Deep desiliconization treatment device and method for hydrocarbon liquid

Abstract

The invention discloses a deep desiliconization treatment device and method for hydrocarbon liquid. The deep desilicication treatment device comprises an electric settler, a membrane filter, a heavy phase adsorption desilicication device and a light phase adsorption desilicication device; the electric settler comprises an electric settling area at the upper part and a slag-slurry separation area at the lower part; an upper electrode plate and a lower electrode plate are arranged in the electro-sedimentation area; the area, located above the upper electrode plate, in the electro-sedimentation area is a light phase storage cavity connected with a light phase adsorption silicon remover, the area, located below the lower electrode plate, in the electro-sedimentation area is a heavy phase storage cavity communicated with the slag slurry separation area, and the area, located between the upper electrode plate and the lower electrode plate, in the electro-sedimentation area is externally connected with a high-emulsification-state mixture containing silicon hydrocarbon liquid and a desiliconization agent; an upper grating plate and a lower grating plate are arranged in the slag slurry separation area, and coalescence separation balls are arranged between the upper grating plate and the lower grating plate; a slag slurry outlet is formed in the bottom of the electric settler; a heavy liquid outlet is formed in the side surface below the lower grating plate; an inlet of the membrane filter is connected with a heavy liquid outlet, and a membrane filtration penetrating fluid outlet is connected with the heavy phase adsorption silicon remover.

Description

Technical Field

[0001] This invention relates to the field of petrochemical technology, specifically to a deep desilication treatment device for hydrocarbon liquids, and a method for deep desilication using the device. Background Technology

[0002] Generally, crude oil and various distillate oils in the oil refining industry contain small amounts of silicon-containing compounds. These silicon-containing compounds mainly come from various silicon-containing additives added during oil processing, such as organosilicon viscosity reducers (the main silicon-containing component is polysiloxane), organosilicon defoamers (the main silicon-containing component is dimethylsiloxane), and organosilicon crude oil demulsifiers (the main silicon-containing component is composed of polyether and methylethoxysiloxane block copolymers). These silicon compounds are distributed in various corresponding distillate oils according to their boiling points, with the silicon content being higher in inferior naphtha. Since naphtha is mainly used as a feedstock for ethylene and catalytic reforming in refineries, it needs to be hydrotreated before entering subsequent units. However, naphtha with high silicon content entering the hydrotreating unit will cause silicon deposition in the hydrotreating catalyst and poisoning and deactivation of subsequent catalysts. Therefore, the existing technology usually involves filling the hydrotreating reactor with a silicon-scavenging agent and completing the desiliconization under high temperature and high pressure conditions. This not only has harsh reaction conditions and high energy consumption, but more importantly, it is difficult to handle feedstocks with high silicon content. This makes it impossible for the existing hydrodesiliconization technology to achieve deep desiliconization of oil products with high silicon content. Therefore, there is an urgent need to develop a new and efficient deep desiliconization technology for liquid hydrocarbons.

[0003] 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. The catalyst primarily achieves its silicon-containing function through its large pore volume.

[0004] 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.

[0005] Patent CN112705223B discloses a silicon-catching agent and its preparation method. The silicon-catching agent comprises a carrier and a hydrogenation active component. The hydrogenation active component consists of Group VIB metal sulfides, Group VIB metal oxides, and Group VIII metal oxides. Based on the total weight of the silicon-catching agent, the Group VIB metal sulfides are 0.3wt% to 18.3wt%, the Group VIB metal oxides are 0.1wt% to 5.0wt%, and the Group VIII metal oxides are 0.2wt% to 12.0wt%. 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 in silicon-containing oil products such as coking dry gas, coking naphtha, and coking diesel.

