Device and method for deeply removing silicon from liquid hydrocarbon

Abstract

The invention discloses a device and a method for deeply removing silicon from liquid hydrocarbon. The device comprises a supergravity mass transfer system and an ultra-deep adsorption system, the supergravity mass transfer system comprises a first supergravity reactor and a second supergravity reactor which are oppositely arranged up and down, and central rotating shafts of the reactors are on the same straight line; each of the first supergravity reactor and the second supergravity reactor comprises a reaction cavity and a rotor arranged in the reaction cavity, and the rotors are externally connected with a driving mechanism through respective central rotating shafts; a rotor of the first supergravity reactor is filled with a mass transfer filler, and a rotor of the second supergravity reactor is filled with a separation filler; the first supergravity reactor reaction cavity and the second supergravity reactor reaction cavity are communicated through a liquid rising channel and a liquid falling channel; a raw material distributor is axially arranged in the inner side area of the mass transfer filler, and a desiliconizing agent distributor is axially arranged in the outer side area of the mass transfer filler; the top of the first supergravity reactor is provided with a light phase outlet connected with the ultra-deep adsorption system, and the bottom of the second supergravity reactor is provided with a heavy phase outlet.

Description

Technical Field

[0001] This invention relates to the field of petrochemical technology, specifically to an apparatus for deep desiliconization of liquid hydrocarbons, and a method for deep desiliconization using the apparatus. Background Technology

[0002] In the oil refining industry, crude oil and various distillate fractions contain small amounts of silicon compounds, mainly from silicon-containing additives used in oil processing. Organosilicon viscosity reducers and diluents primarily contain polysiloxanes, organosilicon defoamers primarily contain dimethylsiloxanes, and organosilicon crude oil demulsifiers primarily contain polyether and methylethoxysiloxane block copolymers. These silicon compounds are distributed in different petroleum fractions according to their boiling points. Among these distillate fractions, low-quality naphtha, such as coking naphtha, has a higher silicon content. Since naphtha is mainly used as feedstock for ethylene and catalytic reforming, it requires hydrotreating before entering subsequent units. However, high-silicon naphtha entering the hydrotreating unit can lead to silicon deposition in the hydrotreating catalyst and subsequent catalyst poisoning and deactivation. Therefore, existing technologies generally achieve silicon removal by loading silicon-scavenging agents into the hydrotreating reactor during the hydrotreating process. This method not only has many problems such as complex process flow, harsh reaction conditions, and high cost, but also has difficulty handling feedstocks with high silicon content. Therefore, developing new and efficient deep desiliconization technologies for liquid hydrocarbons is of great significance.

[0003] Patent document US4176047A discloses a method for removing silicon-containing organic matter from coking gasoline, using an alumina-supported catalyst with Co-Mo as the metal component, and a strip shape with dimensions of 1×10 mm. Since this catalyst is mainly used for hydrodesulfurization and has not been specifically designed or modified for silicon capacity, its silicon removal and capacity is very small. This means it cannot guarantee long-term operation of the equipment, and the amount of silicon-catching agent required is extremely large, making it unsuitable for industrial applications.

[0004] Patent CN104492450B discloses a desilication catalyst for coking gasoline and its preparation method. This catalyst uses Al2O3-TiO2-B2O3 supported oxides as a carrier and Ni-Mo-W-Ce as the active component. Calcined in a steam atmosphere, the catalyst possesses a specific pore size and large pore volume, enabling effective removal of silicon-based organic compounds and protecting the subsequent hydrorefining catalyst.

[0005] Patent CN112705223B discloses a silicon scavenger and its preparation method. The silicon scavenger includes a support and a hydrogenation active component. The hydrogenation active component is a Group VIB metal sulfide, a Group VIB metal oxide, and a Group VIII metal oxide. Based on the total weight of the silicon scavenger, the Group VIB metal sulfide is 0.3wt% to 18.3wt%, the Group VIB metal oxide is 0.1wt% to 5.0wt%, and the Group VIII metal oxide is 0.2wt% to 12.0wt%. The preparation method of the silicon scavenger includes the following: (1) impregnating the catalyst support with an impregnation solution containing a Group VIB metal, and then drying the material. The dried material is then subjected to sulfidation treatment; (2) impregnating the material after sulfidation in step (1) with an impregnation solution containing Group VIB and Group VIII metals, and then drying and calcining it under an inert atmosphere to obtain the silicon scavenger. The active component of the silicon-catching agent prepared by this method has a high degree of sulfidation and a high silicon-containing capacity, making it suitable for desilication and silicon-catching of silicon-containing oil products such as coking dry gas, coking naphtha, and coking diesel.

[0006] In summary, in the existing technology of liquid hydrocarbon desiliconization in the oil refining industry, most of it is used in naphtha hydrotreating units. It achieves desiliconization by first using a hydrosilicon-scavenging agent during the hydrorefining process. Since materials with slightly higher silicon content will affect the hydrorefining effect, there are relatively strict requirements on the silicon content in the feed.

[0007] Due to the limitations of existing technologies, on the one hand, they are not applicable to materials with high silicon content. On the other hand, for scenarios where silicon-containing oils or liquid hydrocarbons only require silicon removal and do not require hydrogenation refining, the hydrogenation process obviously has many problems such as complex process flow, harsh reaction conditions, and high cost. Therefore, it is necessary to develop new, efficient and easily industrialized liquid hydrocarbon silicon removal technologies. This is of great significance for replacing existing hydrogenation silicon removal technologies in the industry, filling existing gaps, and helping to increase the added value of high silicon content oils in the refining industry. Summary of the Invention

[0008] To address the aforementioned technical problems and shortcomings in this field, this invention provides an apparatus and method for deep desiliconization of liquid hydrocarbons. It employs a combination of a novel hypergravity mass transfer system for inorganic silicon removal and a deep adsorption system for organic silicon removal. The novel hypergravity mass transfer system consists of two coupled hypergravity reactors arranged opposite each other along a central axis. Under the action of a composite desiliconizing agent, the two reactors achieve enhanced coupling of mass transfer and separation within the same system but different centrifugal fields through counter-rotation and internal material exchange, reducing the inorganic silicon content to ≤10 ppm. The resulting liquid hydrocarbon then enters the deep adsorption system to further reduce the organic silicon content to ≤10 ppm, ultimately reducing the total silicon content in the liquid hydrocarbon to ≤20 ppm. Compared with traditional hydrogenation desiliconization technology, this method offers advantages such as advanced process flow, high desiliconization efficiency, low equipment investment and operating energy consumption, and wide adaptability to raw materials. It is of great significance for increasing the added value of high-silicon-content liquid hydrocarbons. The specific technical solution is as follows: In a first aspect, the present invention provides an apparatus for deep silicon removal from liquid hydrocarbons, comprising a hypergravity mass transfer system for removing inorganic silicon and a deep adsorption system for removing organic silicon. The hypergravity mass transfer system includes a first hypergravity reactor and a second hypergravity reactor arranged vertically opposite each other with their central axes aligned on the same straight line. Both reactors include a reaction chamber and a rotor located within it, with each rotor connected to an external drive mechanism via its central axis. The rotor of the first hypergravity reactor is filled with mass transfer packing, while the rotor of the second hypergravity reactor is filled with separation packing. The reaction chambers of the first and second hypergravity reactors are connected by a rising liquid channel and a falling liquid channel. A raw material distributor is axially arranged in the inner region of the mass transfer packing, and a desilication agent distributor is axially arranged in the outer region. The top of the first hypergravity reactor is equipped with a light phase outlet (liquid hydrocarbon outlet after organosilicon removal) connected to the ultra-deep adsorption system, and the bottom of the second hypergravity reactor is equipped with a heavy phase outlet.

