Oil phase hydrogenation reaction strengthening system and method

Abstract

The invention relates to an oil phase hydrogenation reaction strengthening system and method, and belongs to the technical field of oil phase hydrogenation processes. The system comprises a hydrogen conveying unit, a liquid phase conveying unit, a hydrogen mixing unit, and a preheating unit, a hydrogenation reaction unit and a separation unit which are communicated in sequence, the hydrogenation reaction unit comprises a hydrogenation reactor, and the hydrogen mixing unit comprises an in-reactor hydrogen mixing device and an out-reactor hydrogen mixing device; the hydrogen conveying unit and the liquid phase conveying unit are respectively communicated with the reactor external hydrogen mixing device, and the reactor external hydrogen mixing device is communicated with the preheating unit. Wherein the in-reactor hydrogen mixing device comprises an annular pipe and a plurality of gas dispersion pipes arranged on the annular pipe in a communicating manner, an in-reactor gas phase inlet is formed in the side wall of the annular pipe, and the in-reactor gas phase inlet is communicated with a hydrogen conveying unit; a plurality of through holes are formed in the side wall of the gas dispersion pipe. When the system is used for oil phase hydrogenation, small and uniform microbubbles can be efficiently formed, so that the hydrogenation reaction efficiency can be improved, and the energy consumption in the hydrogenation process can be reduced.

Description

Technical Field

[0001] This application relates to the field of oil-phase hydrogenation process technology, and particularly to an oil-phase hydrogenation reaction enhancement system and method. Background Technology

[0002] In traditional hydrogenation processes such as trickle bed hydrogenation or liquid phase hydrogenation, hydrogen, oil phase, and hydrogenation catalyst need to undergo hydrogenation reaction at the gas-liquid-solid three-phase interface in the hydrogenation reactor. Due to the low solubility of hydrogen in the oil phase (such as wax oil), the hydrogen and oil phase are not mixed evenly, resulting in a low catalytic reaction rate for wax oil hydrogenation and persistently high energy and material consumption.

[0003] High-efficiency hydrogen mixing with microbubbles has become a research hotspot in recent years. By using a microbubble generator to disperse the gas phase into micron-sized bubbles in the liquid phase, the multiphase mass transfer reaction process can be significantly enhanced. However, in existing hydrogenation reaction systems, the diameter of the generated hydrogen microbubbles is still relatively large and the distribution is uneven, the hydrogenation pressure is high, and the energy consumption of the production process has not been effectively reduced. Summary of the Invention

[0004] To address the aforementioned technical problems, embodiments of this application provide an oil-phase hydrogenation reaction enhancement system and method, which can efficiently form small and uniform microbubbles, improve hydrogen mixing effect and rate, increase hydrogenation reaction efficiency, and reduce energy consumption in the hydrogenation process.

[0005] In a first aspect, embodiments of this application provide an oil-phase hydrogenation reaction enhancement system, including a hydrogen delivery unit, a liquid-phase delivery unit, a hydrogen mixing unit, and a preheating unit, a hydrogenation reaction unit, and a separation unit connected in sequence; the hydrogenation reaction unit includes a hydrogenation reactor, and the hydrogen mixing unit includes an in-reactor hydrogen mixing device disposed within the hydrogenation reactor and an external hydrogen mixing device disposed outside the hydrogenation reactor; the hydrogen delivery unit and the liquid-phase delivery unit are respectively connected to the external hydrogen mixing device, and the external hydrogen mixing device is connected to the preheating unit.

[0006] The reactor includes at least one annular pipe and multiple gas dispersion pipes connected to the annular pipe. The annular pipe has a gas phase inlet on its side wall, which is connected to a hydrogen delivery unit. The gas dispersion pipes have multiple through holes on their side walls.

[0007] In the above technical solution, by setting up an external hydrogen mixing device and an internal hydrogen mixing device inside the hydrogenation reactor, hydrogen can be continuously supplied to the hydrogenation reactor during the hydrogenation reaction, maintaining the saturated dissolved hydrogen state of the liquid phase inside the hydrogenation reactor. Furthermore, hydrogen can be uniformly transported to the gas dispersion pipe through the annular pipe, and dispersed into small and uniform microbubbles by the gas dispersion pipe. These microbubbles then enter the reactor and mix efficiently with the liquid phase, which can effectively improve hydrogen utilization efficiency, significantly increase the mass transfer rate of the hydrogenation reaction, thereby reducing the reaction operating temperature and pressure, eliminating the need for a circulating hydrogen compressor, improving hydrogenation reaction efficiency, and reducing energy consumption in the production process.

[0008] In some embodiments, the hydrogenation reactor contains at least two catalyst beds, with a gas dispersion tube disposed within the catalyst bed. Microbubbles generated by the gas dispersion tube can directly enter the catalyst bed and participate in the hydrogenation reaction, which is beneficial for further improving the hydrogenation reaction efficiency.

[0009] Preferably, the catalyst bed consists of 2 to 4 sections.

[0010] Preferably, the gas dispersion tubes are vertically distributed on the annular tube.

[0011] Preferably, multiple gas dispersion tubes are evenly spaced on the annular tube.

[0012] Preferably, the hydrogen mixing device in the reactor includes multiple annular tubes arranged in concentric circles, and each pair of adjacent annular tubes is connected by a pipeline.

[0013] Preferably, the number of gas dispersion tubes distributed on each annular tube is 4 to 36.

[0014] Preferably, the material of the annular tube and the gas dispersion tube is independently at least one of stainless steel, titanium alloy, Hastelloy, glass or ceramic.

[0015] Preferably, the diameter of the through hole is 100nm~100μm.

[0016] In the above technical solution, by further designing the number and size of the gas dispersion tubes and the distribution of the gas dispersion tubes and the annular tubes, the size uniformity of the generated microbubbles, as well as the uniformity and mixing efficiency in the liquid phase, can be further improved, thereby further improving the hydrogenation reaction efficiency, reducing the reaction pressure and temperature, and thus reducing the energy consumption of the production process.