[0006] In existing desiliconization technologies, the oil refining industry exclusively employs hydrodesiliconization, which involves using a hydrosilicon-scavenging agent during hydrorefining under hydrotreated conditions. However, this method has significant limitations. Firstly, the hydrotreated process has strict requirements on the silicon content of the feedstock; otherwise, even slightly high silicon content can affect hydrotreating performance, rendering existing technologies unable to handle oils with slightly or even very high silicon content. Secondly, hydrodesiliconization during hydrotreated processes suffers from numerous problems, including demanding reaction conditions, high energy costs, and complex processes. Therefore, there is an urgent need to develop low-cost, high-efficiency desiliconization technologies capable of handling high-silicon-content feedstocks, which is of great significance for replacing existing hydrodesiliconization techniques. Summary of the Invention

[0007] To address the aforementioned technical problems and shortcomings in this field, the present invention provides a device and method for deep desilication treatment of hydrocarbon liquids. First, a highly emulsified mixture of silicon-containing hydrocarbon liquid and a desilication agent is prepared. After thorough stabilization and homogenization, the mixture is introduced into a specially designed electrostatic precipitator to obtain a light phase, a heavy phase, and a slurry phase. The heavy phase sequentially passes through a membrane filter and a heavy phase adsorption desilication unit, while the light phase passes through a light phase adsorption desilication unit. Ultimately, ultra-deep removal of organosilicon and inorganic silicon from the hydrocarbon liquid is achieved, resulting in a total silicon content ≤10 ppm and a total desilication rate exceeding 98%. Compared with existing hydrogenation desilication technology, this method significantly simplifies the process flow and achieves low-cost deep desilication under relatively mild process conditions. The specific technical solution is as follows: In a first aspect, the present invention provides a deep desilication treatment device for hydrocarbon liquids, including an electrostatic precipitator, a membrane filter, a heavy phase adsorption desilication device and a light phase adsorption desilication device. The electrostatic precipitator consists of an upper electrostatic precipitation zone and a lower slurry separation zone; The electrosettling zone is equipped with an upper electrode plate and a lower electrode plate; the area above the upper electrode plate in the electrosettling zone is a light phase storage chamber, which is connected to the light phase adsorption desiliconizer; the area below the lower electrode plate in the electrosettling zone is a heavy phase storage chamber, which is connected to the slurry separation zone; the area between the upper and lower electrode plates in the electrosettling zone is externally connected to a highly emulsified mixture containing silane hydrocarbon liquid and desiliconizing agent. The slurry separation zone is equipped with an upper grid plate and a lower grid plate, and coalescing separation balls are installed between the upper grid plate and the lower grid plate. The electrostatic precipitator is equipped with a slurry outlet at the bottom and a heavy liquid outlet on the side below the lower grating plate. The inlet of the membrane filter is connected to the heavy liquid outlet, and the membrane filtration permeate outlet is connected to the heavy phase adsorption desiliconizer.

[0008] Electrostatic precipitators and membrane filters are mainly used for the deep removal of inorganic silicon compounds from hydrocarbon liquids.

[0009] The primary objective of the electrostatic precipitator is to separate the light phase, heavy phase, and slurry. The electrostatic precipitation zone is mainly used for rapid demulsification and separation of the light and heavy phases, while the slurry separation zone is mainly used for efficient agglomeration and separation of the heavy phase and slurry precipitates. The heavy phase adsorption desiliconizer and the light phase adsorption desiliconizer are mainly used for the deep removal of organosilicon compounds from hydrocarbon liquids. The material outlets of the light phase adsorption desiliconizer and the heavy phase adsorption desiliconizer are connected and merged to obtain the deep desiliconization product outlet material of the device of this invention.

[0010] Given the clear separation of the light and heavy phases in the electrostatic settling zone of the electrostatic precipitator, silicon-containing compounds and their precipitates exist entirely in the heavy phase as suspended solids. These suspended solids are difficult to separate effectively using conventional methods and require special removal techniques. Therefore, this invention employs a specially designed multi-stage coalescing separation sphere system in the slurry separation zone to capture, coalesce, grow, and recapture suspended solids, achieving highly efficient and enhanced coalescing separation. Simultaneously, since the smaller suspended solids in the heavy phase material are uniformly dispersed, multi-stage coalescing separation spheres alone cannot effectively remove them, leading to a high inorganic silicon content in the heavy phase. Therefore, the heavy phase material is introduced into a membrane filtration device for nanofiltration, achieving effective removal of suspended solids.

[0011] Furthermore, the upper and lower electrode plates face each other to form an electric field. The electric field can be pulsed or non-pulsed. The electric field strength is preferably 0.15-1.0 kV / cm. In actual operation, the distance between the upper and lower electrode plates can be adjusted according to the separation effect to adjust the electric field strength, forming weak, medium, and strong electric fields, etc.