[0009] The rotor in the first hypergravity reactor primarily enhances mass transfer, while the rotor in the second hypergravity reactor primarily enhances separation. Materials within the reaction chambers of the two reactors are interconnected via rising and falling liquid channels. In the first hypergravity reactor, material from the second reactor undergoes droplet reversal after passing through the rising liquid channel. The droplets rapidly rebound and form a film on the packing surface within the rotor of the first reactor, resulting in rapid surface renewal and intense collisions with liquid hydrocarbons, thus significantly enhancing the mass transfer process. Similarly, in the second hypergravity reactor, material from the first reactor undergoes droplet reversal after passing through the falling liquid channel. The droplets rebound and splash within the rotor of the second reactor, rapidly separating light and heavy materials, thereby greatly enhancing separation efficiency.

[0010] Inside the rotor of the first hypergravity reactor, a liquid-liquid countercurrent operation is employed. The silicon-containing liquid hydrocarbon feedstock is uniformly distributed from a feed distributor near the central shaft, while the desiliconizing agent is fed from the outer edge of the rotor and uniformly distributed via a desiliconizing agent distributor connected at the outer edge. The feed distributor and desiliconizing agent distributor can be atomizing nozzles, spray pipes with strip or circular orifices, or other devices with identical or different structures, as long as they achieve uniform liquid distribution. During the mass transfer process, the liquid hydrocarbon, under the influence of centrifugal force in the first hypergravity reactor and the density difference between the liquid hydrocarbon and the desilication agent, gradually moves towards the edge and the top. After completing the mass transfer, it exits from the light phase outlet at the top of the first hypergravity reactor. Meanwhile, the desilication agent, under the influence of centrifugal force in the first hypergravity reactor and the density difference between the liquid hydrocarbon and the desilication agent, moves downwards. After completing the mass transfer with the liquid hydrocarbon, it enters the reaction chamber of the second hypergravity reactor through the descending channel between the first and second hypergravity reactors for enhanced separation. Inside the rotor of the second hypergravity reactor, the desilication agent undergoes a liquid direction change after passing through the descending channel between the first and second hypergravity reactors, achieving the separation of the light and heavy phases at an extremely high speed. Finally, the separated light phase of liquid hydrocarbon enters the reaction chamber of the first hypergravity reactor through the ascending channel between the rotors of the first and second hypergravity reactors, while the separated heavy phase of the desilication agent liquid exits from the heavy phase outlet at the bottom of the second hypergravity reactor.

[0011] Furthermore, the opposing end faces of the central rotating shafts of the first and second supergravity reactors are connected in a non-contact sealed manner by filling with sealing packing.

[0012] Furthermore, the sealing filler includes one or more of the following: asbestos fabric, polytetrafluoroethylene, carbon fiber, rubber, flexible graphite, metal composite material, and engineering plastic.

[0013] Furthermore, in the aforementioned device for deep desiliconization of liquid hydrocarbons, during operation, the rotational speed of the first hypergravity reactor rotor is greater than or equal to that of the second hypergravity reactor rotor. This is because the purpose of the first hypergravity reactor rotor is to spread the liquid droplets into a film within the microchannels formed by the dense packing material inside the first hypergravity reactor rotor. A higher rotational speed is more conducive to the formation of well-dispersed phase droplets, but excessively high rotational speeds can cause severe emulsification, making subsequent separation difficult. The purpose of the second hypergravity reactor rotor is to cause dense aggregation of dispersed phase droplets on the surface of the fiber packing material within the second hypergravity reactor rotor. A slightly lower rotational speed can avoid emulsification, but excessively low rotational speeds will reduce the collision rate of the dispersed phase droplets, thereby reducing phase separation efficiency. Even further, in the aforementioned device for deep desiliconization of liquid hydrocarbons, during operation: the rotational speed of the first hypergravity reactor rotor is 500~3000 rpm, preferably 1500~2500 rpm; the rotational speed of the second hypergravity reactor rotor is 50~2000 rpm, preferably 500~1500 rpm.

[0014] Furthermore, in the aforementioned device for deep desiliconization of liquid hydrocarbons, during operation, the first and second hypergravity reactors rotate in opposite directions along their respective central axes. That is, the rotation directions of the first and second hypergravity reactors are opposite, and it is not limited to the first or second hypergravity reactor rotors rotating arbitrarily clockwise or counterclockwise.

[0015] Furthermore, the porosity of the mass transfer packing increases from the inside to the outside. Based on the different centrifugal forces on the inside and outside, the centrifugal force of droplets on the inside is smaller, and a lower porosity is beneficial for the formation of microdroplets within the dense microchannels, providing good micro-dispersion conditions for subsequent mass transfer. Conversely, the centrifugal force of droplets on the outside is greater, and a higher porosity is beneficial for the flow, spreading, and contact mass transfer of microdroplets, further enhancing the mass transfer effect. Even further, the preferred porosity on the inside of the mass transfer packing is 10%~30%, more preferably 15%~25%, and the preferred porosity on the outside is 30%~50%, more preferably 35%~45%.

[0016] Furthermore, the mass transfer packing has a dense, three-dimensional, and regular packing structure composed of multiple layers of fiber-woven sheet material wound around a central axis, forming dense microchannels. This can reduce the droplet diameter, increase the liquid-liquid two-phase mass transfer area, and enhance the mass transfer function. The thickness of a single layer of fiber-woven sheet is preferably 0.1~10 cm, and more preferably 0.5~2 cm.

[0017] Furthermore, the mass transfer filler fiber is a first composite fiber filament woven together with hydrophilic and hydrophobic fibers, wherein the weaving ratio of hydrophilic and hydrophobic fibers to hydrophilic and hydrophobic fibers by weight is preferably 10:1 to 1:1, and more preferably 5:1 to 2:1.

[0018] Furthermore, the surface of the mass transfer packing has a first composite fiber filament woven into a first pattern structure. The first pattern structure preferably includes one or more of the following: rhombus, square, rectangle, circle, ellipse, and hexagon. This pattern structure with regular and dense channels on the surface of the mass transfer packing facilitates the formation of microchannels and reduces pressure drop. This is to enable the adhesion and spreading of the two-phase materials, allowing for more sufficient contact between the two phases while achieving good radial diffusion, thereby effectively enhancing the liquid-liquid mass transfer effect.

[0019] Furthermore, the porosity of the separating packing increases from top to bottom. This is because as the droplet size gradually increases, the larger porosity of each droplet facilitates further collision, coalescence, and growth, thereby accelerating droplet sedimentation and separation. Even further, the porosity of the top layer of the separating packing is preferably 30%~60%, more preferably 35%~55%, and the porosity of the bottom layer is preferably 60%~90%, more preferably 65%~85%.

[0020] Furthermore, the separating packing is composed of multiple layers of annular structured packing perpendicular to the central axis of rotation, which allows the material to be separated to undergo droplet aggregation and growth as it passes through the packing layers multiple times, ultimately achieving liquid-liquid two-phase separation.

[0021] Furthermore, the thickness of a single layer of the annular structured packing is preferably 0.5~20cm, and even more preferably 2~5cm.

[0022] Furthermore, the annular structured filler layer is woven from a second composite fiber filament woven together with hydrophilic and hydrophobic fibers, wherein the weaving ratio of hydrophilic and hydrophobic fibers to hydrophilic and hydrophobic fibers by weight is preferably 1:1.1 to 1:10, and more preferably 1:2 to 1:5.