[0017] In some embodiments, the external hydrogen mixing device includes a shell with a liquid phase inlet and a mixture outlet at both ends. An external gas phase inlet is provided on the side wall of the shell. The liquid phase inlet is connected to a liquid phase conveying unit, the external gas phase inlet is connected to a hydrogen conveying unit, and the mixture outlet is connected to a preheating unit. Inside the shell, the liquid inlet is sequentially connected to a liquid phase chamber, a liquid phase channel, a gas-liquid mixing channel, a diffusion channel, a gas release chamber, and a mixture outlet. The diameters of the liquid phase channel and the diffusion channel gradually increase in the direction away from the gas-liquid mixing channel. The gas phase inlet outside the device is connected to a gas phase chamber, and the gas-liquid mixing channel is located inside the gas phase chamber. The sidewall of the gas-liquid mixing channel is perforated, and the surface of the sidewall facing the gas phase chamber is provided with a micro-nano porous membrane. The gas release chamber is provided with spiral guide vanes.

[0018] In the above technical solution, by designing a reactor-external hydrogen mixing device with a specific structure, the oil phase, after passing through the liquid phase channel, experiences accelerated flow velocity due to the Venturi effect, generating negative pressure. This draws hydrogen from the gas phase chamber into the gas-liquid mixing channel, where it is cut and dispersed into uniformly sized microbubbles under the pressure difference across the micro / nano porous membrane. These microbubbles mix efficiently with the oil phase and are then rapidly released into the release chamber through the diffusion channel. Furthermore, the spiral guide vanes rotate under the high-speed impact of the mixture, using centrifugal force to further cut the gas-liquid mixture, achieving secondary bubble breakage and forming even smaller microbubbles. This further improves hydrogen utilization efficiency, significantly increases the mass transfer rate of the hydrogenation reaction, thereby reducing the reaction operating temperature and pressure, eliminating the need for a circulating hydrogen compressor, improving hydrogenation reaction efficiency, and reducing energy consumption in the production process.

[0019] In some embodiments, an electric heating element is embedded within the casing. By incorporating this element within the casing, the gaseous and liquid materials can be preheated during hydrogen mixing. This allows for staged heating in conjunction with a preheating unit, reducing the energy consumption of a single device. Furthermore, it can replace a heating furnace, simplifying the equipment composition of the preheating unit and further simplifying the device, reducing production costs and energy consumption in the production process. Additionally, the electric heating element can melt or vaporize the pore blockages in the micro / nanoporous membrane through high temperatures, thereby ensuring long-term stable operation of the device.

[0020] Preferably, the electric heating element includes an insulating inner layer, a tungsten alloy conductive layer, and a protective outer layer. By configuring the structure of the electric heating element, efficient heating of the material inside the shell can be achieved, and the direction of heat flow can be controlled by the structural design of each layer (e.g., arc shape, spiral shape, etc.), enabling directional heating of the material into the shell.

[0021] Preferably, the shell is made of stainless steel. The stainless steel shell gives the external hydrogen mixing device of the reactor high strength, high corrosion resistance, and sealing performance, which is beneficial for the long-term stable use of the device.

[0022] In some embodiments, the surface of the micro / nanoporous membrane is coated with an oleophobic nanocoating. This oleophobic nanocoating can reduce bubble coalescence, further decrease the size of the microbubbles, and improve their size uniformity.

[0023] Preferably, the material of the micro / nanoporous membrane includes at least one of metal, plastic or ceramic.

[0024] Preferably, the thickness of the micro / nanoporous membrane is 50 μm to 2 mm.

[0025] Preferably, the average diameter of the micro-nanoporous pores on the micro-nanoporous membrane is 100 nm to 100 μm.

[0026] In some embodiments, a drive device is also provided inside the external hydrogen mixing device of the reactor. The drive device is connected to a helical guide vane to drive the helical guide vane to rotate. By driving the helical guide vane to rotate at high speed, a cavitation effect can be generated, which further reduces the size of microbubbles and improves the size uniformity of microbubbles.

[0027] In some embodiments, the preheating unit includes a heat exchanger with interconnected hot material inlet and cold material outlet, and interconnected cold material inlet and preheated material outlet. An external hydrogen mixing device is connected to the cold material inlet of the heat exchanger, the liquid phase outlet of the hydrogenation reactor is connected to the hot material inlet of the heat exchanger, and the preheated material outlet is connected to the feed inlet of the hydrogenation reactor. By incorporating the heat exchanger, the heat from the high-temperature hydrogenation product can be utilized, eliminating the need for a heating furnace and thus reducing energy consumption in the production process.

[0028] Preferably, the preheating unit further includes a circulating oil pump. The outlet of the hydrogenation reaction unit is connected to the inlet of the circulating oil pump, and the outlet of the circulating oil pump is connected to the preheated material outlet of the heat exchange device and the inlet of the hydrogenation reactor. By setting up a circulating oil pump and utilizing the heat from the high-temperature hydrogenation products, the energy consumption of the production process can be further reduced, the quality of the hydrogenation products can be further improved, and the desulfurization effect can be enhanced.

[0029] Preferably, the preheating unit further includes a heating device, which is connected between the heat exchange device and the external hydrogen mixing device. By providing the heating device, heat can be quickly provided at the beginning of system operation, allowing the reaction to proceed rapidly.

[0030] In some embodiments, the separation unit includes a first separation device and a second separation device. The first separation device is located at the top of the hydrogenation reactor and is connected to the liquid phase outlet and the gas phase outlet of the hydrogenation reactor. The gas phase outlet of the hydrogenation reactor and the cold material outlet of the heat exchanger are respectively connected to the second separation device. By setting up the first and second separation devices, the hydrogenation gas phase product and the hydrogenation liquid phase product after heat exchange can be efficiently separated.