[0012] Furthermore, the electric sedimentation device has a horizontal structure, with the upper and lower electrode plates arranged horizontally along the axial direction of the device. One electrode plate is energized, while the other is grounded.

[0013] Furthermore, the upper and lower electrode plates are grid-shaped, and their surfaces are preferably provided with round holes and / or square holes.

[0014] Furthermore, the upper and lower electrode plates are subjected to alternating current, direct current, or a combination of alternating current and direct current. The frequency of the alternating current is preferably 50-60Hz.

[0015] Furthermore, the area between the upper and lower grid plates is divided into several grid spaces by transverse and longitudinal grid baffles. Preferably, each grid space contains at least one coalescing sphere. Preferably, the coalescing sphere has room to move within the grid space and can move and flip in any direction. The grid space can be a cube and / or a cuboid.

[0016] Furthermore, the coalescing separation ball has a hollow structure inside and is wrapped with coalescing packing. This allows the heavy phase separated from the upper electrostatic settling zone of the electrostatic settling device to enter the slurry separation zone. The suspended matter in the material is captured, coalesced, and grown on the surface of the coalescing separation ball to form easily settled suspended sludge that falls off and achieves separation.

[0017] Furthermore, the coalescing packing is composed of oleophilic and hydrophilic fibers and supporting steel wires, giving it coalescing function. The supporting steel wires are used to maintain the shape of the coalescing packing and prevent structural collapse and deformation. Preferably, the supporting steel wires are round stainless steel wires. Preferably, the diameter of the supporting steel wires is 0.5~2.5mm.

[0018] Preferably, the manufacturing process of the coalescing filler includes: first, weaving oleophilic and hydrophilic fibers into patterned sheet-like fiber fillers, then inserting supporting steel wires into its surface to make the sheet-like fiber filler rigid, and then using a spherical mold to make it into a spherical structure.

[0019] Furthermore, the weaving weight ratio of oleophilic fibers to hydrophilic fibers is 1~80:1, preferably 2~20:1.

[0020] Furthermore, the oleophilic fiber includes polyester fiber, nylon fiber, polyurethane fiber, polypropylene fiber, polyacrylonitrile fiber, polyvinyl chloride fiber, and one or more fibers selected from those whose surfaces have been modified for oleophilicity by physical and / or chemical methods.

[0021] Furthermore, the hydrophilic fiber filament includes at least one of the following: a polymer whose main chain and / or side chains contain hydrophilic groups; or a fiber filament that has undergone hydrophilic modification by physical and / or chemical methods. The more hydrophilic groups it contains, the better its hydrophilicity. Preferably, the hydrophilic groups include one or more of carboxyl, amide, amino, and hydroxyl groups. Even further, the hydrophilic fiber filament preferably includes one or more of polyamide fibers and acrylic fibers.

[0022] Furthermore, the coalescing separation spheres are arranged in 1-50 layers, preferably 4-20 layers.

[0023] Furthermore, the height of each coalescing separation sphere is 50-1000mm, preferably 80-400mm.

[0024] Furthermore, the diameter of the coalescing separation spheres is 5-200 mm, preferably 10-80 mm.

[0025] Furthermore, the diameters of the coalescing spheres in each layer may be the same or different. More preferably, for any two adjacent coalescing spheres, the diameter of the lower coalescing sphere is greater than or equal to the diameter of the upper coalescing sphere, the purpose of which is to gradually increase the size of the settled suspended matter and thus enhance the separation rate.

[0026] Furthermore, the membrane filter has an integrated shell structure comprising several inorganic ceramic membrane tube bundles.

[0027] In some preferred embodiments, the integrated shell-and-tube structure includes a shell containing a plurality of inorganic ceramic membrane tube bundles. The two ends of each inorganic ceramic membrane tube bundle are fixed to a first tube sheet and a second tube sheet, which are parallel to each other. The first and second tube sheets are fixedly connected to the inner wall of the shell. An isolation cavity is provided between the first and second tube sheets, communicating with the outlet of the residual liquid from the membrane filtration. One end of each inorganic ceramic membrane tube bundle is connected to the heavy liquid outlet of the slurry separation zone, and the other end is connected to the permeate outlet of the membrane filtration zone.