[0023] Furthermore, the surface of the separating packing has a second composite fiber filament woven into a second pattern structure. The second pattern structure preferably includes one or more of the following: X-shaped, V-shaped, 8-shaped, Ω-shaped, and teardrop-shaped. These node pattern structures can cause small droplets to coalesce and grow into large droplets at the node positions, and a greater number of nodes can effectively enhance the liquid-liquid separation effect.

[0024] The preferred oleophilic and hydrophobic fibers include one or more of the following: polyester fibers, nylon fibers, polyurethane fibers, polypropylene fibers, polyacrylonitrile fibers, polyvinyl chloride fibers, and fibers whose surfaces have been modified with oleophilic and hydrophobic properties.

[0025] The hydrophilic and oleophobic fibers preferably include at least one of the following: polymer fibers with one or more of carboxyl, amino, and hydroxyl groups in the main chain and / or side chain; fibers whose surface has been modified with hydrophilic and oleophobic properties; and more preferably, at least one of acrylic fibers, polyvinyl alcohol fibers, and polyethylene glycol fibers.

[0026] The diameter of the oleophilic and hydrophobic fibers is preferably 5~50μm.

[0027] Furthermore, the first and second hypergravity reactor reaction chambers are integrated and located within the same large reactor shell. That is, the first and second hypergravity reactors share the same reactor shell.

[0028] Furthermore, a support plate is provided between the first hypergravity reactor reaction chamber and the second hypergravity reactor reaction chamber.

[0029] Furthermore, the liquid riser channel includes a liquid riser tube and an upper cover plate covering the liquid riser tube.

[0030] Furthermore, one end of the riser pipe is fixed to the support plate, and the other end extends into the rotor of the second hypergravity reactor.

[0031] Furthermore, the top cover is an inverted U-shaped structure with a closed top and open sides, with its sides fixed to the support plate. During operation, the material in the rotor of the second hypergravity reactor (i.e., the enhanced separation zone) enters the rotor of the first hypergravity reactor (i.e., the enhanced mass transfer zone) through the riser pipe into the inverted U-shaped side of the top cover, thus realizing the flow of material from the enhanced separation zone into the enhanced mass transfer zone.

[0032] Furthermore, the downcomer channel includes a downcomer pipe and a lower cover plate covering the downcomer pipe.

[0033] Furthermore, one end of the downcomer is fixed to the support plate, and the other end extends into the rotor of the first hypergravity reactor. Furthermore, the lower cover plate is a U-shaped structure with a closed bottom and open sides, with its sides fixed to the support plate. During operation, the material in the enhanced mass transfer zone enters the enhanced separation zone through the downcomer via the U-shaped side of the lower cover plate, thus realizing the flow of material from the enhanced mass transfer zone into the enhanced separation zone.

[0034] Furthermore, the ultra-deep adsorption system includes one or more adsorption beds connected in parallel. Two or more adsorption beds connected in parallel allow each adsorption bed to perform continuous adsorption and regeneration operations alternately.

[0035] Furthermore, the top of the adsorption bed is provided with a material inlet connected to the light phase outlet, and the bottom is provided with a liquid hydrocarbon outlet.

[0036] Furthermore, the adsorption and regeneration of the adsorption bed are counter-current. For example, the light phase enters from the top of the adsorption bed, flows downward and exits from the bottom, while the regenerator enters from the bottom of the adsorption bed, flows upward and exits from the top, and finally, a deeply desilicationated liquid hydrocarbon product is obtained at the bottom outlet of the adsorption bed.

[0037] Furthermore, the adsorption bed is a fixed bed, filled with an adsorbent that removes organosilicon. The adsorbent can be commercially available or homemade, preferably including one or more of the following: modified or unmodified activated carbon, silica gel, alumina, molecular sieves, and macroporous adsorption resins.

[0038] Preferably, the adsorbent is soaked in alkaline solution and dried before use.

[0039] Furthermore, the adsorption bed is regenerated using a regenerant. The regenerant is preferably an organic, inorganic, or organic-inorganic mixture with regeneration capabilities; more preferably, it includes one or more of water, acid, alkali, salt, and alcohol; even more preferably, it includes one or more of pure water, formic acid, acetic acid, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, sodium chloride, methanol, ethanol, isopropanol, sodium hydroxide solution, and potassium hydroxide solution.

[0040] Secondly, the present invention provides the apparatus described in the first aspect for the application of deep silicon removal from liquid hydrocarbons.

[0041] Thirdly, the present invention provides a method for deep desiliconization of liquid hydrocarbons, using the apparatus described in the first aspect; The method for deep desiliconization of liquid hydrocarbons includes: feeding silicon-containing liquid hydrocarbon raw materials and desiliconizing agents into a hypergravity mass transfer system via a raw material distributor and a desiliconizing agent distributor, respectively, to remove inorganic silicon. In the hypergravity mass transfer system, the silicon-containing liquid hydrocarbon raw materials and desiliconizing agents first complete enhanced mass transfer in the rotor of the first hypergravity reactor, and then complete enhanced separation in the rotor of the second hypergravity reactor. The separated light phase enters the ultra-deep adsorption system through the light phase outlet to remove organosilicon.

[0042] The supergravity mass transfer system can remove the inorganic silicon content in silicon-containing liquid hydrocarbon feedstock to ≤10ppm.

[0043] The ultra-deep adsorption system can remove organosilicon content from the light phase to ≤10ppm.

[0044] The total silicon content in the liquid hydrocarbons at the outlet of the ultra-deep adsorption system can be ≤20ppm.

[0045] Furthermore, the method for preparing the desilication agent includes: preparing a microemulsion from an extractant, a precipitant, and a flocculant using a microemulsion preparation device to obtain the desilication agent.

[0046] The extractant preferably includes one or more of the following: water, hydrofluoric acid, xylene, butyl acetate, ethyl acetate, tributyl phosphate, dichloromethane, petroleum ether, and trioctylamine.

[0047] The mass fraction of the extractant in the desilication agent is preferably 50% to 98%.

[0048] The precipitant preferably includes at least one of inorganic precipitants and organic precipitants, and more specifically includes one or more of sodium hydroxide, potassium hydroxide, ammonia, sodium sulfate, sodium carbonate, barium chloride, oxalic acid, 8-hydroxyquinoline, and dimethylglyoxime.

[0049] The mass fraction of the precipitant in the desilication agent is preferably 1% to 25%.

[0050] The flocculant preferably includes one or more of the following: aluminum sulfate, aluminum chloride, ferric sulfate, ferric chloride, polyaluminum chloride, polyacrylamide, polyacrylic acid, sodium polyacrylate, calcium polyacrylate, and polyoxyethylene.

[0051] The mass fraction of flocculant in desilication agent is preferably 1% to 25%.

[0052] The mass ratio of the desiliconizing agent to the silicon-containing liquid hydrocarbon raw material is preferably 1:5 to 1:500, and more preferably 1:50 to 1:200.

[0053] The silicon-containing liquid hydrocarbon feedstock is preferably derived from any one or more of the following units: hydrotreating unit, hydrorefining unit, catalytic cracking unit, hydrocracking unit, isomerization unit, liquefied gas hydrogenation unit, etherification unit, coking unit, and condensation unit.

[0054] The preferred silicon-containing liquid hydrocarbon feedstock includes one or more of the following: silicon-containing crude oil, lubricating oil fraction, wax oil fraction, kerosene fraction, gasoline fraction, diesel fraction, heavy oil fraction, liquid light hydrocarbon, and liquefied petroleum gas.

