bed reactors of each stage and the material flow rate; therefore, in an embodiment of the present invention, the height-to-diameter ratio of the multi-stage slurry bed reactor is controlled, and the height-to-diameter ratio of the spiral reaction channel of the slurry bed reactor of the latter stage is 1 to 3 times, preferably 1 to 2 times, of the height-to-diameter ratio of the spiral reaction channel of the slurry bed reactor of the previous stage; further, the preset flow rate of the spiral reaction channel of the slurry bed reactor of the previous stage is controlled to be 1.5 to 3 times, preferably 1.5 to 2 times, of the preset flow rate of the spiral reaction channel of the slurry bed reactor of the latter stage; and based on this, the spiral height, spiral diameter and channel cross-sectional area of ​​the spiral reaction channels of the slurry bed reactors of each stage are set.

[0057] In the embodiment of the present invention, the slurry bed reaction device 7 further includes an online monitoring mechanism, and at least one density meter is provided in the spiral reaction channel of each stage of the slurry bed reactor, and the density meter is electrically connected to the online monitoring mechanism to monitor the cracking reaction depth in the spiral reaction channel according to the density of the cracked product in the spiral reaction channel. Specifically, the number of density meters can be set to one or more. In this embodiment, the density meter is located at the output end of the spiral reaction channel or is arranged near the output end of the spiral reaction channel, that is, the density meter of each stage of the slurry bed reactor is arranged near the reaction inlet or extraction port at the top of the corresponding slurry bed reactor. In other embodiments, the slurry bed reactor at each stage is provided with a plurality of extraction ports, and the plurality of extraction ports are arranged at intervals along the conveying direction of the spiral reaction channel and are connected to the spiral reaction channel. Accordingly, a plurality of density meters are arranged in the spiral reaction channel of each stage of the slurry bed reactor, and the plurality of density meters are arranged near the plurality of extraction ports respectively, therefore, the cracked product in the spiral reaction channel can be selectively extracted from different extraction ports according to the density of the cracked product at different positions monitored by different density meters in the same spiral reaction channel.

[0058] In addition, a plurality of temperature measuring elements are provided in the spiral reaction channel of each stage of the slurry bed reactor, and the plurality of temperature measuring elements are electrically connected to the online analysis mechanism to monitor the reaction temperature in the spiral reaction channel. Specifically, the number of temperature measuring elements can be three to six, or seven to ten, or more. The plurality of temperature measuring elements of each stage of the slurry bed reactor are installed on the outer wall surface of the inner tube, and an auxiliary heating mechanism is installed in the inner tube. The auxiliary heating mechanism is electrically connected to the online monitoring mechanism, and the online analysis mechanism receives the temperature signal of the temperature measuring element and controls the auxiliary heating mechanism to heat the spiral reaction channel according to the temperature signal to adjust the reaction temperature. In an embodiment of the present invention, the auxiliary heating mechanism is an electrically heated salt bath module, which can increase the temperature of the spiral reaction channel 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 residue oil slurry bed hydrocracking method, comprising the following steps:

[0061] Step S1, mixing the crude oil with the catalyst and heating them with hydrogen to form a reaction raw material.

[0062] Specifically, the raw oil and the catalyst are mixed and heated to form a reaction raw material, including the following steps: the catalyst is evenly dispersed in the carrying oil in the catalyst preparation tank 1 to form a first mixture; the first mixture is injected into the raw oil preparation tank 2 to be fully mixed with the raw oil, and then injected into the heat exchanger 4 for heat exchange to form a second mixture; the second mixture is transported to the static heavy oil hydrogen mixer 5 to be fully mixed with hydrogen, and then transported to the raw material heating furnace 6 for heating to form a reaction raw material.

[0063] The feedstock oil is a low-quality oil mixed with at least one or more of high-sulfur residue oil, high-metal residue oil, atmospheric residue oil, vacuum residue oil, super-thick crude oil, catalytic oil slurry and oil sand asphalt; the carrier oil is a mixed oil mixed with at least one or more of a mixture of catalytic diesel, coking diesel, hydrocracking diesel, coal-to-liquid fraction and biodiesel. The carrier oil carries the catalyst and is mixed with the feedstock oil. The feedstock pump 3 injects the mixture into the heat exchanger 4 for heat exchange.

[0064] Step S2, transporting the reaction raw materials from the reaction inlet 71 of the first-stage slurry bed reactor 72 to the slurry bed reactor 7 for cracking reaction step by step; wherein, a portion of the cracking products produced by each stage of the slurry bed reactor below the highest stage enters the next stage of the slurry bed reactor and undergoes cracking reaction step by step. The slurry bed reactor 7 has the same specific structure, working principle and beneficial effects as the slurry bed reactor 7 in the first embodiment, and will not be described in detail here.

