Catalytic apparatus and process for light and heavy oils
By setting up independent setters and internal components in the dual riser reactor, the problem of over-cracking of light oil was solved, the processing capacity of the catalytic unit was improved, and efficient co-catalytic reaction of light and heavy oil was achieved, with the ability to flexibly switch production modes.
Patent Information
- Application Number
- CN202211732529.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-12-30
- Publication Date
- 2026-01-27
- Estimated Expiration
- 2042-12-30
AI Technical Summary
How to avoid over-cracking of light oil in a catalytic unit with a dual riser reactor and improve the processing capacity of the catalytic unit, especially when light oil and heavy oil are co-catalyzed, to ensure that the catalytic reaction of heavy oil is not negatively affected.
The first and second reaction units are connected in parallel, each with an independent settling device. The catalyst after the light oil reaction is fed into the second reaction zone. The first and second internal components are set in the second reaction zone to change the flow state of the gas and the catalyst, thereby widening the adjustment range of the apparent gas velocity in the expansion section.
It effectively avoids the over-cracking problem of light oil, increases the flow rate and activity of catalyst in the second reaction zone, enhances the catalytic reaction of heavy oil, expands the processing capacity of the catalytic unit, and enables flexible switching of production modes.
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Figure CN118272116B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a catalytic device and method for light and heavy oils, and relates to the field of catalytic technology. Background Technology
[0002] Catalytic reaction is one of the main methods of secondary petroleum processing, referring to the process of converting heavy oil into cracked gas, gasoline, and diesel under high temperature and the action of a catalyst. Early catalytic reactions used aluminosilicate microspheres as catalysts and dense-bed reactors. With the advent of highly active and selective zeolite catalysts, the reaction rate between petroleum and the catalyst has been greatly accelerated, and riser reactors have been adopted, which is beneficial for improving the yield and selectivity of liquid products.
[0003] Riser reactors represent a significant advancement over dense-bed reactors in both structure and operation. Due to their superior flexibility and adaptability, riser reactors emphasize primary cracking of heavy oil, achieving ideal yields and selectivity for light oils. This type of reactor remains highly viable. With further technological advancements, adding an expansion section in the middle of the riser—a variable-diameter riser—allows for both primary cracking of heavy oil and secondary conversion of gasoline within the same reactor.
[0004] To further optimize the composition of catalytic products, the re-reaction of light oil in a variable-diameter riser is a research hotspot. For example, light oil can be fed into a variable-diameter riser, allowing light and heavy oils to undergo catalytic reaction under the same catalyst. However, because the molecules formed after light oil comes into contact with the catalyst are relatively small and expand significantly in volume, they affect the catalysis of heavy oil. Therefore, to ensure that the catalytic reaction of heavy oil does not have a negative impact, the proportion of light oil incorporated in this method is relatively low. Using a catalytic device with a dual-riser reactor can effectively increase the proportion of light oil incorporated. That is, by setting up a dual-riser reactor, light and heavy oils are catalyzed in different riser reactors. This device can achieve individual optimized reactions of different feedstocks. However, using this device, light oil is prone to over-cracking. How to improve the catalytic device with a dual-riser reactor to avoid over-cracking of light oil and improve the processing capacity of the catalytic device is one of the ongoing research hotspots for those skilled in the art. Summary of the Invention
[0005] This invention provides a catalytic device for light and heavy oils, comprising a first reaction unit and a second reaction unit connected in parallel. Both the first and second reaction units are equipped with independent settling tanks to avoid over-cracking of the light oil. Furthermore, the catalyst reacting with the light oil is fed into the second reaction zone, which helps to increase the catalyst flow rate and activity within the second reaction zone, thus enhancing the catalytic reaction of the heavy oil. Simultaneously, this invention also incorporates a first internal component and a second internal component within the second reaction zone, altering the flow state of the gas and catalyst, widening the adjustment range of the apparent gas velocity in the expansion section, and allowing the variable-diameter reactor to withstand a wider range of adjustment or fluctuation in the reaction oil and gas flow velocity, thereby improving the processing capacity of the catalytic device.
[0006] The present invention also provides a catalytic method for light oil and heavy oil, using the above-described catalytic apparatus.
[0007] A first aspect of the present invention provides a catalytic device for light oil and heavy oil, the catalytic device comprising a first reaction unit, a second reaction unit, a first settling tank, a second settling tank, and a regeneration unit, wherein:
[0008] The first reaction unit is a heavy oil catalytic reaction unit. The first reaction unit includes a pre-lifting section, a first reaction zone, a second reaction zone, and a third reaction zone that are connected in sequence in the axial direction. The inner diameter of the second reaction zone is larger than the inner diameters of the first reaction zone and the third reaction zone. The outlet of the third reaction zone is connected to the first settling device.
[0009] The second reaction zone is provided with a first internal component and a second internal component. The first internal component is a first conveying pipe with the same diameter as the inner diameter of the third reaction zone. The first conveying pipe is connected to the inlet of the third reaction zone. The pipe wall of the first conveying pipe is provided with a plurality of first openings. The second internal component is a distribution plate or a cap-type distributor.
[0010] The second reaction unit is a light oil catalytic reaction unit, and the outlet of the second reaction unit is connected to the second settler;
[0011] The first settling device includes a first gas phase outlet and a first catalyst outlet, and the second settling device includes a second gas phase outlet and a second catalyst outlet. The second gas phase outlet is connected to the first settling device, and the second catalyst outlet is connected to the second reaction zone. The first gas phase outlet is used to output reaction products, and the first catalyst outlet is connected to the inlet of the regeneration unit. The outlet of the regeneration unit is connected to the inlets of the first reaction unit and the second reaction unit.
[0012] Furthermore, the ratio of the height of the first internal component to the height of the second reaction zone is 0.15 to 0.8:1.
[0013] Furthermore, the distance between the bottom port of the first internal component and the bottom of the second reaction zone is 2 to 8 m, and the height of the first internal component is 2 to 7 m.