[0055] In some embodiments, the total silicon mass content of the silicon-containing liquid hydrocarbon feedstock is ≤500ppm.

[0056] Furthermore, the operating conditions of the hypergravity mass transfer system include: a temperature of room temperature to 200℃, preferably 50 to 80℃; a pressure of 0.1 to 5.0 MPa, preferably 0.5 to 2.0 MPa; a residence time of 1 to 120 min, preferably 5 to 50 min; a rotor speed of 500 to 3000 rpm, preferably 1500 to 2500 rpm; and a rotor speed of 50 to 2000 rpm, preferably 500 to 1500 rpm.

[0057] Furthermore, the operating conditions for the adsorption process of the ultra-deep adsorption system include: a temperature of room temperature to 80℃, preferably 30 to 50℃; a pressure of 0.1 to 5.0 MPa, preferably 0.5 to 2.0 MPa; and a residence time of 1 to 60 min, preferably 2 to 30 min.

[0058] Furthermore, the operating conditions for the regeneration process of the ultra-deep adsorption system include: a temperature of room temperature to 200℃, preferably 50 to 150℃; a pressure of 0.1 to 3.0 MPa, preferably 0.1 to 1.0 MPa; and a residence time of 1 to 200 min, preferably 10 to 90 min.

[0059] Those skilled in the art should understand that existing liquid hydrocarbon desiliconization technologies or methods are limited in two ways. They primarily rely on hydrogenation through the loading of a hydrogenation silica-collecting agent during hydrorefining to achieve desiliconization. Furthermore, the slightly higher silicon content of the material can affect the hydrorefining effect, thus imposing strict requirements on the silicon content of the feedstock. Given the current state of the technology, it is unsuitable for scenarios involving silicon-containing or even high-silicon-content liquid hydrocarbon materials that only require deep desiliconization without hydrorefining. In other words, existing technologies struggle to achieve deep desiliconization of high-silicon-content liquid hydrocarbon feedstocks. Therefore, developing novel, efficient, and easily industrialized deep desiliconization technologies for liquid hydrocarbons is crucial to filling this gap and significantly contributing to increasing the added value of high-silicon-content oil products in the refining industry.

[0060] The apparatus and method of this invention employ a combination of a novel hypergravity mass transfer system and a deep adsorption system. The novel hypergravity mass transfer system consists of two coupled hypergravity reactors arranged opposite each other along a central axis. Under the action of a composite desiliconizing agent, the two hypergravity reactors achieve a enhanced coupling effect of mass transfer and separation within the same system but different centrifugal fields through counter-rotation and internal material exchange, thereby removing inorganic silicon content to ≤10ppm. Then, the organosilicon content is removed to ≤10ppm through a series deep adsorption system, thus ultimately achieving the removal of total silicon content in liquid hydrocarbons to ≤20ppm.

[0061] Compared with the prior art, the beneficial effects of this invention are as follows: 1. This invention removes inorganic and organic silicon from silicon-containing liquid hydrocarbon raw materials by targeting and combining them. This not only reduces the total silicon content in liquid hydrocarbons to a low level, but also has a wide range of sources for silicon-containing liquid hydrocarbon raw materials. In other words, the method of this invention has the advantages of high silicon removal efficiency and wide applicability to raw materials.

[0062] 2. This invention employs a novel, specially designed supergravity mass transfer system that enhances the coupling of the mass transfer and separation processes. Ultimately, under the action of a composite desilication agent, it achieves deep and efficient removal of inorganic silicon from silicon-containing liquid hydrocarbon raw materials, solving many problems of low efficiency, long residence time, numerous equipment stages, and unsatisfactory results in traditional mass transfer and separation processes.

[0063] 3. In the method of the present invention, the first hypergravity reactor and the second hypergravity reactor each have their own special design structure and a coupling design structure between them. That is, the material is interconnected by setting up liquid channels and down liquid channels inside the two relatively set and counter-rotating hypergravity reactors. This allows the material in the first hypergravity reactor to undergo droplet turning, film stretching, and rapid surface renewal during the mass transfer process, thereby achieving the effect of enhanced mass transfer. At the same time, the material in the second hypergravity reactor is forced to undergo droplet turning, rebound, splashing, and rapid coalescence during the separation process, thereby achieving the technical effect of enhanced separation. This method can also effectively solve problems such as material emulsification, thereby maximizing the technical effect of coupled enhanced mass transfer and enhanced separation. Attached Figure Description

[0064] Figure 1 This is a schematic diagram of the structure of a device for deep desiliconization of liquid hydrocarbons according to the present invention. Detailed Implementation

[0065] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Operating methods not specifically specified in the following embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0066] Example 1: See Figure 1 An apparatus for deep silicon removal from liquid hydrocarbons includes a gravity mass transfer system A for removing inorganic silicon and a deep adsorption system B for removing organic silicon.

[0067] The hypergravity mass transfer system A includes a first hypergravity reactor 100 and a second hypergravity reactor 200 arranged opposite each other with their central axes aligned, as well as related pipelines connected to them. The first hypergravity reactor 100 includes a first reaction chamber and a first rotor 105 disposed within the first reaction chamber. The first rotor 105 is externally connected to a first motor 107 via a first central shaft 108, and is filled with mass transfer packing 106. The second hypergravity reactor 200 includes a second reaction chamber and a second rotor 203 disposed within the second reaction chamber. The second rotor 203 is externally connected to a second motor 205 via a second central shaft 206, and is filled with separation packing 204. The opposing end faces of the first central shaft 108 and the second central shaft 206 are sealed without contact by sealing packing 109. The first and second reaction chambers are integrated and located within the same large reactor shell 110. A support plate 207 is provided between the first and second reaction chambers. The first reaction chamber and the second reaction chamber are connected by a rising liquid channel and a falling liquid channel. The rising liquid channel includes a rising liquid pipe 201 and an upper cover plate 209 covering the rising liquid pipe 201. One end of the rising liquid pipe 201 is fixed to the support plate 207, and the other end extends into the second rotor 203. The upper cover plate 209 is an inverted U-shaped structure with a closed top and open sides, and its sides are fixed to the support plate 207. The falling liquid channel includes a falling liquid pipe 104 and a lower cover plate 111 covering the lower part of the falling liquid pipe 104. One end of the falling liquid pipe 104 is fixed to the support plate 207, and the other end extends into the first rotor 105. The lower cover plate 111 is a U-shaped structure with a closed bottom and open sides, and its sides are fixed to the support plate 207. A raw material distributor 113 is axially arranged in the inner region of the mass transfer packing 106 to uniformly distribute the silicon-containing liquid hydrocarbon raw material 1 on the mass transfer packing 106. A desilication agent distributor 112 is axially arranged on the outer region of the mass transfer packing 106 to uniformly distribute the desilication agent 2 on the mass transfer packing 106. This design enables counter-current contact mass transfer between the silicon-containing liquid hydrocarbon feedstock 1 and the desilication agent 2 within the first hypergravity reactor 100. The silicon-containing liquid hydrocarbon feedstock 1 enters the first rotor 105 through the feedstock inlet 101 and the feedstock distributor 113. The desilication agent 2 enters the first rotor 105 through the desilication agent inlet 102 and the desilication agent distributor 112. A light phase outlet package 114 is provided at the top of the first hypergravity reactor 100, and the light phase outlet package 114 has a light phase outlet 103 connected to the ultra-deep adsorption system B. The light phase outlet 103 discharges the liquid hydrocarbon material 4 after the removal of inorganic silicon. A heavy phase outlet package 208 is provided at the bottom of the second hypergravity reactor 200, and the heavy phase outlet package 208 has a heavy phase outlet 202, which discharges the desilication precipitate 3.