[0031] Secondly, embodiments of this application also provide a method for using the above-described oil-phase hydrogenation reaction enhancement system, comprising the following steps: The oil phase is transported to the external hydrogen mixing device through the liquid phase conveying unit, and hydrogen is transported to the external hydrogen mixing device through the hydrogen conveying unit to mix with the oil phase to obtain a gas-liquid mixture. The gas-liquid mixture is transported to the preheating unit for preheating, and then transported to the hydrogenation reactor to contact the hydrogenation catalyst for hydrogenation reaction. At the same time, hydrogen is introduced into the hydrogen mixing device in the reactor through the hydrogen delivery unit and dispersed into microbubbles to participate in the hydrogenation reaction. After the reaction is completed, the hydrogenated product is obtained. The hydrogenation products are transported to a separation unit for separation to obtain hydrogenated oil products.

[0032] In the above-mentioned technical solution, the method in this application can form smaller and more uniform microbubbles from hydrogen, thereby improving hydrogen utilization, increasing the mass transfer efficiency of hydrogen-oil mixing, and thus effectively improving the efficiency of hydrogenation reaction. Compared with the traditional trickle bed hydrogenation process, under the same hydrogenated oil properties, the reaction temperature can be reduced by more than 10°C, the reaction pressure can be reduced by more than 4 MPa, the hydrogen-oil ratio can be reduced by more than 50%, and the overall energy consumption of the device can be reduced by more than 50%. Under the same hydrogenation reaction conditions, the sulfur content in the hydrogenation products can be reduced by more than 50%. That is, the method in this application has significant energy-saving, carbon-reducing, quality-improving, and efficiency-enhancing effects.

[0033] In some implementations, the size of the microbubbles is 50 nm to 1000 μm.

[0034] In some embodiments, the oil phase includes at least one of wax oil, residue oil, lubricating oil, diesel oil, kerosene, or reformed oil.

[0035] In some embodiments, the hydrogenation reaction is carried out at a temperature of 350°C to 450°C and a pressure of 8 MPa to 15 MPa.

[0036] In some embodiments, the volume ratio of hydrogen to oil phase input into the hydrogen mixing device in the reactor is (50~300):1. Attached Figure Description

[0037] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0038] Figure 1 This is a schematic diagram of an oil-phase hydrogenation reaction enhancement system provided in an embodiment of this application.

[0039] Figure 2 for Figure 1 A schematic diagram of the external hydrogen mixing device in the reactor.

[0040] Figure 3 for Figure 1A schematic diagram of the hydrogen mixing device inside the reactor.

[0041] Explanation of reference numerals in the attached figures: 1-Hydrogen; 2-Hydrogen filtration device; 3-Hydrogen buffer tank; 4-Hydrogen compressor; 5-Oil phase; 6-Oil phase filtration device; 7-Oil phase feed pump; 8-External hydrogen mixing device; 81-Shell; 82-Liquid inlet; 821-Liquid chamber; 823-Liquid channel; 83-Gas-liquid mixing channel; 832-Pore; 834-Micro / nano porous membrane; 84-External gas inlet; 841-Gas chamber; 85-Diffusion channel; 86-Release chamber; 8 62-Helical guide vane; 864-Drive device; 87-Mixed material outlet; 9-Hydrogenation reactor; 10-Catalyst bed; 11-Hydrogen mixing device inside the reactor; 110-Gas phase inlet inside the reactor; 112-Annular pipe; 114-Annular gas chamber; 116-Gas dispersion pipe; 12-First separation device; 13-Circulating oil pump; 14-Heating device; 15-Heat exchange device; 16-Second separation device; 17-Hydrogenated oil; 18-Gas phase separation product. Detailed Implementation

[0042] The embodiments of the oil-phase hydrogenation reaction enhancement system and method of this application are hereby specifically disclosed in detail with appropriate reference to the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for the purpose of enabling those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0043] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for a specific parameter, it is also expected that ranges of 60~110 and 80~120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0044] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0045] Figure 1 Please refer to the structural schematic diagram of an oil-phase hydrogenation reaction enhancement system provided in one embodiment of this application. Figure 1 The oil-phase hydrogenation reaction enhancement system provided in the first aspect of this application includes: a hydrogen delivery unit, a liquid-phase delivery unit, a hydrogen mixing unit, and a preheating unit, a hydrogenation reaction unit, and a separation unit connected in sequence. The hydrogenation reaction unit includes a hydrogenation reactor 9, and the hydrogen mixing unit includes an external hydrogen mixing device 8 and an internal hydrogen mixing device 11 disposed within the hydrogenation reactor 9.

[0046] Please see also Figure 2 The reactor external hydrogen mixing device 8 includes a shell 81. The shell 81 has a liquid phase inlet 82 and a mixture outlet 87 at both ends. The side wall of the shell 81 has an external gas phase inlet 84. The liquid phase inlet 82 is connected to the liquid phase conveying unit, the external gas phase inlet 84 is connected to the hydrogen conveying unit, and the mixture outlet 87 is connected to the preheating unit.

[0047] Inside the casing 81, the liquid inlet 82 is sequentially connected to a liquid phase chamber 821, a liquid phase channel 823, a gas-liquid mixing channel 83, a diffusion channel 85, a gas release chamber 86, and a mixture outlet 87. The diameters of the liquid phase channel 823 and the diffusion channel 85 gradually increase in the direction away from the gas-liquid mixing channel 83. An external gas phase inlet 84 is connected to a gas phase chamber 841. The gas-liquid mixing channel 83 is located within the gas phase chamber 841. The sidewall of the gas-liquid mixing channel 83 has through-holes 832, and a micro / nano porous membrane 834 is provided on the side of the sidewall facing the gas phase chamber 841. A spiral guide vane 862 is provided inside the gas release chamber 86.

[0048] In some embodiments, the surface of the micro / nanoporous membrane 834 is provided with an oleophobic nanocoating. As an example, the oleophobic nanocoating may be a fluorine-based nanocoating comprising fluoropolymers (such as perfluoropolyether PFPE, fluorosilanes, etc.).