[0014] Furthermore, the distance between the first opening and the inlet of the third reaction zone is no greater than 0.5 to 2 m; the total area of the first opening is 5% to 30% of the cross-sectional area of the first internal component.
[0015] Furthermore, the diameter ratio of the first reaction zone, the second reaction zone, and the third reaction zone is 1:2 to 5:0.7 to 1.5, and the height ratio of the first reaction zone, the second reaction zone, and the third reaction zone is 1:0.3 to 2:0.5 to 2.
[0016] Furthermore, the diameter ratio of the first reaction zone to the second reaction unit is 1:0.2 to 1, and the height ratio of the first reaction unit to the second reaction unit is 1:0.4 to 0.8.
[0017] Furthermore, when the second internal component is a distribution plate, the distribution plate is one of an arched distribution plate, an irregularly shaped distribution plate, or a concave distribution plate.
[0018] Furthermore, when the second internal component is a cap-type distributor, the cap-type distributor includes a cap and a second conveying pipe, the cap being disposed on the side of the second conveying pipe near the outlet of the second reaction zone, and the second conveying pipe being connected to the outlet of the first reaction zone;
[0019] The cap has several second openings, and the wall of the second conveying pipe has several third openings. The wall of the third opening extends outward to form a gas channel.
[0020] Furthermore, the total area of the second opening is 8% to 15% of the total area of the vertical projection of the cap, and the total area of the third opening is 60% to 400% of the cross-sectional area of the first reaction zone.
[0021] A second aspect of the present invention provides a catalytic method for light oil and heavy oil, using any of the catalytic devices described above, comprising the following steps:
[0022] The steam-atomized heavy oil and the regenerated catalyst are fed into the first reaction zone through the pre-lift section of the first reaction unit. The mixed oil and gas and the regenerated catalyst rise in the first reaction unit and enter the first settling tank after passing through the first reaction zone, the second reaction zone and the third reaction zone.
[0023] The atomized light oil and regenerated catalyst are fed into the second reaction unit. The mixed oil and gas and the regenerated catalyst rise in the second reaction unit and enter the second settling tank.
[0024] The first settling device performs gas-solid separation on the mixed reactants output from the third reaction zone. The separated catalyst enters the regeneration unit through the first catalyst outlet. The second settling device performs gas-solid separation on the mixed reactants output from the second reaction unit. The separated catalyst enters the second reaction zone through the second catalyst outlet. The separated gaseous product enters the first settling device through the second gaseous outlet and is mixed with the gaseous product separated by the first settling device before being output through the first gaseous outlet.
[0025] The regeneration unit regenerates the catalyst to be generated from the outlet of the first catalyst and returns the regenerated catalyst to the first reaction unit and the second reaction unit for recycling.
[0026] This invention provides a catalytic device comprising a first reaction unit and a second reaction unit connected in parallel, both of which are equipped with independent settling devices to avoid the problem of over-cracking of light oil. Furthermore, the catalyst reacting with the light oil is fed into the second reaction zone, which helps to increase the catalyst flow rate and activity within the second reaction zone, thereby enhancing the catalytic reaction of heavy oil. Simultaneously, this invention also incorporates a first internal component and a second internal component within the second reaction zone, altering the flow state of the gas and catalyst, widening the adjustment range of the apparent gas velocity in the expansion section, and allowing the first reaction unit to withstand a wider range of adjustment or fluctuation in the reaction oil and gas flow velocity, thus improving the processing capacity of the device.
[0027] Using the device provided by this invention for the catalysis of light and heavy oils, the production modes of producing ultra-low olefin gasoline and producing more cracked gas can be switched by changing the catalyst and adjusting the operating conditions, thereby achieving flexible control of product properties and product distribution. Attached Figure Description
[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0029] Figure 1 This is a schematic diagram of the structure of a catalytic device provided in an embodiment of the present invention;
[0030] Figure 2 This is a schematic diagram of the structure of the first internal component provided in an embodiment of the present invention;
[0031] Figure 3 This is a schematic diagram of the structure of the second internal component provided in an embodiment of the present invention;
[0032] Figure 4 This is a structural schematic diagram of the second internal component provided in another embodiment of the present invention.
[0033] Explanation of reference numerals in the attached figures:
[0034] 1-First reaction unit; 1a-First reaction zone; 1b-Second reaction zone; 1c-Third reaction zone; 2-First settling tank; 3-Regeneration unit; 4-Heat extractor; 5-Catalyst delivery pipe; 6-First regenerated catalyst delivery pipe; 7-Second regenerated catalyst delivery pipe; 8-First internal component; 9-Second internal component;
[0035] 10-First pre-lift gas; 11-Heavy oil; 12-Quick coolant; 13-Reaction product; 14-First stripping steam; 15-Low-temperature steam; 16-High-temperature steam; 17-Regenerated air; 18-Regenerated flue gas;
[0036] 19-Second pre-lift gas; 20-Light oil; 21-Second reaction unit; 22-Second settler; 23-Gas phase product conveying pipe; 24-Second stripping steam; 25-Catalyst conveying pipe. Detailed Implementation
[0037] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0038] Figure 1 This is a schematic diagram of the structure of a catalytic device provided in an embodiment of the present invention, as shown below. Figure 1 As shown, the device includes a first reaction unit 1, a second reaction unit 21, a first settling tank 2, a second settling tank 22, and a regeneration unit 3. The first settling tank 2 is connected to the first reaction unit 1, and the second settling tank 22 is connected to the second reaction unit 21. These devices are used to perform gas-solid separation on the reaction products of the first reaction unit 1 and the second reaction unit 21, respectively. The following is a detailed description of each unit:
[0039] The first reaction unit 1 is a heavy oil catalytic reaction unit, specifically a variable diameter riser reactor, which includes a pre-lifting section, a first reaction zone 1a, a second reaction zone 1b, and a third reaction zone 1c connected in sequence in the axial direction. The pre-lifting section is used to input the first pre-lifting gas 10, the heavy oil 11 after steam atomization, and the regenerated catalyst output from the regeneration unit 3. Under the action of the first pre-lifting gas 10, the heavy oil 11 and the regenerated catalyst rise and enter the first reaction zone 1a.