[0028] Furthermore, the inorganic ceramic membrane bundle is a hollow tubular structure, with single or multiple channels. Preferably, both the inner and outer surfaces of the channels have nano-micropore structures with a pore size of 1 nm to 1 μm. During membrane filter operation, heavy phase material enters the internal space of the inorganic ceramic membrane bundle and undergoes permeation filtration along the nano-micropores on the tube wall under pressure differential. The material that passes through the tube wall is the permeate, while the material that does not pass through is the residual liquid. The residual liquid contains fine slurry material and requires further circulation filtration.

[0029] Furthermore, the membrane filter's residual liquid outlet is connected to the side below the lower grid plate of the electrostatic precipitator. The residual liquid discharged from the membrane filter's residual liquid outlet is the residual oil after membrane filtration, which is returned to the lower part of the slurry separation zone as heavy phase circulating material.

[0030] Furthermore, the light phase adsorption desiliconizer includes one or more light phase adsorption columns arranged in parallel, preferably two or more light phase adsorption columns arranged in parallel, so that the light phase adsorption columns can adsorb alternately.

[0031] Furthermore, the light phase adsorption column is filled with a light phase adsorbent for removing small molecule organosilicon. Even further, the light phase adsorbent is not regenerated. The light phase adsorbent can be commercially available or homemade, preferably including one or more of the following: modified or unmodified activated carbon, molecular sieves, resins, and silica gel.

[0032] Furthermore, the light phase adsorption column is a downward fixed bed flow pattern, for example, the material enters from the top, flows from top to bottom, and exits from the bottom.

[0033] Furthermore, the heavy phase adsorption desiliconizer includes one or more heavy phase adsorption columns arranged in parallel, preferably two or more heavy phase adsorption columns arranged in parallel, so that the heavy phase adsorption columns can alternately realize continuous operation of adsorption and regeneration.

[0034] Furthermore, the heavy-phase adsorption column is filled with a heavy-phase adsorbent for removing macromolecular organosilicon. Even further, the heavy-phase adsorbent can be commercially available or homemade, preferably including one or more of modified or unmodified activated carbon, macroporous alumina, and macroporous resins.

[0035] Furthermore, the adsorption and regeneration of the heavy phase adsorption column are countercurrent. For example, the material enters from the top of the heavy phase adsorption column, flows downwards, and exits from the bottom, while the regenerator enters from the bottom of the heavy phase adsorption column, flows upwards, and exits from the top.

[0036] Furthermore, the bottom of the heavy phase adsorption column is connected to the membrane filtration permeate outlet for feeding, and the top discharges to obtain hydrocarbon liquid products.

[0037] Furthermore, a desorbent is used to regenerate the heavy phase adsorption column. The desorbent preferably comprises organic, inorganic, and / or organic-inorganic mixtures with regeneration capabilities; more preferably, it comprises one or more of water, acid, alkali, salt, and alcohol; and even more preferably, it comprises 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.

[0038] Secondly, the present invention provides the deep desilication treatment apparatus for hydrocarbon liquids described in the first aspect for the desilication of silicon-containing hydrocarbon liquids.

[0039] Thirdly, the present invention provides a method for deep desilication treatment of hydrocarbon liquids, using the deep desilication treatment apparatus for hydrocarbon liquids described in the first aspect; The deep desilication treatment method for hydrocarbon liquids includes the following steps: (1) First, the silicon-containing hydrocarbon liquid and the desiliconizing agent are prepared into a highly emulsified mixture, and after being fully stabilized and homogenized, it is introduced into the electrostatic precipitator to complete the efficient separation of light phase, heavy phase and slurry phase; (2) The heavy phase material separated by the electrodeposition device is introduced into the membrane filter for further deep treatment to remove inorganic silicon; (3) The light phase material separated by the electrostatic precipitator and the permeate of the heavy phase material that has been deeply treated by the membrane filter are introduced into the light phase adsorption desiliconizer and the heavy phase adsorption desiliconizer respectively for deep adsorption desiliconization.

[0040] The total silicon mass content of the silicon-containing hydrocarbon liquid to which this invention is applicable is 500-1000 ppm.

[0041] Steps (1) and (2) can remove the inorganic silicon content in silane-containing liquids to ≤5 ppm.

[0042] Step (3) can remove the organosilicon mass content in the permeate of light phase material and heavy phase material to ≤5ppm.

[0043] The deep desilication treatment method for hydrocarbon liquids can ultimately remove the total silicon content in silicon-containing hydrocarbon liquids to ≤10ppm.