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

[0066] Step S3, extracting another part of the cracked products produced by each slurry bed reactor below the highest level and the cracked products produced by the highest level slurry bed reactor.

[0067] Specifically, another part of the cracked products produced by the slurry bed reactors at the lower level and the cracked products produced by the highest level slurry bed reactor are extracted; including the following steps: monitoring the density of the cracked products at the output end of the spiral reaction channel of each level of slurry bed reactor; when the density of the cracked products of the slurry bed reactor decreases by 0.5% to 5%, 10% to 30% of the material inventory of the slurry bed reactor is extracted from the slurry bed reactor. Preferably, when the density of the cracked products of the slurry bed reactor decreases by 1% to 2.5%, 10% to 20% of the material inventory of the slurry bed reactor is extracted from the slurry bed reactor. The remaining cracked products in the slurry bed reactors at the lower level can enter the next level slurry bed reactor for cracking reaction.

[0068] Step S4, separating and treating the extracted cracked product to obtain at least one final product and an intermediate product.

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

[0070] The final products include naphtha, light hydrocarbons and coke, among which naphtha is the target product, and light hydrocarbons (i.e., C1-C4 components) and coke are by-products produced by over-cracking; the intermediate products include diesel, wax oil and hydrogenation tailings, and the intermediate products can be converted into the final products, i.e., naphtha, light hydrocarbons and coke, by cracking again.

[0071] Step S5, circulating the intermediate product to the corresponding level of slurry bed reactor for cracking reaction, and repeating the cycle until the intermediate product is converted into at least one final product. By circulating the intermediate product to the corresponding level of slurry bed reactor for cracking reaction again, it is beneficial to control the depth of the cracking reaction, thereby facilitating the conversion rate of the intermediate product into the target product and reducing the conversion rate of the intermediate product into the by-product.

[0072] Combination Figure 1 and Figure 2As shown, in some embodiments of the present invention, the intermediate product is circulated to the corresponding level of slurry bed reactor for cracking reaction, including the following steps: diesel is circulated to the third-level slurry bed reactor 78 for cracking reaction; wax oil is circulated to the second-level slurry bed reactor 75 for cracking reaction; hydrogenation tailings are treated by hydrogen mixing and heating in the static heavy oil hydrogen mixer 5 and the raw material heating furnace 6 and then mixed with the reaction raw materials and circulated to the first-level slurry bed reactor 72 for cracking reaction.

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

[0074] In addition, the present invention also 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 product in the high-pressure separator 8 is circulated to the circulating hydrogen compressor 14 via the hydrogen compressor deliquidation 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 a plurality of extraction ports, and the plurality of extraction ports are arranged at intervals along the conveying direction of the spiral reaction channel and are connected to the spiral reaction channel. Accordingly, a plurality of density meters are arranged in the spiral reaction channel of each stage of the slurry bed reactor, and the plurality of density meters are respectively arranged close to the plurality of extraction ports. Therefore, when the density meter near any extraction port in the same spiral reaction channel monitors that the density of the cracking product decreases by 0.5% to 5%, 10% to 20% of the cracking product is extracted from the corresponding extraction port.

[0076] Implementation Method 3

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

[0078] In order to better understand and implement the slurry bed reaction device and the 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, preferred embodiment 1 and preferred embodiment 2 are respectively slurry reaction bed devices of some embodiments of the present invention.

[0080] The slurry reaction bed device of the residue oil slurry bed hydrocracking system in the comparative example is different from the slurry reaction bed device of the present invention in that no spiral reaction channel is provided in the slurry bed reactor, that is, it is an empty cylinder structure.

[0081] However, the process methods adopted in each preferred embodiment, each more preferred embodiment and comparative example are all the residue oil slurry bed hydrocracking methods of the present invention.

[0082] The raw oil used in each preferred embodiment, each more preferred embodiment and comparative example is the same, and the catalysts used are all oil-soluble highly dispersed molybdenum-based catalysts, which do not require pre-sulfurization when used and can be used directly after heating to the activation temperature.

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

[0084]

[0085] The information of crude oil is shown in the table below.