[0040] Heavy oil 11 and the regenerated catalyst react in the first reaction zone 1a and continue upward into the second reaction zone 1b. The second reaction zone 1b is the expansion section, with an inner diameter larger than that of the first reaction zone 1a. The second reaction zone 1b includes a main zone and a connecting zone. The connecting zone is the transition area connecting the main zone with the first reaction zone 1a and the third reaction zone 1c. The main zone can be... Figure 1 The cylindrical shape shown can be a frustum of a cone that gradually expands in diameter from bottom to top, or a cylinder with two or three stages of diameter expansion, etc.; the connecting area can be... Figure 1 The shape shown is frustum-shaped, or it could be dome-shaped, etc. The connecting zone is mainly used to rapidly reduce the high-speed gas-solid particles transported from the first reaction zone 1a to the gas-solid fluidization state required by the second reaction zone 1b.
[0041] The study of catalyst particle distribution in the second reaction zone 1b revealed that, axially, the catalyst particle density exhibits an "S-shaped" distribution, with a lower concentration and a higher concentration. Although the height of the concentrated phase is affected by gas velocity and particle delivery rate, it remains concentrated in the bottom section, below 60% of the height of the second reaction zone 1b. Radially, at any cross-section of the reactor, the maximum catalyst particle velocity is located at the center of the riser. The particle velocity maintains a relatively large and constant value in the central region, decreasing slowly towards the pipe wall. After r / R (where r represents the distance from the central axis and R is the pipe radius) reaches a certain value, the particle velocity suddenly decreases, becoming almost zero near the sidewalls. The sidewall effect exists throughout the variable-diameter riser. In the lower pneumatic conveying riser, where the gas velocity is above 10 m / s and r / R < 0.8, the axial velocity of the catalyst particles is relatively high. However, in the expansion section, where the apparent gas velocity is between 1.5 and 3 m / s, the sidewall effect is more pronounced. In the lower part of the expansion section, where r / R < 0.7, the catalyst particle velocity is relatively high, but the axial velocity of the catalyst particles near the sidewall is zero or even negative. In the upper part of the expansion section, where r / R < 0.6, the catalyst particle velocity is relatively high, but the velocity of the catalyst particles near the sidewall remains near zero. This means that a large portion of the catalyst is suspended in this section, and this portion of the catalyst may remain in the expansion section for too long, affecting the optimal process effect.
[0042] Based on the above research, the present invention provides a first internal component 8 at the outlet of the second reaction zone 1b, such as... Figure 2 As shown, the first internal component 8 is a first conveying pipe with the same diameter as the inner diameter of the third reaction zone 1c. The first internal component 8 is arranged parallel to the axial direction of the second reaction zone 1b and is connected to the inlet of the third reaction zone 1c, so that the oil and gas and catalyst in the second reaction zone 1b enter the third reaction zone 1c through the first internal component 8.
[0043] The first internal component 8 provided by the present invention can produce the following two effects: (1) When the apparent gas velocity in the expansion section decreases and a turbulent bed is formed, when the upper interface of the turbulent bed submerges the bottom port of the first internal component 8, the catalyst at the top of the turbulent bed can be drawn away, thus controlling the height of the turbulent bed in the expansion section and avoiding excessive bed pressure caused by an excessively high turbulent bed height. (2) The upper part of the expansion section, which is coaxial with the first internal component 8 and at the same height, can serve as the dilute phase section of the turbulent bed. Gas carries a large amount of particulate solids and throws them into the dilute phase section above the turbulent bed. As the gas flow velocity decreases, a free space for solid particles to settle is formed. The catalyst particles carried up by the turbulent bed will fall back into the lower part of the expansion section, increasing the catalyst density at the bottom of the expansion section and strengthening gas-solid mixing and contact. Since a considerable amount of gas is stored in the free space, it can provide a buffer space for gas pulsation in the reactor. The above two effects can, to a certain extent, avoid the rapid and sudden increase and fluctuation of the catalyst and gas pressure in the expansion section, and broaden the range of apparent gas velocity for optimal operation in the expansion section. For example, in a conventional MIP-CGP reactor, if the apparent gas velocity in the expansion section is too low, it is insufficient to carry the catalyst to the third reaction zone, which can easily lead to choking or even catalyst accumulation in the expansion section, causing equipment accidents. If the apparent gas velocity is too high, a dense phase section of the catalyst cannot be formed in the expansion section, which cannot meet the process requirements. Therefore, the apparent gas velocity in the expansion section of a conventional MIP-CGP is 1.4 to 2.8 m / s, and in industrial operation, it is generally preferred to be 1.5 to 2.0 m / s. However, the apparent gas velocity in the expansion section provided by this invention can reach 0.7 to 3.5 m / s, and further 0.9 to 2.5 m / s, while meeting the process requirements.
[0044] Furthermore, the height of the first internal component 8 is H1, and the height of the second reaction zone 1b is H2, with H1 / H2 = (0.15~0.8):1; even further, H1 / H2 = (0.2~0.6):1, and the height of the second reaction zone 1b is the sum of the heights of the main body zone and the connecting zone.
[0045] When the apparent gas velocity in the expansion section is low, the expansion section is prone to forming a turbulent bed. Therefore, it is necessary to appropriately increase the height of the first internal component 8. Specifically, the ratio of the height of the first internal component 8 to that of the second reaction zone 1b is (0.3~0.8):1, which helps to improve the gas-solid contact efficiency.