[0044] The highly emulsifiable mixture of this invention refers to a stable mixture system formed by uniformly dispersing desilication agent liquid as extremely small droplets in a hydrocarbon liquid, and which does not undergo phase separation within a short period of time (generally 24 hours) during natural sedimentation. Generally, for emulsifiable mixtures, the shorter the time for phase separation during natural sedimentation, the lower the degree of emulsification, while the longer the time for phase separation during natural sedimentation, the higher the degree of emulsification.

[0045] Furthermore, in the highly emulsified mixture, the size of the desilicifying agent droplets is more than 90% nano- or micro-sized, preferably between 10 nm and 1000 μm. Preferably, the nano- or micro-sized droplets are formed using one or more combinations of metal film mixers, static mixers, jet mixers, mechanical shear mixers (e.g., stirred tanks), impact mixers, nanofilm mixers, and microchannel mixers.

[0046] Furthermore, the preparation conditions for the highly emulsified mixture include: a temperature of room temperature to 150°C and a pressure of 0.1 to 20.0 MPa, preferably 1.0 to 5.0 MPa.

[0047] After the highly emulsified mixture is formed, it is preferable to stabilize it for a period of time before it enters the electrodeposition tank. This is mainly to achieve more complete two-phase contact mass transfer, which is beneficial for achieving deep desilication. Furthermore, in step (1), the stabilization time is 1~10h, preferably 2~5h.

[0048] Furthermore, the desilication agent is prepared into a microemulsion by means of an extractant, a precipitant, and a flocculant using a microemulsion preparation device.

[0049] The extractant preferably includes any one or more of water, hydrofluoric acid, xylene, butyl acetate, ethyl acetate, tributyl phosphate, dichloromethane, petroleum ether, and trioctylamine.

[0050] The mass fraction of the extractant in the desilication agent is preferably 50% to 98%.

[0051] The precipitant preferably includes inorganic precipitants and / or organic precipitants, and more preferably includes any one or more of sodium hydroxide, potassium hydroxide, ammonia, sodium sulfate, sodium carbonate, barium chloride, oxalic acid, 8-hydroxyquinoline, and dimethylglyoxime.

[0052] The mass fraction of the precipitant in the desilication agent is preferably 1% to 25%.

[0053] The flocculant preferably includes any one or more of aluminum sulfate, aluminum chloride, ferric sulfate, ferric chloride, polyaluminum chloride, polyacrylamide, polyacrylic acid, sodium polyacrylate, calcium polyacrylate, and polyethylene oxide.

[0054] The mass fraction of flocculant in desilication agent is preferably 1% to 25%.

[0055] Furthermore, the mass ratio of the desilication agent to the silicon-containing hydrocarbon liquid is 1:1 to 200, preferably 1:10 to 100.

[0056] Furthermore, the silicon-containing hydrocarbon liquids come from any one or more of the following devices: hydrotreating device, hydrorefining device, catalytic cracking device, hydrocracking device, isomerization device, liquefied gas hydrogenation device, etherification device, coking device, and condensation device.

[0057] Furthermore, silicon-containing hydrocarbon liquids 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.

[0058] Furthermore, the operating conditions of the electrostatic precipitator 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; and a residence time of 1 to 180 min, preferably 10 to 60 min.

[0059] Furthermore, the operating conditions of the light phase adsorption desiliconizer 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.

[0060] Furthermore, the operating conditions for the adsorption process of the heavy phase adsorption desiliconizer 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 10 to 90 min, preferably 20 to 60 min.

[0061] Furthermore, the operating conditions for the regeneration process of the heavy phase adsorption silica remover 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 10 to 200 min, preferably 50 to 120 min.

[0062] Those skilled in the art should understand that existing methods for desilication of hydrocarbon liquids mainly involve using silicon-catching agents during hydrogenation. This process is not only complex but also operates under high temperature and pressure conditions, resulting in high equipment investment and energy consumption. More importantly, the silicon-catching agents used in this method have extremely limited silicon-holding capacity, requiring frequent replacement to prevent permanent deactivation of the hydrogenation catalyst. Consequently, strict requirements are placed on the silicon content of the feedstock during actual operation. For example, the silicon content in the feedstock for hydrogenation of coking naphtha is limited to no more than 10 ppm. Therefore, existing desilication technologies cannot handle hydrocarbon feedstocks with high silicon content. The hydrocarbon liquid desilication method developed in this invention has significant practical implications for improving the production flexibility and added value of oil products in the refining industry.