[0068] In the first hypergravity reactor 100, the light phase material after enhanced mass transfer and removal of inorganic silicon enters the subsequent ultra-deep adsorption system B through the light phase outlet 103 for further removal of organosilicon, while the heavy phase material enters the separation packing 204 through the downcomer channel for further enhanced separation. In the second hypergravity reactor 200, the light phase after enhanced separation enters the first hypergravity reactor 100 through the upcomer channel, while the heavy phase, the desiliconized precipitate 3, exits from the heavy phase outlet 202.

[0069] The ultra-deep adsorption system B includes two adsorption beds connected in parallel, namely a first adsorption bed 300 and a second adsorption bed 400. The tops of the first adsorption bed 300 and the second adsorption bed 400 are respectively provided with a first material inlet 301 and a second material inlet 401 connected to a light phase outlet 103, and the bottoms are respectively provided with a first liquid hydrocarbon outlet 302 and a second liquid hydrocarbon outlet 402, from which liquid hydrocarbon material 7 after deep removal of organosilicon is discharged. The light phase outlet 103 is connected to the first material inlet 301 and the second material inlet 401 to allow the first adsorption bed 300 and the second adsorption bed 400 to switch between adsorption and regeneration operations. The adsorption and regeneration of the adsorption beds are counter-current. The bottoms of the first adsorption bed 300 and the second adsorption bed 400 are respectively provided with a first regenerator inlet 303 and a second regenerator inlet 403, and the tops are respectively provided with a first regenerator outlet 304 and a second regenerator outlet 404. Fresh regenerator 5 enters from the first regenerator inlet 303 and the second regenerator inlet 403. The regenerant after regeneration is discharged from the first regenerant outlet 304 and the second regenerant outlet 404.

[0070] Example 2: Deep desiliconization was performed using the apparatus of Example 1. Tables 1 and 2 show two types of silicon-containing liquid hydrocarbon raw materials to be treated, denoted as silicon-containing liquid hydrocarbon raw material I and silicon-containing liquid hydrocarbon raw material II, respectively; Tables 3, 4, and 5 show three types of composite desiliconizing agents, denoted as composite desiliconizing agent I, composite desiliconizing agent II, and composite desiliconizing agent III, respectively.

[0071] Table 1. Silicon-containing liquid hydrocarbon feedstock I to be processed Table 2. Silicon-containing liquid hydrocarbon feedstock II to be processed Table 3 Composite Desilication Agent I Table 4 Composite Desilication Agent II Table 5 Composite Desilication Agent III The silicon-containing liquid hydrocarbon raw material I in Table 1 and the composite desilication agent I in Table 3 are sent to the hypergravity mass transfer system. The two are then sequentially subjected to enhanced mass transfer and enhanced separation in the first and second hypergravity reactors to remove the inorganic silicon content in the liquid hydrocarbon raw material to ≤10ppm. Then, the silicon-containing liquid hydrocarbon is sent to the ultra-deep adsorption system to remove the organic silicon to ≤10ppm, that is, the total silicon content in the liquid hydrocarbon raw material is finally reduced to ≤20ppm.

[0072] Operating conditions of the hypergravity mass transfer system: temperature 50℃, pressure 0.85MPa, residence time 42.8min.

[0073] First hypergravity reactor: Both the raw material distributor and the desiliconizing agent distributor are atomizing nozzles; The composite desilication agent is first prepared into a microemulsion using a microfluidic homogenizer before entering the first hypergravity reactor; The mass ratio of the composite desilication agent to the silicon-containing liquid hydrocarbon raw material is 1:110; The mass transfer packing is made of fiber-braided packing sheets wound together. These sheets are composed of composite fibers woven together in a 5:1 weight ratio of hydrophilic to oleophobic fibers. Each layer of the fiber-braided sheet is 0.5 cm thick and has a diamond-shaped pattern on its surface. During packing, the packing is divided into two layers: an inner layer of 20 layers (23.7% porosity) and an outer layer of 20 layers (39.6% porosity). Viewed from top to bottom, the first central shaft rotates clockwise at a speed of 1760 rpm.

[0074] Second hypergravity reactor: The separating packing is composed of stacked annular fiber braided packing sheets. These sheets are made of composite fibers woven together in a 1:5 weight ratio of hydrophilic to oleophobic fibers. Each layer of the braided packing sheet is 2 cm thick and has an X-shaped pattern on its surface. The separating packing is filled in two layers: the upper layer contains 12 packing layers (with a porosity of 38.1%), and the lower layer contains 12 packing layers (with a porosity of 69.4%). Viewed from top to bottom, the second central shaft rotates counterclockwise at a speed of 960 rpm.

[0075] In both the first and second hypergravity reactors, the packing sheets are made of 50μm polypropylene fibers (oil-loving and hydrophobic fibers) and 50μm polyvinyl alcohol fibers (hydrophobic and oleophobic fibers).

[0076] Ultra-deep desorption system: The adsorbent is prepared by soaking, washing, and drying commercially available 5A molecular sieves in a 5wt% sodium hydroxide solution before filling and using it. The regenerator is a 0.5% dilute hydrofluoric acid aqueous solution.

[0077] Adsorption process operating conditions: temperature 30℃, pressure 0.5MPa, residence time 10.6min; The operating conditions for the regeneration process are: temperature 60℃, pressure 1.1MPa, and residence time 55min.

[0078] The results of the deep desiliconization technology for liquid hydrocarbons after treatment using the above methods are shown in Table 6.

[0079] Example 3: Deep silicon removal was performed using the apparatus of Example 1, and the deep silicon removal method was similar to that of Example 2.

[0080] The silicon-containing liquid hydrocarbon raw material I to be treated was used, and the composite desilication agent II was used, as shown in Table 4.

[0081] Operating conditions for the hypergravity mass transfer system: temperature 50℃, pressure 0.85MPa, residence time 45min.

[0082] First hypergravity reactor: Both the raw material distributor and the desiliconizing agent distributor are atomizing nozzles; The composite desilication agent is first prepared into a microemulsion using a microfluidic homogenizer before entering the first hypergravity reactor; The mass ratio of the composite desilication agent to the silicon-containing liquid hydrocarbon raw material is 1:180; The mass transfer packing is made of fiber-braided packing sheets wound together. These sheets are composed of composite fibers woven together in a 5:1 weight ratio of hydrophilic to oleophobic fibers. Each layer of the fiber-braided sheet is 0.5 cm thick and has a diamond-shaped pattern on its surface. During packing, the packing is divided into two layers: an inner layer of 15 layers (16.4% porosity) and an outer layer of 25 layers (42.7% porosity). Viewed from top to bottom, the first central shaft rotates clockwise at a speed of 2460 rpm.

[0083] Second hypergravity reactor: The separating packing is composed of stacked annular fiber braided packing sheets. These sheets are made of composite fibers woven together in a 1:5 weight ratio of hydrophilic to oleophobic fibers. Each layer of the fiber braided sheet is 2 cm thick and has an X-shaped pattern on its surface. During filling, the separating packing is divided into two layers: the upper layer contains 12 layers of packing with a porosity of 38.1%, and the lower layer contains 12 layers of packing with a porosity of 69.4%. Viewed from top to bottom, the second central shaft rotates counterclockwise at a speed of 550 rpm.

[0084] In both the first and second hypergravity reactors, the packing sheets are made of 50μm polypropylene fibers (oil-loving and hydrophobic fibers) and 50μm polyvinyl alcohol fibers (hydrophobic and oleophobic fibers).