[0046] Furthermore, the distance H3 between the bottom port of the first internal component 8 and the bottom of the second reaction zone 1b is 2-8m, and the height H1 of the first internal component 8 is 2-7m; even further, the distance H3 between the bottom port of the first internal component 8 and the bottom of the second reaction zone 1b is 3-6m, and the height H1 of the first internal component 8 is 3-5m.
[0047] In addition, the tube wall of the first internal component 8 is provided with a number of first openings, through which the gas in the upper part of the second reaction zone 1b and the gas inside the first internal component 8 can flow to each other, so as to prevent the appearance of a dead zone without gas flow in the upper part of the second reaction zone.
[0048] The inner wall of the first opening is provided with a ceramic wear-resistant layer to improve wear resistance.
[0049] Furthermore, the distance between the first opening and the entrance of the third reaction zone 1c is no greater than 0.5 to 2m, that is, the first opening is located within a 0.5 to 2m range of the first internal component 8 near the upper part of the third reaction zone 1c.
[0050] Furthermore, the total area of the plurality of first openings is 5% to 30% of the cross-sectional area of the first inner component 8.
[0051] The second reaction zone 1b is equipped with a second internal component 9 near the entrance. The second internal component 9 is a distribution plate or a cap-shaped distributor.
[0052] When the second inner component 9 is a cap-type distributor, it can be used as follows: Figure 3 The conical cap distributor shown or such Figure 4 The umbrella-shaped cap distributor shown includes a cap and a second delivery pipe below the cap, wherein the cap is a central axis rotationally symmetric body with a shape similar to a cone or umbrella cap.
[0053] The cap has several second openings. The axial direction of the second openings is parallel to the axial direction of the second reaction zone 1b, that is, the second openings are set vertically, and the total area of the second openings is 8% to 15% of the total vertical projection area of the cap. The second openings can make the gas above the cap flow smoothly and prevent the catalyst from accumulating on the cap.
[0054] Furthermore, the ratio of the vertical projected area of the cap to the cross-sectional area of the second reaction zone 1b is 0.7 to 0.85:1, and the gas velocity at the edge of the cap is controlled to be above 2.5 m / s, preferably above 3.5 m / s, to ensure that catalyst accumulation does not occur at the bottom of the second reaction zone 1b or even in the transition section, thus preventing equipment operation accidents.
[0055] The second delivery pipe is located on the side of the cap near the entrance of the second reaction zone and is connected to the outlet of the first reaction zone 1a, so that the oil and gas and catalyst output from the first reaction zone 1a enter the second reaction zone 1b through the second delivery pipe; the pipe wall of the second delivery pipe is provided with several third openings, and the walls of the third openings extend outward to form gas channels.
[0056] Furthermore, the third opening is rectangular or elliptical in shape, and the total area of the third opening is 60% to 400% of the cross-sectional area of the first reaction zone 1a. The wall of the third opening is provided with a ceramic wear-resistant layer.
[0057] Furthermore, such as Figure 3 As shown, the plane formed by the axial and radial directions of the second reaction zone 1b is the projection plane. The orthogonal projection of the gas channel on this projection plane includes a first straight line and a second straight line parallel to the radial direction. The first straight line is located on the side closer to the third reaction zone 1c, and the second straight line is located on the side closer to the first reaction zone 1a. The length of the first straight line is greater than the length of the second straight line. That is, the end face of the gas channel is inclined downward, and the extension direction of the end face has a certain angle with the axial direction of the second reaction zone 1b, so as to avoid the outlet of the gas channel being blocked by the catalyst as much as possible and ensure the smoothness of the outlet.
[0058] When the second inner component 9 is a distribution plate, the distribution plate is one of an arched distribution plate, an irregular distribution plate, or a concave distribution plate. Several fourth openings are uniformly arranged on the distribution plate. The total area of the fourth openings is 15% to 25% of the vertical projection area of the distribution plate. A ceramic wear-resistant layer is arranged in the channel of the fourth opening.
[0059] Furthermore, the diameter of the fourth opening is 8–80 mm, and further, 10–50 mm.
[0060] The third reaction zone 1c is located above the second reaction zone 1b. Its inlet is connected to the outlet of the first internal component 8, and its inner diameter is smaller than that of the second reaction zone 1b. By reducing the inner diameter, the gas and catalyst in the second reaction zone 1b will be rapidly extracted to the first settling device 2.
[0061] The arrangement of the first internal component 8 and the second internal component 9 helps to broaden the range of apparent gas velocity in the second reaction zone 1b, making the diameter ratio of the second reaction zone 1b to other reaction zones wider. Specifically, the diameter ratio of the first reaction zone, the second reaction zone and the third reaction zone is 1:2 to 5:0.7 to 1.5, and the height ratio of the first reaction zone, the second reaction zone and the third reaction zone is 1:0.3 to 2:0.5 to 2.
[0062] Furthermore, the diameter ratio of the first reaction zone, the second reaction zone, and the third reaction zone is 1:2.5 to 4:0.7 to 1.5.
[0063] The second reaction unit 21 is a light oil catalytic reaction unit, comprising a pre-lifting section and a main reaction section for oil-catalyst contact reaction connected sequentially in the axial direction. The inner diameter of the pre-lifting section is less than or equal to the inner diameter of the main reaction section. The pre-lifting section is equipped with a pre-lifting gas inlet, a regenerated catalyst inlet, and a light oil feedstock inlet, used for inputting the second pre-lifting gas 19, light oil 20, and regenerated catalyst, respectively. Under the action of the second pre-lifting gas 19, the input light oil 20 and regenerated catalyst come into contact and rise, entering the main reaction section for catalytic reaction.
[0064] Furthermore, the diameter ratio of the first reaction zone 1a and the second reaction unit 21 is 1:(0.2~1), the height ratio is 1:(0.4~0.8), and further, the height ratio is 1:(0.5~0.7).