[0049] In some embodiments, the material of the micro / nanoporous membrane 834 includes at least one of metal, plastic or ceramic.

[0050] Furthermore, the thickness of the micro / nanoporous membrane is 50μm to 2mm, for example, it can be 50μm, 100μm, 200μm, 400μm, 600μm, 800μm, 1000μm, 1200μm, 1400μm, 1600μm, 1800μm or 2000μm, etc.

[0051] Furthermore, the diameter of the micro-nanoporous pores on the micro-nanoporous membrane is 100nm~100μm, for example, it can be 0.1μm, 0.5μm, 1μm, 5μm, 10μm, 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm or 100μm, etc.

[0052] In some embodiments, the external hydrogen mixing device 8 further includes a drive device 864 connected to a helical guide vane 862, which can drive the helical guide vane 862 to rotate at high speed. As an example, the drive device 864 can be an adjustable speed motor.

[0053] In this embodiment, after passing through the gas-liquid mixing channel 83, the diameter of the microbubbles can reach 100μm~1000μm; after passing through the spiral guide vane 862, the diameter of the microbubbles can be reduced to 10μm~100μm; after being connected to the driving device 864 and rotated at high speed, the diameter of the microbubbles can be reduced to 50nm~10μm.

[0054] In some embodiments, an electric heating element (not shown) is embedded within the housing 81. Preferably, the electric heating element includes an insulating inner layer, a tungsten alloy conductive layer, and a protective outer layer. Further, the housing 81 is made of stainless steel.

[0055] As an example, a tungsten alloy electric heating element is embedded inside the stainless steel wall of the housing 81. The tungsten alloy heating material can be arranged inside the circular wall of the housing 81. This material consists of an inner insulating layer (alumina insulating layer), a middle layer (tungsten alloy conductive layer), and an outer layer (alumina protective layer), forming a physical isolation barrier to prevent current leakage. Current is input from an external power source to the housing 81, enters the tungsten alloy electric heating element through conductive leads, flows through the tungsten alloy conductive layer, and returns to the circuit to form a loop. Furthermore, the tungsten alloy electric heating element can control the direction of heat flow through geometric design (arc, spiral, swirling structure), achieving directional heating of the equipment's interior. The electric heating temperature can be flexibly adjusted within the range of 0~1000℃.

[0056] Please see Figure 1 and Figure 3 The hydrogen mixing device 11 inside the reactor includes at least one annular pipe 112 and multiple gas dispersion pipes 116 connected to the annular pipe 112. The side wall of the annular pipe 112 is provided with an internal gas phase inlet 110, which is connected to a hydrogen delivery unit. The side wall of the gas dispersion pipes 116 is provided with multiple through holes (not shown in the figure). An annular gas chamber 114 is formed inside the annular pipe 112. Hydrogen 1 enters the gas dispersion pipes 116 from the hydrogen delivery unit through the internal gas phase inlet 110 and through the annular gas chamber 114. After being dispersed into microbubbles, it diffuses into the oil phase inside the hydrogenation reactor 9.

[0057] Understandably, during the hydrogenation reaction, the hydrogen in the gas-liquid mixture will be gradually consumed. By setting up the hydrogen mixing device 11 in the reactor to continuously replenish the liquid phase material with microbubbles, it is beneficial to always maintain the liquid phase saturated dissolved hydrogen state and improve the efficiency of the hydrogenation reaction.

[0058] In some embodiments, the gas dispersion tube 116 is vertically distributed on the annular tube 112. Understandably, the length direction of the gas dispersion tube 116 is perpendicular to the plane direction of the annular tube 112. The gas dispersion tube 116 may be connected to the annular tube 112 at one end, or it may be connected to the annular tube 112 at the middle portion.

[0059] Furthermore, multiple gas dispersion tubes 116 are evenly spaced on the annular tube 112.

[0060] In some embodiments, the annular tube 112 and the gas dispersion tube 116 may be made of at least one of stainless steel, titanium alloy, Hastelloy, glass, or ceramic, preferably stainless steel, or a stainless steel / ceramic composite material. The annular tube 112 and the gas dispersion tube 116 may be integrally formed.

[0061] Furthermore, the diameter of the through hole on the gas dispersion tube 116 is 100 nm to 100 μm, for example, it can be any one of 100 nm to 1 μm, 1 to 10 μm, 10 to 20 μm, 20 to 30 μm, 30 to 40 μm, 40 to 50 μm, 50 to 60 μm, 60 to 70 μm, 70 to 80 μm, 80 to 90 μm or 90 to 100 μm.

[0062] In some embodiments, the hydrogen mixing device 11 in the reactor includes multiple annular pipes 112, which are arranged in concentric circles and connected to each adjacent pair of annular pipes 112 by a pipeline.

[0063] Furthermore, the number of annular tubes 112 can be 1 to 5, thereby forming 1 to 5 layers of annular air chamber passages.

[0064] Furthermore, the number of gas dispersion tubes 116 provided on each annular tube 112 can be 4 to 36, with a length of 1m to 5m, for example, 4, 6, 10, 15, 20, 25, 30, 36, etc.

[0065] Understandably, when multiple annular tubes 112 are arranged in concentric circles, the number of gas dispersion tubes 116 provided on each annular tube 112 can be different, for example, they can be reduced sequentially from the outside to the inside.

[0066] In some embodiments, the hydrogenation reactor 9 is provided with at least two catalyst beds 10, and the gas dispersion pipe 116 is disposed in the catalyst bed 10.

[0067] In some embodiments, the catalyst bed 10 has 2 to 4 segments, for example, 2, 3 or 4 segments.

[0068] Furthermore, in the hydrogenation reactor 9, the bottom first section catalyst bed 10 can be filled with ceramic balls, wax oil hydrogenation protective agent, wax oil hydrogenation refining agent, and ceramic balls in sequence from bottom to top; the second section to the top last section catalyst bed 10 can be filled with ceramic balls, wax oil hydrogenation refining catalyst, and ceramic balls in sequence from bottom to top.