[0063] Compared with the prior art, the beneficial effects of this invention are as follows: 1) This invention classifies the total silicon compounds in hydrocarbon liquids according to their mode of existence (organosilicon compounds and inorganic silicon compounds), and then removes them in an effective manner according to their respective characteristics. On the one hand, it can process hydrocarbon liquid raw materials with high silicon content (500-1000ppm), and on the other hand, it can process the total silicon content to a level of ≤10ppm.

[0064] 2) In this invention, on the one hand, the removal of inorganic silicon compounds is mainly achieved through a formulated composite desilication agent. However, composite desilication agents generally contain inorganic liquids, resulting in poor miscibility with hydrocarbon liquid raw materials. This leads to low contact mass transfer efficiency and poor desilication effect. To address this issue, this invention adopts a process coupling method of high emulsified raw material preparation, electric field enhanced separation, and multi-stage agglomeration separation of suspended solids to capture and form slurry, thereby achieving the technical effect of enhanced contact mass transfer between the two phases and effective separation of slurry. On the other hand, inorganic silicon compounds mainly settle gradually in the slurry as suspended solids during the removal process. However, due to the presence of many fine suspended solids in the inorganic silicon compound slurry, fine separation is difficult to achieve. To address this, this invention employs an inorganic membrane permeation circulation filtration method to separate the heavy phase material from the inorganic silicon compound slurry, thereby achieving deep removal of inorganic silicon compounds.

[0065] 3) In the method of the present invention, in view of the fact that the organosilicon compounds in the light phase hydrocarbon liquid and the heavy phase hydrocarbon liquid separated by the electrostatic precipitator have different molecular sizes, and that the same adsorbent has problems such as low adsorption efficiency and poor selectivity, the organosilicon is removed from the light phase hydrocarbon liquid and the heavy phase hydrocarbon liquid separately. In addition, combined with the characteristics of high content of macromolecular compounds and easy regeneration, a mode of operation in which the adsorbent of the light phase hydrocarbon liquid is not regenerated and the heavy phase hydrocarbon liquid is regenerated is designed to achieve deep removal of organosilicon compounds. Attached Figure Description

[0066] Figure 1 This is a schematic diagram of the structure of a deep desilication treatment device for hydrocarbon liquids according to the present invention. Detailed Implementation

[0067] 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.

[0068] Example 1: See Figure 1 A deep desilication treatment device for hydrocarbon liquids includes an electrostatic precipitator 5, a membrane filter 23, a heavy phase adsorption desilication device and a light phase adsorption desilication device, as well as related connecting pipelines.

[0069] The electrostatic settling device 5 includes a housing 6, which contains an upper electrostatic settling zone 5-1 and a lower slurry separation zone 5-2.

[0070] The electrosettling zone 5-1 is equipped with an upper electrode plate 7 and a lower electrode plate 8. The area above the upper electrode plate 7 within the electrosettling zone 5-1 is a light phase storage chamber 9, and the area below the lower electrode plate 8 is a heavy phase storage chamber 10 connected to the slurry separation zone 5-2. A feed distributor 11 is located in the area between the upper electrode plate 7 and the lower electrode plate 8, which is connected to a highly emulsified mixture 4 containing silicon hydrocarbon liquid 1 and desiliconizing agent 2. The highly emulsified mixture 4 is formed by mixing the silicon hydrocarbon liquid 1 and the desiliconizing agent 2 via a mixer 3. A light liquid outlet 12 is located at the top of the light phase storage chamber 9, and the light liquid outlet 12 is connected to a light phase adsorption desiliconizer via a light liquid discharge pump 13.

[0071] The slurry separation zone 5-2 is equipped with an upper grid plate 16 and a lower grid plate 20, with coalescing separation balls 17 positioned between them. The area between the upper grid plate 16 and the lower grid plate 20 is divided into several grid spaces by transverse grid baffles 18 and longitudinal grid baffles 19. Each grid space contains at least one coalescing separation ball 17, which has room to move and rotate in any direction within the grid space. The coalescing separation ball 17 has a hollow internal structure and is externally wrapped with coalescing packing. The coalescing packing is composed of oleophilic and hydrophilic fibers and supporting steel wires. The manufacturing process includes: first, weaving the oleophilic and hydrophilic fibers into patterned sheet-like fiber packing; then, inserting supporting steel wires into its surface to give the sheet-like fiber packing rigidity; and finally, using a spherical mold to create a spherical structure.