[0065] The second settling device 22 is connected to the outlet of the second reaction unit 21 and is used to perform gas-solid separation on the mixed reactants output by the second reaction unit 21. The second settling device 22 is a simple fast separation device with a cyclone arm. Unlike the cyclone separator in the first settling device 2, it can save the volume of the catalytic device and save space.
[0066] The second settling device 22 includes a second gas phase outlet and a second catalyst outlet. The second gas phase outlet is connected to the first settling device 2, allowing the gaseous products generated by the catalytic reaction of light oil to enter the first settling device 2 for further separation to remove catalyst powder entrained in the gaseous products. The second catalyst outlet is connected to the bottom of the second reaction zone 1b through the catalyst delivery pipe 25, allowing the catalyst to be input into the second reaction zone 1b to continue the catalysis of heavy oil, thereby increasing the catalyst flow rate and catalyst activity in the second reaction zone 1b and enhancing the catalytic reaction in the second reaction zone 1b. Furthermore, the separated gaseous products do not enter the first reaction unit 1, thus not affecting the oil and gas flow rate, velocity, and gas-solid fluidization in the first reaction unit 1. At the same time, it shortens the residence time of light oil in the high-temperature reaction zone and reduces the degree of thermal cracking reaction.
[0067] In addition, a second stripping steam 24 can be introduced at the bottom of the second settling tank 22 for stripping the catalyst. It should be noted that both the first stripping steam 14 and the second stripping steam 24 are stripping steam, differing only in their dosage, which can be achieved using conventional techniques in the field.
[0068] The first settling device 2 is located above the first reaction unit 1 in the axial direction and is connected to the outlet of the third reaction zone 1c. It is used to perform gas-solid separation on the mixed reactants output from the third reaction zone 1c and the second reaction unit 21. The first settling device 2 specifically includes a cyclone separator and a stripping section below the cyclone separator. The specific structure can be set according to conventional technical means in this field.
[0069] The cyclone separator separates the reaction product 13 and the catalyst to be developed. The separated reaction product 13 is output through the first gas phase outlet of the first settling tank 2, while the catalyst to be developed settles and enters the stripping section below. After removing the oil and gas adsorbed on the catalyst and displacing the oil and gas between the catalyst particles, it is output through the first catalyst outlet. Therefore, the bottom of the first settling tank 2 is also provided with a stripping steam inlet for inputting the first stripping steam 14.
[0070] The regeneration unit 3 is located on one side of the first reaction unit 1 and the first settling tank 2. The inlet of the regeneration unit 3 is connected to the first catalyst outlet of the first settling tank 2 through the catalyst delivery pipe 5. The regeneration unit 3 includes a regeneration air inlet and a regeneration flue gas outlet. Regeneration air 17 is delivered into the regeneration unit 3 through the regeneration air inlet, so that the regeneration air 17 comes into contact with the catalyst to be generated and undergoes an oxidation reaction to regenerate the catalyst. The regenerated catalyst enters the bottom inlet of the first reaction unit 1 and the second reaction unit 21 through the first regeneration catalyst delivery pipe 6 and the second regeneration catalyst delivery pipe 7. A heat exchanger 4 is connected between the first regeneration catalyst delivery pipe 6 and the second regeneration catalyst delivery pipe 7. The regenerated catalyst is cooled by injecting low-temperature water vapor 15 into the heat exchanger 4. After heat exchange, the low-temperature water vapor 15 generates high-temperature water vapor 16 and is discharged from the outlet of the heat exchanger 4. The regenerated flue gas 18 is output from the top of the regeneration unit 3 through the regeneration flue gas outlet and enters the flue gas turbine for further energy recovery and treatment.
[0071] The apparatus provided by the present invention further includes a raw material feeding unit and a quench agent feeding unit. The raw material feeding unit is connected to the bottom of the first reaction unit 1 and the bottom of the second reaction unit 21, and is used to deliver steam-atomized heavy oil 11 into the first reaction unit 1 and atomized light oil 20 into the second reaction unit 21. The quench agent feeding unit is connected to the bottom of the second reaction zone 1b, and is used to inject quench agent 12 into the second reaction zone 1b to reduce the temperature in the second reaction zone 1b, promote the occurrence of hydrogen transfer reaction, and prevent coking. The specific configuration can be made according to conventional technical means in the art.
[0072] In summary, this invention provides a catalytic device comprising a first reaction unit and a second reaction unit connected in parallel, both of which are equipped with independent settling tanks to avoid the problem of over-cracking of light oil. Furthermore, inputting the catalyst after reaction with the light oil into the second reaction zone helps to increase the catalyst flow rate and activity within the second reaction zone, thereby enhancing the catalytic reaction of heavy oil. Simultaneously, this invention also incorporates a first internal component and a second internal component within the second reaction zone, altering the flow state of the gas and catalyst, widening the adjustment range of the apparent gas velocity in the expansion section, and allowing the variable-diameter reactor to withstand a wider range of adjustment or fluctuation in the reaction oil and gas flow velocity, thus improving the processing capacity of the catalytic device.
[0073] A second aspect of the present invention provides a catalytic method for light oil and heavy oil, using any of the catalytic devices described above, comprising the following steps:
[0074] The steam-atomized heavy oil and the regenerated catalyst are fed into the first reaction zone through the pre-lift section of the first reaction unit. The mixed oil and gas and the regenerated catalyst rise in the first reaction unit and enter the first settling tank after passing through the first reaction zone, the second reaction zone and the third reaction zone.
[0075] The atomized light oil and regenerated catalyst are fed into the second reaction unit. The mixed oil and gas and the regenerated catalyst rise in the second reaction unit and enter the second settling tank.
[0076] The first settling device performs gas-solid separation on the mixed reactants output from the third reaction zone. The separated catalyst enters the regeneration unit through the first catalyst outlet. The second settling device performs gas-solid separation on the mixed reactants output from the second reaction unit. The separated catalyst enters the second reaction zone through the second catalyst outlet. The separated gaseous product enters the first settling device through the second gaseous outlet and is mixed with the gaseous product separated by the first settling device before being output through the first gaseous outlet.