[0086]

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

[0088]

[0089]

[0090] The evaluation and analysis methods are shown in the following table:

[0091]

[0092] The evaluation and analysis results are shown in the following table:

[0093]

[0094]

[0095] Comparative analysis:

[0096] First, by comparing the preferred embodiment 2 and the comparative example, it can be seen that under the same reaction conditions and the number of slurry bed reactors, when the slurry bed reactor of the present invention is used, its single-pass conversion rate (the conversion rate of raw oil into light hydrocarbons, naphtha, diesel and vacuum wax oil) is 87.7%, the total conversion rate (the conversion rate of raw oil into light hydrocarbons and naphtha after the cyclic reaction) is 90.03%, the single-pass coking rate is 2.1%, the total coking rate is 9.97%, and the total recovery of naphtha is 85.5%; while when a slurry bed reactor with a multi-stage hollow cylinder structure is used, 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 recovery of naphtha is 73.18%; therefore, the slurry bed reactor of the present invention has obvious advantages, and in terms of the removal rate of impurities such as sulfur, nitrogen, residual carbon, and metals, the test results of the present invention are also better than those of the slurry bed reactor with an empty cylinder structure.

[0097] Secondly, by comparing the preferred embodiments, the more preferred embodiments and the comparative examples, it can be seen that within the range of process conditions of all preferred embodiments, the more preferred embodiments and the comparative examples, with the increase in the number of stages of slurry bed reactors, the aspect ratio of two adjacent slurry bed reactors, the severity of reaction conditions, and the decrease in the material inventory in the slurry bed reactor (that is, the increase in the amount extracted from the top of each stage of slurry bed reactor), the density (that is, the specific gravity) of the reaction product gradually decreases, the impurity removal rate increases, the total recovery of naphtha first increases and then decreases, while the recovery of light hydrocarbons (that is, C1-C4 components) and coke first decreases and then increases.

[0098] It should be noted that the above rules are obtained in the preferred operating range of the present invention. When the key factors such as the number of reactor stages, the height-to-diameter ratio of two adjacent slurry bed reactors, the material inventory in the slurry bed reactor, and the severity of the reaction conditions are out of this range, the design cost, manufacturing cost, complexity, high functional concentration and operating cost of the device will be increased, but a more ideal total naphtha yield will not be obtained, but the yield of light hydrocarbons and coke will be increased.

[0099] In summary, the present invention optimizes the flow form of materials inside the slurry bed reactor, effectively inhibits the deposition of reaction coke that blocks the reaction equipment and the excessive cracking of light components caused by backmixing of reaction materials, and adopts the idea of ​​combining "graded reaction", "precision cycle reaction" and "gradual residence time". Under the premise of ensuring continuous and stable operation of the device, this method can produce chemical raw materials in large quantities from inferior oil without discharging tailings, thereby realizing an efficient and deep conversion process of inferior oil.

[0100] The above are only several embodiments of the present invention. Those skilled in the art may make various changes or modifications to the embodiments of the present invention based on the contents disclosed in the application documents without departing from the spirit and scope of the present invention.

Claims

1. A slurry bed reaction device, characterized in that: It comprises a multi-stage slurry bed reactor arranged step by step from the reaction inlet to the reaction outlet; each stage of the slurry bed reactor is provided with a spiral reaction channel, the spiral reaction channel is arranged spirally around the axis of the slurry bed reactor, and the spiral reaction channels of the slurry bed reactors at each stage are connected; Wherein, the spiral diameter of the spiral reaction channel of the multi-stage slurry bed reactor decreases step by step, and the aspect ratio of the spiral height to the spiral diameter of the spiral reaction channel of the multi-stage slurry bed reactor increases step by step; Among them, each level of the slurry bed reactor below the highest level slurry bed reactor is provided with an extraction outlet connected to the output end of its spiral reaction channel, and at least one level of the slurry bed reactor above the lowest level slurry bed reactor is provided with a circulation inlet connected to the input end of its spiral reaction channel.

2. The slurry bed reaction device according to claim 1, characterized in that: The number of stages of the slurry bed reactor is three to six.

3. The slurry bed reaction device according to claim 1, characterized in that: The height-to-diameter ratio of the spiral reaction channel of the slurry bed reactor of the latter stage is 1 to 3 times the height-to-diameter ratio of the spiral reaction channel of the slurry bed reactor of the former stage.

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

5. The slurry bed reaction device according to claim 1, characterized in that: All the slurry bed reactors at levels higher than the lowest level slurry bed reactor are provided with the circulation inlet connected to the input end of the spiral reaction channel; or only the second level slurry bed reactor is provided with the circulation inlet connected to the input end of the spiral reaction channel.

6. The slurry bed reaction device according to claim 5, characterized in that: The multi-stage slurry bed reactors are coaxially arranged step by step from bottom to top, the reaction inlet is located at the bottom of the first-stage slurry bed reactor, the reaction outlet is located at the top of the highest-stage slurry bed reactor, the extraction outlet is located at the top of the corresponding slurry bed reactor, and the circulation inlet is located at the bottom of the corresponding slurry bed reactor.