[0085] Ultra-deep adsorption system: The adsorbent is prepared by soaking, washing, and drying commercially available 5A molecular sieves in a 1wt% sodium hydroxide solution before filling and using it. Methanol is used as the regenerant.

[0086] Adsorption process operating conditions: temperature 30℃, pressure 0.5MPa, residence time 17.2min; The operating conditions for the regeneration process are: temperature 60℃, pressure 1.1MPa, and residence time 32min.

[0087] The results of the deep desiliconization technology for liquid hydrocarbons after treatment using the above methods are shown in Table 6.

[0088] Example 4: Deep silicon removal was performed using the apparatus of Example 1, and the deep silicon removal method was similar to that of Example 2.

[0089] The silicon-containing liquid hydrocarbon raw material I to be treated was used, and the composite desilication agent III was used, as shown in Table 5.

[0090] Operating conditions of the hypergravity mass transfer system: temperature 50℃, pressure 1.0MPa, residence time 37.6min.

[0091] First hypergravity reactor: Both the raw material distributor and the desiliconizing agent distributor are atomizing nozzles; The composite desilication agent is first prepared into a microemulsion using a microfluidic homogenizer before entering the first hypergravity reactor; The mass ratio of the composite desilication agent to the silicon-containing liquid hydrocarbon raw material is 1:60; The mass transfer packing is made of fiber-braided packing sheets wound together. These sheets are composed of composite fibers woven together in a 5:1 weight ratio of hydrophilic to oleophobic fibers. Each layer of the fiber-braided sheet is 0.5 cm thick and has a diamond-shaped pattern on its surface. During packing, the packing is divided into two layers: an inner layer of 25 layers (23.7% porosity) and an outer layer of 15 layers (36.5% porosity). Viewed from top to bottom, the first central shaft rotates clockwise at a speed of 1580 rpm.

[0092] Second hypergravity reactor: The separating packing is composed of stacked annular fiber braided packing sheets. These sheets are made of composite fibers woven together in a 1:5 weight ratio of hydrophilic to oleophobic fibers. Each layer of the braided packing sheet is 2 cm thick and has an X-shaped pattern on its surface. During filling, the separating packing is installed in two layers: the upper layer contains 12 layers of packing with a porosity of 51.2%, and the lower layer contains 12 layers of packing with a porosity of 78.5%.

[0093] Viewed from top to bottom, the second central shaft rotates counterclockwise at a speed of 750 rpm.

[0094] In both the first and second hypergravity reactors, the packing sheets are made of 50μm polypropylene fibers (oil-loving and hydrophobic fibers) and 50μm polyvinyl alcohol fibers (hydrophobic and oleophobic fibers).

[0095] Ultra-deep adsorption system: The adsorbent is prepared by soaking, washing, and drying commercially available macroporous resin adsorbent with a 0.5 wt% sodium hydroxide solution before filling and use. The regenerant is a 5% sodium hydroxide solution.

[0096] Adsorption process operating conditions: temperature 30℃, pressure 0.5MPa, residence time 13.6min; The operating conditions for the regeneration process are: temperature 60℃, pressure 1.1MPa, and residence time 25min.

[0097] The results of the deep desiliconization technology for liquid hydrocarbons after treatment using the above methods are shown in Table 6.

[0098] Example 5: Deep silicon removal was performed using the apparatus of Example 1, and the deep silicon removal method was similar to that of Example 2.

[0099] The silicon-containing liquid hydrocarbon raw material II to be treated was used, and the composite desilication agent I was used, as shown in Table 3.

[0100] Operating conditions for the hypergravity mass transfer system: temperature 50℃, pressure 0.85MPa, residence time 17.5min.

[0101] First hypergravity reactor: Both the raw material distributor and the desiliconizing agent distributor are atomizing nozzles; The composite desilication agent is first prepared into a microemulsion using a microfluidic homogenizer before entering the first hypergravity reactor; The mass ratio of the composite desilication agent to the silicon-containing liquid hydrocarbon raw material is 1:100; The mass transfer packing is made of fiber-braided packing sheets wound together. The fiber-braided packing sheets are woven from composite fiber filaments, consisting of hydrophilic and oleophobic fibers woven together in a 5:1 weight ratio. Each layer of the fiber-braided sheet is 0.5 cm thick and has a diamond-shaped pattern on its surface. During packing, the mass transfer packing is filled in two layers: an inner layer of 10 layers (16.5% porosity) and an outer layer of 30 layers (44.5% porosity). Viewed from top to bottom, the first central shaft rotates clockwise at a speed of 1280 rpm.

[0102] Second hypergravity reactor: The separating packing is composed of stacked annular fiber braided packing sheets. These sheets are made of composite fibers woven together in a 1:5 weight ratio of hydrophilic to oleophobic fibers. Each layer of the braided packing sheet is 2 cm thick and has an X-shaped pattern on its surface. The separating packing is filled in two layers: the upper layer contains 12 packing layers (with a porosity of 52.4%), and the lower layer contains 12 packing layers (with a porosity of 78.5%).

[0103] Viewed from top to bottom, the second central shaft rotates counterclockwise at a speed of 1260 rpm.

[0104] In both the first and second hypergravity reactors, the packing sheets are made of 50μm polypropylene fibers (oil-loving and hydrophobic fibers) and 50μm polyvinyl alcohol fibers (hydrophobic and oleophobic fibers).

[0105] Ultra-deep adsorption system: The adsorbent is prepared by soaking, washing, and drying commercially available 5A molecular sieves in a 5wt% sodium hydroxide solution before filling and using it. The regenerator is a 0.5% dilute hydrofluoric acid aqueous solution.

[0106] Adsorption process operating conditions: temperature 30℃, pressure 0.5MPa, residence time 18min; The operating conditions for the regeneration process are: temperature 60℃, pressure 1.1MPa, and residence time 45min.

[0107] The results of the deep desiliconization technology for liquid hydrocarbons after treatment using the above methods are shown in Table 6.

[0108] Example 6: Deep silicon removal was performed using the apparatus of Example 1, and the deep silicon removal method was similar to that of Example 2.

[0109] The silicon-containing liquid hydrocarbon raw material II to be treated was used, as shown in Table 2, and the composite desilication agent II was used, as shown in Table 4.

[0110] Operating conditions of the hypergravity mass transfer system: temperature 50℃, pressure 0.85MPa, residence time 22.4min.

[0111] First hypergravity reactor: Both the raw material distributor and the desiliconizing agent distributor are atomizing nozzles; The composite desilication agent is first prepared into a microemulsion using a microfluidic homogenizer before entering the first hypergravity reactor; The mass ratio of the composite desilication agent to the silicon-containing liquid hydrocarbon raw material is 1:80; The mass transfer packing is made of fiber-braided packing sheets wound together. The fiber-braided packing sheets are woven from composite fiber filaments, consisting of hydrophilic and oleophobic fibers woven together in a 5:1 weight ratio. Each layer of the fiber-braided sheet is 0.5 cm thick and has a diamond-shaped pattern on its surface. During packing, the mass transfer packing is filled in two layers: an inner layer of 20 layers (with a porosity of 20.2%) and an outer layer of 20 layers (with a porosity of 36.8%). Viewed from top to bottom, the first central shaft rotates clockwise at a speed of 1800 rpm.

[0112] Second hypergravity reactor: The separating packing is composed of stacked annular fiber braided packing sheets. These sheets are made of composite fibers woven together in a 1:5 weight ratio of hydrophilic to oleophobic fibers. Each layer of the braided packing sheet is 2 cm thick and has an X-shaped pattern on its surface. During filling, the separating packing is installed in two layers: the upper layer contains 12 layers of packing with a porosity of 45.2%, and the lower layer contains 12 layers of packing with a porosity of 79.6%.