[0077] The regeneration unit regenerates the catalyst to be generated from the outlet of the first catalyst and returns the regenerated catalyst to the first reaction unit and the second reaction unit for recycling.
[0078] In one specific embodiment, the heavy oil in this invention includes petroleum hydrocarbons and / or other mineral oils, wherein the petroleum hydrocarbons are selected from one or more of vacuum gas oil (VGO), atmospheric gas oil (AGO), coking gas oil (CGO), deasphalted oil (DAO), vacuum residue (VR), atmospheric residue (AR), and hydrotreated heavy oil, and the petroleum hydrocarbons may be unhydrogenated full fractions or partial fractions, or hydrogenated full fractions or partial fractions; the other mineral oils are selected from one or more of coal liquefaction oil, oil sands oil, and shale oil.
[0079] In this invention, light oils include light oils rich in olefins / light oils not rich in olefins. Light oils rich in olefins include gasoline and / or diesel. Gasoline includes one or more of the following: gasoline produced in this invention, conventional catalytic cracking gasoline, other catalytic cracking gasoline, coking gasoline, thermal cracking gasoline, and thermally cracked gasoline. Light oils not rich in olefins include one or more of the following: straight-run naphtha, straight-run gasoline, hydrotreated naphtha, alkanes with 4 to 8 carbon atoms, and raffinate.
[0080] The mass of light oil is 10% to 150% of the mass of heavy oil, and further 10% to 60%.
[0081] Furthermore, some of the light oil can be derived from reaction intermediates, that is, the light oil generated by the reaction is returned to the second reaction unit 21 for reprocessing; the content of the reprocessed light oil can be adjusted according to the content of light oil generated by the catalytic unit, and external light oil feedstock can be appropriately supplemented.
[0082] In this invention, the catalyst is a catalyst suitable for catalytic cracking or catalytic pyrolysis, and its active component is selected from one or more of the following: amorphous silica-alumina catalyst, Y or HY type zeolite with or without rare earth elements, ultra-stable Y type zeolite with or without rare earth elements, ZSM-5 series zeolite, or high silica zeolite with a five-membered ring structure prepared by other methods; the temperature of the regenerated catalyst transported from the second regeneration inclined tube 7 is 660℃~760℃.
[0083] The first pre-lift gas 10 is input from the pre-lift section at the bottom of the first reaction unit 1. The steam-atomized heavy oil 11 and the regenerated catalyst are then input into the pre-lift section, mixed, and ascend. The ascending oil and gas, along with the catalyst, enter the second reaction zone 1b via the first reaction zone 1a and the second internal component 9, where they are fully mixed and react. The arrangement of the first internal component 8 and the second internal component 9 causes the oil and gas to change direction and its apparent velocity to decrease, resulting in a turbulent bed or dense phase transport bed state for the catalyst, thus enhancing the contact between the oil and the catalyst. The oil and gas, along with the catalyst, enter the third reaction zone 1c via the first internal component 8.
[0084] Due to the narrowing of the third reaction zone 1c, oil, gas and catalyst rapidly enter the first settling tank 2 for gas-solid separation.
[0085] Furthermore, the apparent residence times of oil and gas in the first reaction zone 1a, the second reaction zone 1b, and the third reaction zone 1c are 0.8–2 seconds, 5–15 seconds, and 0.5–1.5 seconds, respectively.
[0086] Meanwhile, the light oil 20 after steam atomization or direct mechanical spraying and the regenerated catalyst are introduced into the second reaction unit 21, rise under the action of the second pre-lifting gas 19, and come into contact and react in the second reaction unit 21. The oil and gas generated by the reaction and the catalyst are injected into the second settling tank 22 through the outlet.
[0087] The second settling tank 22 is used to perform gas-solid separation on the mixed reactants output from the second reaction unit 21. The separated gaseous products are fed into the first settling tank 2 for further separation via the gaseous product conveying pipe 23. The separated catalyst is stripped with or without the second stripping steam 24 and then fed into the bottom of the second reaction zone 1b via the catalyst conveying pipe 25 to be mixed with the heavy oil 11 feedstock for further catalysis.
[0088] The mixed reactants input into the third reaction zone 1c and the gaseous products input into the second reaction unit 21 enter the first settling tank 2 for gas-solid separation. The separated reaction product 13 is output through the first gas phase outlet. The carbonized spent catalyst obtained from the separation enters the stripping section at the bottom of the first settling tank 2. After being stripped by the first stripping steam 14, it is output and enters the regeneration unit 3 through the spent catalyst conveying pipe 5. Regeneration air 17 is input into the regeneration unit 3, so that the spent catalyst comes into contact with the regeneration air 17 and undergoes an oxidation reaction to obtain the regenerated catalyst. The regenerated catalyst enters the heat exchanger 4 through the first regenerated catalyst conveying pipe 6. After being cooled by low-temperature water vapor 15, it returns to the bottom of the first reaction unit 1 and the second reaction unit 21 through the second regenerated catalyst conveying pipe 7 for recycling. The low-temperature water vapor 15 is converted into high-temperature water vapor 16 after heat exchange and discharged. The regenerated flue gas 18 is output from the top of the regeneration unit 3 and enters the flue gas turbine for further energy recovery and treatment.
[0089] In addition, to control the reaction temperature, a quenching agent 12 can be injected into the connecting area between the first reaction zone 1a and the second reaction zone 1b; further, it can be injected into the top of the first reaction zone 1a or the bottom of the second reaction zone 1b. The quenching agent 12 includes one or more of water, recycled oil, gasoline, diesel, and sludge, and the injection amount is 1 to 10 wt% of the catalyst feedstock. The temperature of the quenching agent is room temperature to 200°C.
[0090] Regenerated catalyst, cooled regenerated catalyst, or regenerating agent can be injected into the upper part of the first reaction zone 1a or the middle and lower part of the second reaction zone 1b to replenish the catalyst activity in the second reaction zone 1b.