[0069] In some embodiments, the preheating unit includes a heat exchange device 15, which includes a hot material inlet and a cold material outlet connected to each other, as well as a cold material inlet and a preheated material outlet connected to each other. The external hydrogen mixing device 8 is connected to the cold material inlet of the heat exchange device 15, the liquid phase outlet of the hydrogenation reactor 9 is connected to the hot material inlet of the heat exchange device 15, and the preheated material outlet is connected to the feed inlet of the hydrogenation reactor 9.

[0070] Furthermore, the preheating unit also includes a circulating oil pump 13. The outlet of the hydrogenation reactor 9 is connected to the inlet of the circulating oil pump 13. The outlet of the circulating oil pump 13 is connected to the preheated material outlet of the heat exchange device 15 and to the inlet of the hydrogenation reactor 9.

[0071] Furthermore, the preheating unit also includes a heating device 14, which is connected between the heat exchange device 15 and the external hydrogen mixing device 8. As an example, the heating device 14 can be a gas-fired furnace or a tubular electric heating device.

[0072] Please see again Figure 1 The separation unit includes a first separation device 12 and a second separation device 16. The first separation device 12 is located at the top of the hydrogenation reactor 9 and is connected to the liquid phase outlet and the gas phase outlet of the hydrogenation reactor 9. The gas phase outlet of the hydrogenation reactor 9 and the cold material outlet of the heat exchange device 15 are respectively connected to the second separation device 16.

[0073] In some embodiments, the hydrogen delivery unit includes a hydrogen filter 2, a hydrogen buffer tank 3, and a hydrogen compressor 4 connected in sequence, whereby hydrogen can be purified by the hydrogen filter 2 and pressurized by the hydrogen buffer tank 3 and the hydrogen compressor 4; the liquid phase delivery unit includes an oil phase filter 6 and an oil phase feed pump 7 connected in sequence, whereby the oil phase can be purified by the oil phase filter 6 and pressurized by the oil phase feed pump 7. The purified and pressurized hydrogen 1 and oil phase 5 can be efficiently mixed in the hydrogen mixing device 8 outside the reactor.

[0074] Furthermore, the hydrogen filtration device 2 filters impurity particles with a particle size range of 1μm to 10μm, for example, 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm or 10μm, etc.

[0075] Furthermore, the oil phase filtration device 6 filters impurity particles with a particle size range of 1μm to 50μm, for example, 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, 15μm, 20μm, 25μm or 50μm, etc.

[0076] By setting up hydrogen filtration device 2 and oil phase filtration device 6 to filter out impurity particles, the efficiency of hydrogenation reaction can be improved, the purity of hydrogenation products can be increased, and the blockage of the micro-nano porous membrane 834 in the external hydrogen mixing device 8 can be further prevented.

[0077] Please see Figure 1 The second aspect of this application also provides a method for enhancing oil-phase hydrogenation reaction using the above-described system, comprising the following steps: Oil phase 5 is transported to the external hydrogen mixing device 8 through the liquid phase conveying unit, and hydrogen 1 is transported to the external hydrogen mixing device 8 through the hydrogen conveying unit for mixing to obtain a gas-liquid mixture. The gas-liquid mixture is transported to the preheating unit for heating, and then to the hydrogenation reaction unit to contact the hydrogenation catalyst for hydrogenation reaction. At the same time, hydrogen is introduced into the hydrogen mixing device in the reactor through the hydrogen delivery unit and dispersed into microbubbles. After the reaction is completed, the hydrogenation product is obtained. The hydrogenation products are transported to a separation unit for separation to obtain hydrogenated oil products.

[0078] In some embodiments, the method includes the following steps: hydrogen gas 1 is sequentially passed through a hydrogen filter device 2, a hydrogen buffer tank 3, and a hydrogen compressor 4 to obtain purified and pressurized hydrogen gas 1; and oil phase 5 is sequentially passed through an oil phase filter device 6 and an oil phase feed pump 7 to obtain purified and pressurized oil phase 5. A portion of hydrogen gas 1 and oil phase 5 are introduced into an external hydrogen mixing device 8 for efficient mixing to obtain a gas-liquid mixture. The gas-liquid mixture is heated by a heating device 14 and then heat-exchanged with the hydrogenated liquid phase product by a heat exchange device 15. It is then further mixed and preheated with the high-temperature hydrogenated liquid phase product from a circulating oil pump 13 to obtain the reaction feedstock. The reaction feedstock is introduced into a hydrogenation reactor 9 to react with the hydrogenation catalyst in the catalyst bed 10. Simultaneously, hydrogen gas 1 is added to the catalyst bed 10. The hydrogen gas 1 is dispersed into microbubbles by the internal hydrogen mixing device 11 and diffuses into the liquid phase, maintaining a saturated hydrogen state in the liquid phase. After the reaction is completed, the product is separated into a hydrogenated liquid phase product and a hydrogenated gas phase product by a first separation device at the top of the hydrogenation reactor 9. Part of the hydrogenated liquid phase product enters the circulating oil pump 13 from the liquid phase outlet and mixes with the heat-exchanged gas-liquid mixture. Another part of the hydrogenated liquid phase product exchanges heat with the gas-liquid mixture in the heat exchange device 15 and then enters the second separation device 16. The hydrogenated gas phase product (unreacted hydrogen and gas produced by the reaction) is output from the gas phase outlet and enters the second separation device 16. After secondary separation, hydrogenated oil 17 and gas phase separation product 18 are obtained.

[0079] In some embodiments, after preheating by the preheating unit, the temperature of the material before reaction is 350°C to 420°C, for example, it can be 350°C, 365°C, 375°C, 385°C, 400°C, 410°C or 420°C.