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

8. The slurry bed reaction device according to claim 7, characterized in that: A plurality of temperature measuring elements are arranged in the spiral reaction channel of each stage of the slurry bed reactor, 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.

9. The slurry bed reaction device according to claim 8, characterized in that: The slurry bed reactor comprises an outer cylinder, an inner cylinder and a spiral blade, wherein the spiral blade is spirally arranged around the axis of the slurry bed reactor, the inner cylinder is placed in the outer cylinder and connected via the spiral blade, and the annulus between the inner cylinder and the outer cylinder is separated by the spiral blade to form the spiral reaction channel; The density meter and the temperature measuring element are installed on the outer wall surface 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.

10. A residue oil slurry bed hydrocracking method, characterized in that: The following steps are involved: The raw oil is mixed with the catalyst and heated with hydrogen to form a reaction raw material; The reaction raw materials are transported to the first-stage slurry bed reactor of the slurry bed reaction device for cracking reaction; wherein a part of the cracking products produced by the slurry bed reactors at each stage below the highest stage enter the slurry bed reactor at the next stage to carry out cracking reaction step by step; extracting another part of the cracked products produced by the slurry bed reactors at lower levels than the highest level and the cracked products produced by the slurry bed reactor at the highest level; Separating and treating the extracted cracked products to obtain final products and intermediate products; The intermediate product is circulated to the slurry bed reactor of the corresponding level for cracking reaction, and the cycle is repeated until the intermediate product is converted into the final product.

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

12. The residue oil slurry bed hydrocracking method according to claim 10, characterized in that: The reaction conditions for the cracking reaction in the slurry bed reactor include: a reaction temperature of 380°C to 450°C, a reaction pressure of 10.0MPa to 20.0MPa, and a volume space velocity of 0.5 to 1.5h -1 , the volume ratio of hydrogen to oil is 300-1000.

13. The residue oil slurry bed hydrocracking method according to claim 10, characterized in that: The step of extracting another part of the cracked products produced by the slurry bed reactors at levels lower than the highest level and the cracked products produced by the slurry bed reactor at the highest level comprises the following steps: Monitoring the density of the cracked product at the output end of the spiral reaction channel of each stage of the slurry bed reactor; When the density of the cracked products in the slurry bed reactor decreases by 0.5% to 5%, 10% to 30% of the cracked products accounting for the material inventory of the slurry bed reactor are extracted from the slurry bed reactor.

14. The residue oil slurry bed hydrocracking method according to claim 11, characterized in that: The extraction of the cracked product and separating it to obtain the final product and the intermediate product comprises the following steps: transporting the cracked product to a high-pressure separator for gas-liquid separation; The liquid phase product in the high-pressure separator is transported to the low-pressure separator through a pressure reducing valve for deep gas-liquid separation; The liquid product in the low-pressure separator is filtered to remove large solid impurities, then enters a fractionation heating furnace for heating, and then enters a fractionation tower for separation to obtain the final product and the intermediate product.

15. The residue oil slurry bed hydrocracking method according to claim 14, characterized in that: The following steps are also included: The hydrogen source is transported to the static heavy oil hydrogen mixer via a circulating hydrogen compressor; The gas phase product in the high-pressure separator is circulated to the circulating hydrogen compressor through the hydrogen compressor deliquescence buffer tank, and then transported to the static heavy oil hydrogen mixer.

16. The residue oil slurry bed hydrocracking method according to claim 11, characterized in that: The raw oil is a low-quality oil mixed with at least one or more of high-sulfur residue oil, high-metal residue oil, atmospheric residue oil, vacuum residue oil, extra-thick crude oil, catalytic oil slurry and oil sand asphalt; The carrier oil is a mixed oil formed by mixing at least one or more of catalytic diesel, coker diesel, hydrocracking diesel, coal-to-liquid fraction and biodiesel; The intermediate products include diesel, wax oil and hydrogenation 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.

17. The residue oil slurry bed hydrocracking method according to claim 16, characterized in that: The step of recycling the intermediate product to the slurry bed reactor of the corresponding level for cracking reaction comprises the following steps: The diesel is circulated to the third-stage slurry bed reactor for cracking reaction, the wax oil is circulated to the second-stage slurry bed reactor for cracking reaction, and the hydrogenation tailings are mixed with the reaction raw materials and then circulated to the first-stage slurry bed reactor for cracking reaction after being treated by hydrogen mixing and heating in the static heavy oil hydrogen mixer and the raw material heating furnace; or The intermediate products are all circulated to the second-stage slurry bed reactor for cracking reaction.

18. A residue oil slurry bed hydrocracking system, characterized in that: Used to implement the residue oil slurry bed hydrocracking method according to any one of claims 10 to 17.

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