[0072] A slurry outlet 14 is provided at the bottom of the electrostatic precipitator, and a heavy liquid outlet 15 is provided on the side below the lower grid plate 20. The heavy liquid outlet 15 is connected to the inlet 22 of the membrane filter 23 through a heavy liquid discharge pump 21.

[0073] The membrane filter 23 has an integral shell structure 25 comprising several inorganic ceramic membrane tube bundles 24. The inorganic ceramic membrane tube bundles 24 are hollow tubular, single-channel or multi-channel, and both the inner and outer surfaces of the channels have nano- and microporous structures. The membrane filtration permeate outlet 29 of the membrane filter 23 is connected to a heavy phase adsorption silica remover. The membrane filtration residue outlet 26 of the membrane filter 23 is connected to the side below the lower grid plate 20 of the electrostatic precipitator 5 via a residue discharge pump 27, for circulating the residue 28 back to the electrostatic precipitator 5.

[0074] The light phase adsorption silica remover includes a first light phase adsorption column 361 and a second light phase adsorption column 362 arranged in parallel. The first light phase adsorption column 361 and the second light phase adsorption column 362 are respectively filled with a first light phase adsorbent 371 and a second light phase adsorbent 372 for removing small molecule organosilicon. The first light phase adsorbent 371 and the second light phase adsorbent 372 are not regenerated, and the first light phase adsorption column 361 and the second light phase adsorption column 362 are in a downward fixed bed flow mode.

[0075] The first light phase adsorption column 361 has a first light phase inlet 351 at the top and a first light phase outlet 381 at the bottom. The light liquid outlet 12 discharges light liquid 35 through the light liquid discharge pump 13. The light liquid 35 enters the first light phase adsorption column 361 through the first light phase inlet 351 and flows out from the first light phase outlet 381 to obtain the final hydrocarbon liquid product 38.

[0076] The second light phase adsorption column 362 has a second light phase inlet 352 at the top and a second light phase outlet 382 at the bottom. The light liquid outlet 12 discharges light liquid 35 through the light liquid discharge pump 13. The light liquid 35 enters the second light phase adsorption column 362 through the second light phase inlet 352 and flows out from the second light phase outlet 382 to obtain the final hydrocarbon liquid product 38.

[0077] The heavy-phase adsorption silica remover includes a first heavy-phase adsorption column 301 and a second heavy-phase adsorption column 302 arranged in parallel. The first heavy-phase adsorption column 301 and the second heavy-phase adsorption column 302 are respectively filled with a first heavy-phase adsorbent 311 and a second heavy-phase adsorbent 312 for removing macromolecular organosilicon. The adsorption and regeneration of the first heavy-phase adsorption column 301 and the second heavy-phase adsorption column 302 are counter-current.

[0078] The first heavy phase adsorption column 301 has a first heavy phase outlet 321 and a first desorbent inlet 331 at the top, and a first heavy phase inlet 291 and a first desorbent outlet 341 at the bottom. The membrane filter 23's permeate outlet 29 is connected to the first heavy phase inlet 291. The material is fed from the bottom of the first heavy phase adsorption column 301, flowing upwards within the column and exiting from the first heavy phase outlet 321 to obtain the heavy phase product 32, which can be used as the final hydrocarbon liquid product 38. Fresh desorbent 33 enters the first heavy phase adsorption column 301 from the first desorbent inlet 331, flows downwards, and exits from the first desorbent outlet 341 to obtain the regenerated desorbent 34.

[0079] The second heavy phase adsorption column 302 has a second heavy phase outlet 322 and a second desorbent inlet 332 at the top, and a second heavy phase inlet 292 and a second desorbent outlet 342 at the bottom. The membrane filter 23's permeate outlet 29 is connected to the second heavy phase inlet 292. The material is fed from the bottom of the second heavy phase adsorption column 302, flowing upwards within the column and exiting from the second heavy phase outlet 322 to obtain the heavy phase product 32, which can be used as the final hydrocarbon liquid product 38. Fresh desorbent 33 enters the second heavy phase adsorption column 302 from the second desorbent inlet 332, flows downwards, and exits from the second desorbent outlet 342 to obtain the regenerated desorbent 34.