[0080] Furthermore, when hydrogen 1 and oil phase 5 enter the external hydrogen mixing device 8 of the reactor, the volume ratio under standard conditions is (50~300):1, for example, it can be 50:1, 100:1, 200:1 or 300:1, etc.

[0081] Furthermore, when hydrogen 1 enters the hydrogen mixing device 11 inside the reactor, the volume ratio of hydrogen 1 to oil phase 5 under standard conditions is (50~300):1, for example, it can be 50:1, 100:1, 200:1 or 300:1, etc.

[0082] In some embodiments, the size of the microbubbles is 50 nm to 1000 μm, for example, it can be 50 nm, 100 nm, 500 nm, 1 μm, 10 μm, 100 μm, 1000 μm, etc. Further, the size of the microbubbles is 100 nm to 10 μm.

[0083] In some embodiments, the oil phase is wax oil, the hydrogenation reaction temperature is 350°C to 450°C, and the pressure is 8 MPa to 15 MPa. As an example, the hydrogenation reaction temperature can be 350°C, 360°C, 380°C, 400°C, 420°C, 450°C, etc.; and the pressure can be 8 MPa, 10 MPa, 12 MPa, 14 MPa, 15 MPa, etc.

[0084] Understandably, the oil phase used in the methods and systems of this application is not limited to wax oil, but can also be diesel oil, wax oil, lubricating oil, kerosene, residual oil or reformed oil, etc.

[0085] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0086] Example 1 Please see Figures 1 to 3 This embodiment provides an oil-phase hydrogenation reaction enhancement system and a method for using the system, the method comprising the following steps: (1) Hydrogen 1 is passed sequentially through hydrogen filter 2, hydrogen buffer tank 3 and hydrogen compressor 4 to obtain purified and pressurized hydrogen 1. Oil phase 5 (wax oil) is passed sequentially through oil phase filter 6 and oil phase feed pump 7 to obtain purified and pressurized oil phase 5. Part of hydrogen 1 and oil phase 5 are fed into the external hydrogen mixing device 8 of the reactor for efficient mixing to obtain a gas-liquid mixture.

[0087] The reactor external hydrogen mixing device 8 includes a micro-nano porous membrane 834, a spiral guide vane 862, and a drive device 864. The volume ratio of hydrogen 1 and oil phase 5 entering the reactor external hydrogen mixing device 8 is 50:1 under standard conditions, and the size of the generated hydrogen microbubbles is 50~100μm.

[0088] (2) The gas-liquid mixture is heated by the heating device 14 and then heat exchanged with the hydrogenated liquid phase product by the heat exchange device 15. It is then further mixed and preheated with the high-temperature hydrogenated liquid phase product from the circulating oil pump 13 to obtain the reaction raw material at a temperature of 370°C.

[0089] (3) The reaction raw materials are introduced into the hydrogenation reactor 9 and react with the hydrogenation catalyst in the catalyst bed 10. At the same time, hydrogen gas 1 is added to the catalyst bed 10. The hydrogen gas 1 is dispersed into microbubbles through the hydrogen mixing device 11 in the reactor and diffuses into the liquid phase to maintain the liquid phase saturated with hydrogen.

[0090] The hydrogenation reactor 9 is equipped with four catalyst bed layers 10, three of which are each equipped with an in-reactor hydrogen mixing device 11. Each in-reactor hydrogen mixing device 11 includes two concentric annular tubes 112. The outer annular tube 112 has eight gas dispersion tubes 116 evenly spaced vertically, while the inner annular tube 112 has four gas dispersion tubes 116 evenly spaced. The gas dispersion tubes 116 are made of stainless steel, are 3m long, and have through-hole diameters of 40μm~50μm, producing hydrogen microbubbles with a size of 300μm~400μm. The volume ratio of hydrogen 1 to oil phase 5 feedstock entering the hydrogenation reactor 9 under standard conditions is 100:1. The hydrogen-to-oil volume ratios distributed from bottom to top by the three in-reactor hydrogen mixing devices 11 are 33.3:1, 33.3:1, and 33.3:1, respectively.

[0091] The pressure of the hydrogenation reaction is 10 MPa, and the average temperature of the hydrogenation reaction is 370℃.

[0092] (4) After the reaction is completed, the hydrogenated liquid phase product and the hydrogenated gas phase product are separated by the first separation device at the top of the hydrogenation reactor 9. Among them, part of the hydrogenated liquid phase product enters the circulating oil pump 13 from the liquid phase outlet and mixes with the heat-exchanged gas-liquid mixture. The other part of the hydrogenated liquid phase product enters the second separation device 16 after exchanging heat with the gas-liquid mixture in the heat exchange device 15. The hydrogenated gas phase product (hydrogen and the gas produced by the reaction) is output from the gas phase outlet and enters the second separation device 16. After secondary separation, hydrogenated oil 17 and gas phase separation product 18 are obtained.

[0093] Example 2 This embodiment provides an oil phase hydrogenation reaction enhancement system and a method for using the system. The only difference between this method and Embodiment 1 is that in step (3), 36 gas dispersion tubes 116 are uniformly and vertically spaced on the outer annular tube 112. Example 3 This embodiment provides an oil phase hydrogenation reaction enhancement system and a method for using the system. The only difference between this method and Embodiment 1 is that in step (3), the diameter of the through hole of the gas dispersion tube 116 is 100 nm to 1 μm, and the size of the generated hydrogen microbubbles is 100 nm to 1 μm. Example 4 This embodiment provides an oil phase hydrogenation reaction enhancement system and a method for using the system. The only difference between this method and Embodiment 1 is that in step (3), the hydrogen-oil volume ratios distributed from bottom to top in the hydrogen mixing device 11 in the three-stage reactor are 50:1, 30:1, and 20:1, respectively. Example 5 This embodiment provides an oil phase hydrogenation reaction enhancement system and a method for using the system. The only difference between this method and Embodiment 1 is that in step (1), the hydrogen mixing device 8 outside the reactor does not include the driving device 864, and the size of the generated hydrogen microbubbles is 200-300μm.