[0113] Viewed from top to bottom, the second central shaft rotates counterclockwise at a speed of 850 rpm.

[0114] In both the first and second hypergravity reactors, the packing sheets are made of 50μm polypropylene fibers (oil-loving and hydrophobic fibers) and 50μm polyvinyl alcohol fibers (hydrophobic and oleophobic fibers).

[0115] Ultra-deep adsorption system: The adsorbent is prepared by soaking, washing, and drying commercially available 5A molecular sieves in a 1wt% sodium hydroxide solution before filling and using it. Methanol is used as the regenerant.

[0116] Adsorption process operating conditions: temperature 30℃, pressure 0.5MPa, residence time 18.6min; The operating conditions for the regeneration process are: temperature 60℃, pressure 1.1MPa, and residence time 55min.

[0117] The results of the deep desiliconization technology for liquid hydrocarbons after treatment using the above methods are shown in Table 6.

[0118] Example 7: Deep silicon removal was performed using the apparatus of Example 1, and the deep silicon removal method was similar to that of Example 2.

[0119] The silicon-containing liquid hydrocarbon raw material II to be treated was used, and the composite desilication agent III was used, as shown in Table 5.

[0120] Operating conditions of the hypergravity mass transfer system: temperature 50℃, pressure 1.0MPa, residence time 16.6min.

[0121] First hypergravity reactor: Both the raw material distributor and the desiliconizing agent distributor are atomizing nozzles; The composite desilication agent is first prepared into a microemulsion using a microfluidic homogenizer before entering the first hypergravity reactor; The mass ratio of the composite desilication agent to the silicon-containing liquid hydrocarbon raw material is 1:150; The mass transfer packing is made of fiber-braided packing sheets wound together. The fiber-braided packing sheets are composed of composite fiber filaments woven together in a 5:1 weight ratio of hydrophilic to oleophobic fibers. Each layer of the fiber-braided sheet is 0.5 cm thick and has a diamond-shaped pattern on its surface. During packing, the mass transfer packing is filled in two layers: an inner layer of 15 layers (18.5% porosity) and an outer layer of 25 layers (40.8% porosity). Viewed from top to bottom, the first central shaft rotates clockwise at a speed of 2010 rpm.

[0122] Second hypergravity reactor: The separating packing is composed of stacked annular fiber braided packing sheets. These sheets are made of composite fibers woven together in a 1:5 weight ratio of hydrophilic to oleophobic fibers. Each layer of the braided packing sheet is 2 cm thick and has an X-shaped pattern on its surface. During filling, the separating packing is divided into two layers: the upper layer contains 12 layers of packing with a porosity of 46.5%, and the lower layer contains 12 layers of packing with a porosity of 70.3%.

[0123] Viewed from top to bottom, the second central shaft rotates counterclockwise at a speed of 1250 rpm.

[0124] In both the first and second hypergravity reactors, the packing sheets are made of 50μm polypropylene fibers (oil-loving and hydrophobic fibers) and 50μm polyvinyl alcohol fibers (hydrophobic and oleophobic fibers).

[0125] Ultra-deep adsorption system: The adsorbent is prepared by soaking, washing, and drying commercially available macroporous resin adsorbent with a 0.5 wt% sodium hydroxide solution before filling and use. The regenerant is a 3% sodium hydroxide solution.

[0126] Adsorption process operating conditions: temperature 30℃, pressure 0.5MPa, residence time 18min; The operating conditions for the regeneration process are: temperature 50℃, pressure 1.1MPa, and residence time 40min.

[0127] The results of the deep desiliconization technology for liquid hydrocarbons after treatment using the above methods are shown in Table 6.

[0128] Table 6 As shown in Table 6, Examples 2-7 employ the liquid hydrocarbon deep desiliconization device and method of the present invention. Specifically, the combined process of the novel hypergravity mass transfer system and the ultra-deep adsorption system utilizes two specially designed hypergravity reactors to achieve a enhanced coupling effect between mass transfer and separation under the action of a composite desiliconizing agent. Furthermore, through series combination with the ultra-deep adsorption system, the total silicon content in the liquid hydrocarbon is removed to ≤20ppm. This method has advantages such as high desiliconization efficiency, low equipment investment and operating energy consumption, wide adaptability to raw materials, and strong feasibility, which is of great significance for increasing the added value of high-silicon-content liquid hydrocarbons.

[0129] Furthermore, it should be understood that after reading the above description of the present invention, those skilled in the art can make various alterations or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. A device for deep silicon removal from liquid hydrocarbons, characterized in that, This includes a hypergravity mass transfer system for removing inorganic silicon and an ultra-deep adsorption system for removing organic silicon. The hypergravity mass transfer system includes a first hypergravity reactor and a second hypergravity reactor arranged vertically opposite each other with their central axes aligned on the same straight line. Both reactors include a reaction chamber and a rotor disposed within it, with each rotor connected to an external drive mechanism via its central axis. The rotor of the first hypergravity reactor is filled with mass transfer packing, while the rotor of the second hypergravity reactor is filled with separation packing. The reaction chambers of the first and second hypergravity reactors are connected by a rising liquid channel and a falling liquid channel. A raw material distributor is axially arranged in the inner region of the mass transfer packing, and a desilication agent distributor is axially arranged in the outer region. A light phase outlet connected to an ultra-deep adsorption system is located at the top of the first hypergravity reactor, and a heavy phase outlet is located at the bottom of the second hypergravity reactor.

2. The apparatus for deep desiliconization of liquid hydrocarbons according to claim 1, characterized in that, The opposing end faces of the central rotating shaft of the first and second supergravity reactors are connected by filling with sealing packing material to achieve a non-contact sealing connection. Sealing fillers include one or more of the following: asbestos fabric, polytetrafluoroethylene, carbon fiber, rubber, flexible graphite, metal composite materials, and engineering plastics.

3. The apparatus for deep desiliconization of liquid hydrocarbons according to claim 1, characterized in that, During operation: The rotor speed of the first hypergravity reactor is greater than or equal to the rotor speed of the second hypergravity reactor; The first and second hypergravity reactors rotate in opposite directions along their respective central axes.

4. The apparatus for deep desiliconization of liquid hydrocarbons according to claim 1, characterized in that, The mass transfer packing has a dense, three-dimensional, and regular packing structure composed of multiple layers of fiber-woven sheet material wound around a central axis, forming dense microchannels. The thickness of a single layer of fiber-woven sheet is 0.1~10 cm, preferably 0.5~2 cm. The porosity of the mass transfer packing increases from the inside to the outside, with the inner porosity being 10%~30%, preferably 15%~25%, and the outer porosity being 30%~50%, preferably 35%~45%. The mass transfer filler fiber is a first composite fiber filament woven together with hydrophilic and hydrophobic fiber filaments, wherein the weaving ratio of hydrophilic and hydrophobic fiber filaments to hydrophilic and hydrophobic fiber filaments by weight is 10:1 to 1:1, preferably 5:1 to 2:

1. The surface of the mass transfer packing has a first composite fiber filament woven into a first pattern structure, the first pattern structure including one or more of the following: rhombus, square, rectangle, circle, ellipse, and hexagon; The separating packing is composed of multiple layers of annular structured packing stacked perpendicular to the central axis of rotation; The thickness of a single layer of the annular structured packing is 0.5~20cm, preferably 2~5cm; The porosity of the separating packing increases from top to bottom, with the top layer having a porosity of 30%~60%, preferably 35%~55%, and the bottom layer having a porosity of 60%~90%, preferably 65%~85%. The annular structured filler layer is woven from a second composite fiber filament woven together with hydrophilic and hydrophobic fibers, wherein the weaving ratio of hydrophilic and hydrophobic fibers to hydrophilic and hydrophobic fibers by weight is 1:1.1 to 1:10, preferably 1:2 to 1:5; The surface of the separating packing has a second composite fiber filament woven into a second pattern structure, the second pattern structure including one or more of the following: X-type, V-type, 8-type, Ω-type, and teardrop-shaped; Oleophilic and hydrophobic fibers include one or more of the following: polyester fibers, nylon fibers, polyurethane fibers, polypropylene fibers, polyacrylonitrile fibers, polyvinyl chloride fibers, and fibers whose surfaces have been modified with oleophilic and hydrophobic properties. The hydrophilic and oleophobic fiber includes at least one of the following: high molecular polymer fiber with one or more of carboxyl, amino, and hydroxyl groups in the main chain and / or side chain; fiber with surface hydrophilic and oleophobic modification treatment; and further includes at least one of acrylic fiber, polyvinyl alcohol fiber, and polyethylene glycol fiber. The diameters of the oleophilic and hydrophobic fibers are 5~50μm.

5. The apparatus for deep desiliconization of liquid hydrocarbons according to claim 1, characterized in that, The first and second hypergravity reactor reaction chambers are integrated and located within the same large reactor shell. A support plate is provided between the reaction chamber of the first hypergravity reactor and the reaction chamber of the second hypergravity reactor; The riser channel includes a riser tube and a cover plate covering the riser tube; One end of the riser pipe is fixed to the support plate, and the other end extends into the rotor of the second hypergravity reactor. The top cover is an inverted U-shaped structure with a closed top and openings on the sides, and its sides are fixed to the support plate. The downcomer channel includes a downcomer pipe and a lower cover plate covering the bottom of the downcomer pipe; One end of the downcomer is fixed to the support plate, and the other end extends into the rotor of the first hypergravity reactor. The lower cover plate is a U-shaped structure with a closed bottom and openings on the sides, and its sides are fixed to the support plate.

6. The apparatus for deep desiliconization of liquid hydrocarbons according to claim 1, characterized in that, The ultra-deep adsorption system consists of one or more adsorption beds connected in parallel; The top of the adsorption bed is provided with a material inlet connected to the light phase outlet, and the bottom is provided with a liquid hydrocarbon outlet; The adsorption and regeneration of the adsorption bed are in countercurrent flow. The adsorption bed is a fixed bed, filled with an adsorbent that removes organosilicon. The adsorbent includes one or more of the following: modified or unmodified activated carbon, silica gel, alumina, molecular sieve, and macroporous adsorption resin. The adsorbent should be soaked in alkaline solution and dried before use. The adsorption bed is regenerated using a regenerant, which is an organic, inorganic, or organic-inorganic mixture with regeneration function, including one or more of water, acid, alkali, salt, and alcohol, and further including one or more of pure water, formic acid, acetic acid, sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid, sodium chloride, methanol, ethanol, isopropanol, sodium hydroxide solution, and potassium hydroxide solution.

7. The apparatus according to any one of claims 1 to 6 is used for deep desiliconization of liquid hydrocarbons.

8. A method for deep desiliconization of liquid hydrocarbons, characterized in that, The apparatus according to any one of claims 1 to 6 may be used; The method for deep desiliconization of liquid hydrocarbons includes: feeding silicon-containing liquid hydrocarbon raw materials and desiliconizing agents into a hypergravity mass transfer system via a raw material distributor and a desiliconizing agent distributor, respectively, to remove inorganic silicon. In the hypergravity mass transfer system, the silicon-containing liquid hydrocarbon raw materials and desiliconizing agents first complete enhanced mass transfer in the rotor of the first hypergravity reactor, and then complete enhanced separation in the rotor of the second hypergravity reactor. The separated light phase enters the ultra-deep adsorption system through the light phase outlet to remove organosilicon.

9. The method for deep desiliconization of liquid hydrocarbons according to claim 8, characterized in that, The high-gravity mass transfer system removes the inorganic silicon content in silicon-containing liquid hydrocarbon feedstock to ≤10ppm; The ultra-deep adsorption system removes organosilicon from the light phase to ≤10ppm. The total silicon content in the liquid hydrocarbons at the outlet of the ultra-deep adsorption system is ≤20ppm.

10. The method for deep desiliconization of liquid hydrocarbons according to claim 8 or 9, characterized in that, The method for preparing the desilication agent includes: preparing a microemulsion from an extractant, a precipitant, and a flocculant using a microemulsion preparation device to obtain the desilication agent; The extractant includes one or more of the following: water, hydrofluoric acid, xylene, butyl acetate, ethyl acetate, tributyl phosphate, dichloromethane, petroleum ether, and trioctylamine. The extractant has a mass fraction of 50% to 98% in the desilication agent; The precipitant includes at least one of inorganic precipitants and organic precipitants, and more specifically includes one or more of sodium hydroxide, potassium hydroxide, ammonia, sodium sulfate, sodium carbonate, barium chloride, oxalic acid, 8-hydroxyquinoline, and dimethylglyoxime. The mass fraction of the precipitant in the desilication agent is 1%~25%; Flocculants include one or more of the following: aluminum sulfate, aluminum chloride, ferric sulfate, ferric chloride, polyaluminum chloride, polyacrylamide, polyacrylic acid, sodium polyacrylate, calcium polyacrylate, and polyoxyethylene. The mass fraction of flocculant in desilication agent is 1%~25%; The mass ratio of the desiliconizing agent to the silicon-containing liquid hydrocarbon raw material is 1:5 to 1:500, preferably 1:50 to 1:200; The silicon-containing liquid hydrocarbon feedstock comes from any one or more of the following units: hydrotreating unit, hydrorefining unit, catalytic cracking unit, hydrocracking unit, isomerization unit, liquefied gas hydrotreating unit, etherification unit, coking unit, and condensation unit. Silicon-containing liquid hydrocarbon feedstocks include one or more of the following: crude oil, lubricating oil fractions, wax oil fractions, kerosene fractions, gasoline fractions, diesel fractions, heavy oil fractions, liquid light hydrocarbons, and liquefied petroleum gas. The total silicon content of silicon-containing liquid hydrocarbon feedstock is ≤500ppm by mass; The operating conditions of the hypergravity mass transfer system include: a temperature of room temperature to 200℃, preferably 50 to 80℃; a pressure of 0.1 to 5.0 MPa, preferably 0.5 to 2.0 MPa; a residence time of 1 to 120 min, preferably 5 to 50 min; a rotor speed of 500 to 3000 rpm, preferably 1500 to 2500 rpm, and a rotor speed of 50 to 2000 rpm, preferably 500 to 1500 rpm, for the second hypergravity reactor. The operating conditions for the adsorption process of the ultra-deep adsorption system include: temperature of room temperature to 80℃, preferably 30 to 50℃; pressure of 0.1 to 5.0 MPa, preferably 0.5 to 2.0 MPa; and residence time of 1 to 60 min, preferably 2 to 30 min. The operating conditions for the regeneration process of the ultra-deep adsorption system include: temperature of room temperature to 200℃, preferably 50 to 150℃; pressure of 0.1 to 3.0 MPa, preferably 0.1 to 1.0 MPa; and residence time of 1 to 200 min, preferably 10 to 90 min.

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