[0091] By changing the catalyst and adjusting the operating conditions, this invention can achieve switching between two operating modes: 1. Ultra-low olefin gasoline production mode: controlling the temperature at the inlet of the first internal component 8 to 510℃~540℃, further to 515℃~530℃; controlling the temperature of the regenerated catalyst or the catalyst to be generated injected into the upper part of the first reaction zone 1a or the middle and lower part of the second reaction zone 1b to 560℃~660℃; 2. High-crack gas production mode: controlling the temperature at the inlet of the first internal component 8 to 550℃~640℃, further to 560℃~600℃; controlling the temperature of the regenerated catalyst or the catalyst to be generated injected into the upper part of the first reaction zone 1a or the middle and lower part of the second reaction zone 1b to 580℃~680℃.
[0092] In summary, by using the device provided by this invention to catalyze light and heavy oils, the production modes of ultra-low olefin gasoline and high-volume cracked gas production can be switched by changing the catalyst and adjusting the operating conditions, thus achieving flexible control over product properties and product distribution.
[0093] The following examples will further illustrate the present invention, but are not intended to limit the invention. The properties of the catalytic feedstock and catalyst used in the examples and comparative examples are listed in Tables 1 and 2, respectively. The catalysts in Table 2 were produced by Lanzhou Catalyst Plant of China National Petroleum Corporation.
[0094] Example 1
[0095] The catalytic device provided in this embodiment has Figure 1 The structure shown includes a first reaction unit comprising a pre-lifting section, a first reaction zone 1a, a second reaction zone 1b, and a third reaction zone 1c, with a total height of 18 meters. The pre-lifting section has a diameter of 0.25 meters and a height of 1.5 meters. The first reaction zone has a diameter of 0.30 meters and a height of 4 meters; the second reaction zone has a diameter of 1.2 meters and a height of 7.6 meters; and the third reaction zone has a diameter of 0.30 meters and a height of 4 meters. The longitudinal section of the junction between the first / third reaction zone and the second reaction zone is an isosceles trapezoid, with the lateral line of the isosceles trapezoid forming an angle of 45° with the axis, and the height of the isosceles trapezoid is 0.45 meters.
[0096] The second reaction zone 1b is provided with a first internal component 8 and a second internal component 9. The diameter of the first internal component 8 is 0.30 meters and the height is 2.5 meters. Several first openings are provided above the first internal component 8. The first openings are concentrated in the range of 0.5 to 2 meters above the first internal component 8. The total area of the first openings is 10% of the cross-sectional area of the first internal component.
[0097] The second internal component 9 is a conical cap distributor, the structure of which is as follows: Figure 3 As shown, the system includes a cap and a second conveying pipe located below the cap. The cap is a cone with an isosceles triangle cross-section, and the base angle of the isosceles triangle is 15°. A second opening parallel to the axial direction of the second reaction zone is provided on the cap. The diameter of the second opening is 0.01–0.05 m, and the total area of the second opening accounts for 10% of the total vertical projection area of the cap. The ratio of the vertical projection area of the cap to the cross-sectional area of the second reaction zone 1b is 0.8:1. The second conveying pipe has a height of 3 m and an inner diameter identical to that of the first reaction zone 1a. A third opening is provided on the second conveying pipe, and the total area of the third opening is 150% of the cross-sectional area of the first reaction zone 1a.
[0098] The second reaction unit 21 has a total height of 17 meters, of which the pre-lifting section and the main reaction section are 2 meters and 15 meters respectively, and the diameters are 0.12 meters and 0.15 meters respectively; the second settling tank 22 has a rapid separation system with a cyclone arm, and the diameter of the light hydrocarbon settling tank is 1 meter; the diameter of the gas phase product conveying pipe 23 is 0.2 meters.
[0099] Based on the above-mentioned apparatus, using the heavy oil and light gasoline A shown in Table 1 as raw materials, and catalyst A shown in Table 2, ultra-low olefin gasoline is produced. The mass of light gasoline A is 30% of the heavy oil raw material, half of which is light gasoline produced by the apparatus itself, and half of which comes from other apparatus outside this apparatus. The production conditions, product distribution, and main properties of the gasoline are shown in Table 3.
[0100] Example 2
[0101] The apparatus and catalytic process provided in this embodiment are similar to those in Embodiment 1, except that the second internal component is a cap-shaped distributor, with the structure as follows: Figure 4 As shown, catalyst B from Table 2 was used, and the operating conditions, product distribution, and main properties of gasoline are shown in Table 3.
[0102] Comparative Example 1
[0103] The catalytic device provided in this comparative example is the same as that in Example 1, except that it does not include a second reaction unit and a second settler.
[0104] Using the above-described apparatus, ultra-low olefin gasoline was produced with the same raw materials and catalyst A as in Example 1. The operating conditions, product distribution, and main properties of the gasoline are shown in Table 3.
[0105] Comparative Example 2
[0106] The catalytic device provided in this comparative example can be referenced from Comparative Example 1, except that the first internal component 8 is not provided in the second reaction zone 1b, and the inner diameter of the second reaction zone is 0.9 meters.
[0107] Ultra-low olefin gasoline was produced using the same raw materials and catalyst A as in Example 1. The operating conditions, product distribution, and main properties of the gasoline are shown in Table 3.
[0108] Comparative Example 3
[0109] The catalytic device provided in this comparative example can be referred to in Example 2, except that it does not include a second reaction unit and a second settler.
[0110] Using the above-described apparatus, with the same raw materials and catalyst B as in Example 2, a multi-product cracked gas operation mode was performed. The operating conditions, product distribution, and main properties of gasoline are shown in Table 3.
[0111] Comparative Example 4
[0112] The catalytic device provided in this comparative example can be referenced from Comparative Example 3, except that the first internal component 8 is not provided in the second reaction zone 1b, and the inner diameter of the second reaction zone is 0.9 meters.