[0094] Example 6 This embodiment provides an oil phase hydrogenation reaction enhancement system and a method for using the system. The only difference between this method and Embodiment 1 is that in step (1), the external hydrogen mixing device 8 does not include the spiral guide vane 862 and the driving device 864, and the size of the generated hydrogen microbubbles is 400-500μm.

[0095] Comparative Example 1 This comparative example provides an oil-phase hydrogenation reaction enhancement system and a method for using the system. The only difference between this method and Example 1 is that only an external hydrogen mixing device 8 is provided, and an internal hydrogen mixing device 11 is not provided.

[0096] Comparative Example 2 This comparative example provides an oil-phase hydrogenation reaction enhancement system and a method for using the system. The only difference between this method and Example 1 is that the external hydrogen mixing device 8 and the internal hydrogen mixing device 11 are not provided.

[0097] Comparative Example 3 This comparative example provides an oil-phase hydrogenation reaction enhancement system and a method for using the system. The only difference between this method and Example 1 is that the external hydrogen mixing device 8 and the internal hydrogen mixing device 11 are not provided.

[0098] The hydrogenation reaction is carried out at a pressure of 15 MPa and at an average temperature of 400 °C. Comparative Example 4 This comparative example provides a conventional wax oil trickle bed hydrogenation process, referring to the system in Example 1, but without the external hydrogen mixing device 8 or the internal hydrogen mixing device 11. Hydrogen 1 and oil phase 5 enter from the top of the hydrogenation reactor 9, with a hydrogen-to-oil feed volume ratio of 800:1. A new circulating hydrogen system is added, the hydrogenation reaction pressure is 15 MPa, and the average temperature of the hydrogenation reaction is 400°C.

[0099] Performance testing and results analysis (1) Sulfur content: The sulfur content of the hydrogenated oil products obtained in the examples and comparative examples was tested according to the standard GB / T17040-2019 Determination of Sulfur Content of Petroleum Products (Energy Dispersive X-ray Fluorescence Spectroscopy).

[0100] (2) Production process energy consumption: The energy consumption of the oil hydrogenation process is calculated according to the energy consumption calculation method of GB / T 30251-2013 Energy Consumption Limits of Refining Unit Products.

[0101] The reaction conditions and performance test results of the above embodiments and comparative examples are shown in Table 1.

[0102] Table 1 Hydrogenation reaction conditions and performance test results

[0103] As shown in Table 1, compared to Comparative Examples 1-4, the systems and methods in Examples 1-6 of this application can effectively reduce the sulfur content in hydrogenated oils under the same hydrogenation reaction temperature and pressure. While maintaining comparable product properties, they can effectively reduce reaction temperature and pressure, thus lowering production process energy consumption. In Examples 1-6, the sulfur content in the hydrogenated oils is ≤188 mg / kg, and the production process energy consumption is ≤12 Etoa / t.

[0104] The results of Comparative Example 1 and Example 1 show that when the process flow does not include the hydrogen mixing device 11 in the reactor, the desulfurization effect of wax oil hydrotreating is reduced. This is mainly because the hydrogen in the reactor cannot be replenished into the liquid phase in a timely and efficient manner, the rate of dissolved hydrogen in the bed does not match the rate of hydrogen consumption in the reaction, and the energy consumption of the reaction process is further increased.

[0105] The results of Comparative Example 2 and Example 1 show that when the external hydrogen mixing device 8 and the internal hydrogen mixing device 11 are not set, the desulfurization effect of wax oil hydrotreating is greatly reduced, and the energy consumption is also greatly increased. This is mainly because hydrogen cannot be uniformly dispersed in the liquid phase, and the hydrogen dissolution rate of the reaction process is far from meeting the hydrogen consumption rate of the catalyst surface reaction.

[0106] The results of Comparative Example 3 and Example 1 show that when the high-efficiency hydrogen mixing device 8 outside the reactor and the high-efficiency hydrogen mixing device 11 inside the reactor are not set, the desulfurization effect of wax oil hydrotreating can be further improved by increasing the reaction pressure and temperature, but the desulfurization depth still cannot reach the effect when the microbubble high-efficiency hydrogen mixing device is used, and the energy consumption cannot be reduced.

[0107] The results from Comparative Example 4 and Example 1 show that the traditional wax oil trickle bed hydrogenation process, without a hydrogen mixing unit, requires a significant increase in the pressure, temperature, and hydrogen-to-oil ratio of the reaction process to achieve the same desulfurization effect. At the same time, it also requires the addition of a circulating hydrogen device, resulting in a much higher energy consumption for the reaction process than in Example 1.

[0108] As can be seen from the above embodiments and comparative examples, this application significantly enhances the hydrogenation reaction characteristics at the phase interface of hydrogen, oil phase, and catalyst by improving the mixing and mass transfer process of hydrogen and oil phase. This fully utilizes the catalyst, improves the efficiency of the oil phase hydrogenation process, and significantly reduces the hydrogenation reaction temperature, pressure, and hydrogen-to-oil ratio, resulting in a substantial decrease in energy and material consumption. Compared to the traditional wax oil trickle bed hydrogenation process, under the same conditions for achieving the same wax oil hydrogenation product properties, the reaction temperature can be reduced by more than 10°C, the reaction pressure by more than 4 MPa, and the hydrogen-to-oil ratio by more than 50%, with an overall energy consumption reduction of more than 50%. Under the same hydrogenation reaction conditions, the sulfur content in the hydrogenation product can be reduced by more than 50%, demonstrating significant energy-saving, carbon-reducing, and quality-improving effects.

[0109] The embodiments described above are some, but not all, of the embodiments of this application. The detailed description of the embodiments of this application is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

Claims

1. An oil-phase hydrogenation reaction enhancement system, characterized in that, It includes a hydrogen delivery unit, a liquid phase delivery unit, a hydrogen mixing unit, and a preheating unit, a hydrogenation reaction unit, and a separation unit connected in sequence. The hydrogenation reaction unit includes a hydrogenation reactor, and the hydrogen mixing unit includes an in-reactor hydrogen mixing device disposed inside the hydrogenation reactor and an external hydrogen mixing device disposed outside the hydrogenation reactor; the hydrogen delivery unit and the liquid phase delivery unit are respectively connected to the external hydrogen mixing device, and the external hydrogen mixing device is connected to the preheating unit. The reactor-internal hydrogen mixing device includes at least one annular pipe and multiple gas dispersion pipes connected to the annular pipe. The annular pipe has an internal gas phase inlet on its side wall, which is connected to the hydrogen delivery unit. The gas dispersion pipes have multiple through holes on their side walls.

2. The system according to claim 1, characterized in that, The hydrogenation reactor is provided with at least two catalyst beds, and the gas dispersion pipe is disposed within the catalyst beds; Preferably, the gas dispersion tubes are vertically distributed on the annular tube; Preferably, the multiple gas dispersion tubes are evenly spaced on the annular tube; Preferably, the hydrogen mixing device in the reactor includes multiple annular tubes arranged in concentric circles, and each pair of adjacent annular tubes is connected by a pipeline. Preferably, the number of gas dispersion tubes distributed on each of the annular tubes is 4 to 36; Preferably, the diameter of the through hole is 100 nm to 100 μm; Preferably, the annular tube and the gas dispersion tube are each made of at least one of stainless steel, titanium alloy, Hastelloy, glass, or ceramic.

3. The system according to claim 1, characterized in that, The reactor external hydrogen mixing device includes a shell, with a liquid phase inlet and a mixture outlet at both ends of the shell. An external gas phase inlet is provided on the side wall of the shell. The liquid phase inlet is connected to the liquid phase conveying unit, the external gas phase inlet is connected to the hydrogen conveying unit, and the mixture outlet is connected to the preheating unit. Within the housing, the liquid inlet is sequentially connected to a liquid phase chamber, a liquid phase channel, a gas-liquid mixing channel, a diffusion channel, a gas release chamber, and the outlet of the mixture. The diameters of the liquid phase channel and the diffusion channel gradually increase in the direction away from the gas-liquid mixing channel. The external gas phase inlet is connected to a gas phase chamber, and the gas-liquid mixing channel is located within the gas phase chamber. The sidewall of the gas-liquid mixing channel has through-holes, and the surface of the sidewall facing the gas phase chamber is provided with a micro / nano porous membrane. A spiral guide vane is provided within the gas release chamber.

4. The system according to claim 3, characterized in that, An electric heating element is embedded inside the housing; Preferably, the electric heating element comprises an insulating inner layer, a tungsten alloy conductive layer, and a protective outer layer; Preferably, the shell is made of stainless steel.

5. The system according to claim 3, characterized in that, The surface of the micro-nano porous membrane is coated with an oleophobic nano-coating. Preferably, the material of the micro / nanoporous membrane includes at least one of metal, plastic or ceramic; Preferably, the thickness of the micro / nanoporous membrane is 50 μm to 2 mm; Preferably, the diameter of the micro-nanoporous pores on the micro-nanoporous membrane is 100 nm to 100 μm.

6. The system according to claim 3, characterized in that, The reactor external hydrogen mixing device is also equipped with a driving device, which is connected to the spiral guide vane to drive the spiral guide vane to rotate.

7. The system according to any one of claims 1 to 6, characterized in that, The preheating unit includes a heat exchange device, which includes a hot material inlet and a cold material outlet that are interconnected, as well as a cold material inlet and a preheated material outlet that are interconnected. The external hydrogen mixing device is connected to the cold material inlet of the heat exchange device. The liquid phase outlet of the hydrogenation reactor is connected to the hot material inlet of the heat exchange device. The preheated material outlet is connected to the feed inlet of the hydrogenation reactor. Preferably, the preheating unit further includes a circulating oil pump, the liquid phase outlet of the hydrogenation reaction unit is connected to the inlet of the circulating oil pump, the outlet of the circulating oil pump is connected to the preheated material outlet of the heat exchange device, and is also connected to the inlet of the hydrogenation reactor. Preferably, the preheating unit further includes a heating device, which is connected between the heat exchange device and the external hydrogen mixing device of the reactor.

8. The system according to claim 7, characterized in that, The separation unit includes a first separation device and a second separation device. The first separation device is located at the top of the hydrogenation reactor and is connected to the liquid phase outlet and the gas phase outlet of the hydrogenation reactor. The gas phase outlet of the hydrogenation reactor and the cold material outlet of the heat exchange device are respectively connected to the second separation device.

9. A method for enhancing oil-phase hydrogenation reaction, employing the system as described in any one of claims 1 to 8, characterized in that, Includes the following steps: The oil phase is transported to the external hydrogen mixing device of the reactor through the liquid phase conveying unit, and hydrogen is transported to the external hydrogen mixing device of the reactor through the hydrogen conveying unit to mix with the oil phase to obtain a gas-liquid mixture. The gas-liquid mixture is transported to the preheating unit for heating, and then transported to the hydrogenation reactor to contact the hydrogenation catalyst for hydrogenation reaction. At the same time, hydrogen is transported to the hydrogen mixing device in the reactor through the hydrogen delivery unit and dispersed into microbubbles to participate in the hydrogenation reaction. After the reaction is completed, the hydrogenation product is obtained. The hydrogenation product is transported to the separation unit for separation to obtain hydrogenated oil.

10. The method according to claim 9, characterized in that, The size of the microbubbles is 50nm~1000μm; Preferably, the oil phase includes at least one of wax oil, residual oil, lubricating oil, diesel oil, kerosene, or reformed oil; Preferably, the temperature of the hydrogenation reaction is 350℃~450℃, and the pressure is 8MPa~15MPa; Preferably, the volume ratio of hydrogen to oil phase input into the hydrogen mixing device in the reactor is (50~300):1.

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