[0113] Using the above-described apparatus, with the same raw materials and catalyst B as in Example 2, a multi-product cracked gas operation mode was performed. The operating conditions, product distribution, and main properties of gasoline are shown in Table 3.
[0114] Table 1 Properties of Crude Oil
[0115]
[0116]
[0117] Table 2 Catalyst Properties
[0118]
[0119] Table 3 Operating Conditions and Product Distribution
[0120]
[0121]
[0122] As shown in Table 3, Examples 1, 1 (Comparative Example), and 2 (Comparative Example) all operate in a mode for producing ultra-low olefin gasoline. Compared to Comparative Example 2, Comparative Example 1 incorporates a first internal component in the second reaction zone, which helps to increase the diameter ratio. Compared to Comparative Example 1, Example 1, which reprocesses 30% of light gasoline A, shows a 1.3 percentage point reduction in olefin content. Examples 2, 3 (Comparative Example), and 4 (Comparative Example) all operate in a mode for producing more cracked gas. Compared to Comparative Examples 3-4, Example 2, which reprocesses 30% of light gasoline B, also shows an increased cracked gas yield.
[0123] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A catalytic converter for light oil and heavy oil, characterized in that, The catalytic device includes a first reaction unit, a second reaction unit, a first settling tank, a second settling tank, and a regeneration unit, wherein: The first reaction unit is a heavy oil catalytic reaction unit. The first reaction unit includes a pre-lifting section, a first reaction zone, a second reaction zone, and a third reaction zone that are connected in sequence in the axial direction. The inner diameter of the second reaction zone is larger than the inner diameters of the first reaction zone and the third reaction zone. The outlet of the third reaction zone is connected to the first settling device. The second reaction zone is provided with a first internal component and a second internal component. The first internal component is a first conveying pipe with the same diameter as the inner diameter of the third reaction zone. The first conveying pipe is connected to the inlet of the third reaction zone. The pipe wall of the first conveying pipe is provided with a plurality of first openings. The second internal component is a distribution plate or a cap-type distributor. The second internal component is located near the inlet of the second reaction zone. The second reaction unit is a light oil catalytic reaction unit, and the outlet of the second reaction unit is connected to the second settler; The first settling device includes a first gas phase outlet and a first catalyst outlet, and the second settling device includes a second gas phase outlet and a second catalyst outlet. The second gas phase outlet is connected to the first settling device, and the second catalyst outlet is connected to the second reaction zone. The first gas phase outlet is used to output reaction products, and the first catalyst outlet is connected to the inlet of the regeneration unit. The outlet of the regeneration unit is connected to the inlets of the first reaction unit and the second reaction unit.
2. The catalytic device according to claim 1, characterized in that, The height ratio of the first internal component to the height of the second reaction zone is 0.15 to 0.8:
1.
3. The catalytic device according to claim 1 or 2, characterized in that, The distance between the bottom port of the first internal component and the bottom of the second reaction zone is 2 to 8 m, and the height of the first internal component is 2 to 7 m.
4. The catalytic device according to claim 1, characterized in that, The distance between the first opening and the entrance to the third reaction zone is no greater than 0.5 to 2 m; the total area of the first opening is 5% to 30% of the cross-sectional area of the first internal component.
5. The catalytic device according to claim 1 or 2, characterized in that, The diameter ratio of the first reaction zone, the second reaction zone, and the third reaction zone is 1:2 to 5:0.7 to 1.5, and the height ratio of the first reaction zone, the second reaction zone, and the third reaction zone is 1:0.3 to 2:0.5 to 2.
6. The catalytic device according to claim 1, characterized in that, The diameter ratio of the first reaction zone to the second reaction unit is 1:0.2 to 1, and the height ratio of the first reaction unit to the second reaction unit is 1:0.4 to 0.
8.
7. The catalytic device according to claim 1, characterized in that, When the second internal component is a distribution plate, the distribution plate is one of an arched distribution plate, an irregularly shaped distribution plate, or a concave distribution plate.
8. The catalytic device according to claim 1, characterized in that, When the second internal component is a cap-type distributor, the cap-type distributor includes a cap and a second conveying pipe. The cap is disposed on the side of the second conveying pipe near the outlet of the second reaction zone, and the second conveying pipe is connected to the outlet of the first reaction zone. The cap has several second openings, and the wall of the second conveying pipe has several third openings. The wall of the third opening extends outward to form a gas channel.
9. The catalytic device according to claim 8, characterized in that, The total area of the second opening is 8% to 15% of the total area of the vertical projection of the cap, and the total area of the third opening is 60% to 400% of the cross-sectional area of the first reaction zone.
10. A catalytic method for light oil and heavy oil, characterized in that, The process, performed using the catalytic apparatus according to any one of claims 1 to 9, includes the following steps: The steam-atomized heavy oil and the regenerated catalyst are fed into the first reaction zone through the pre-lift section of the first reaction unit. The mixed oil and gas and the regenerated catalyst rise in the first reaction unit and enter the first settling tank after passing through the first reaction zone, the second reaction zone and the third reaction zone. The atomized light oil and regenerated catalyst are fed into the second reaction unit. The mixed oil and gas and the regenerated catalyst rise in the second reaction unit and enter the second settling tank. The first settling device performs gas-solid separation on the mixed reactants output from the third reaction zone. The separated catalyst enters the regeneration unit through the first catalyst outlet. The second settling device performs gas-solid separation on the mixed reactants output from the second reaction unit. The separated catalyst enters the second reaction zone through the second catalyst outlet. The separated gaseous product enters the first settling device through the second gaseous outlet and is mixed with the gaseous product separated by the first settling device before being output through the first gaseous outlet. The regeneration unit regenerates the catalyst to be generated from the outlet of the first catalyst and returns the regenerated catalyst to the first reaction unit and the second reaction unit for recycling.
Citation Information
Patent Citations
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