[0080] Silicon-containing hydrocarbon liquid 1 and desilication agent 2 are mixed in mixer 3 to form a highly emulsified mixture 4. This mixture then enters the region between the upper electrode plate 7 and the lower electrode plate 8 within the electrostatic precipitator 5 via feed distributor 11. Driven by the electric field and density difference, the light phase enters the light phase storage chamber 9, and the heavy phase enters the heavy phase storage chamber 10. The light phase leaving the electrostatic precipitator 5 enters the light phase adsorption desilication unit to remove small organic molecule silicon compounds. The heavy phase material in the heavy phase storage chamber 10 enters the slurry separation zone 5-2 to remove inorganic silicon compounds from the slurry precipitate. The separated slurry is discharged from the slurry outlet 14. The heavy liquid separated from the slurry separation zone 5-2 leaves the electrostatic precipitator 5 through the heavy liquid outlet 15, and is then pumped out by the heavy liquid discharge pump 21 and sent to the membrane filter 23. It is filtered by the inorganic ceramic membrane tube bundle 24 to obtain the residual liquid 28 and the permeate. The residual liquid 28 is pumped out by the residual liquid discharge pump 27 and returned to the electrostatic precipitator 5 for circulation sedimentation and separation. The permeate enters the heavy phase adsorption desiliconizer to perform deep desiliconization of macromolecular organic compounds. The discharge of the heavy phase adsorption desiliconizer (heavy phase product 32) after deep desiliconization is mixed with the discharge of the light phase adsorption desiliconizer to become the final hydrocarbon liquid product 38.

[0081] Example 2: The deep desiliconization treatment device of Example 1 was used to perform deep desiliconization on hydrocarbon liquids with high silicon content.

[0082] Table 1 lists the hydrocarbon liquids with high silicon content to be treated. Table 2 lists the three composite desilication agents, denoted as Composite Desilication Agent-1, Composite Desilication Agent-2, and Composite Desilication Agent-3, respectively.

[0083] Table 1. Hydrocarbon liquids with high silicon content to be treated Table 2 Composite Desilication Agent The high-silicon hydrocarbon liquids in Table 1 were prepared into highly emulsified mixtures with composite desilication agent-1, composite desilication agent-2, and composite desilication agent-3, respectively. After stabilization for a period of time, the mixtures were introduced into an electrostatic precipitator for desilication. In the electrostatic precipitator, the highly emulsified mixtures passed through the electrostatic precipitation zone and the slurry separation zone in sequence to complete the enhanced separation of the light phase, heavy phase, and slurry phase, removing the inorganic silicon content in the high-silicon hydrocarbon liquid to ≤5ppm. Then, the light phase silicon-containing liquid hydrocarbon material and the heavy phase silicon-containing liquid hydrocarbon material were sent to the light phase adsorption desiliconizer and the heavy phase adsorption desiliconizer, respectively, for deep adsorption, removing the organosilicon compounds to ≤5ppm, that is, finally reducing the total silicon content in the hydrocarbon liquid to ≤10ppm.

[0084] Preparation conditions for highly emulsifiable mixtures: The temperature is 25℃ and the pressure is 2.5 MPaG; The stability time of the highly emulsified mixture was 5.5 h. The mass ratio of the composite desilication agent to the liquid containing high silicon hydrocarbons to be treated is 1:65; The mixer employs a series connection of a static mixer and a microchannel mixer. First, the static mixer premixes the material, then introduces the premixed material into the microchannel mixer for secondary mixing. The microchannel mixer uses channels with an equivalent characteristic size of 10 μm. The resulting highly emulsified mixture has a natural settling time of approximately 32 hours. High-frequency camera images show that the composite desilication agent droplet size ranges from 200 μm to 1000 μm (≥90%).

[0085] Electrostatic precipitator: The operating conditions for the electric sedimentation unit are as follows: The temperature was 50℃, the pressure was 1.0 MPaG, and the residence time was 55 min. A circular hole is made on the surface of the electrode plate of the electric sedimentation device, and an alternating current with a frequency of 50Hz is applied to the electrode plate. The slurry separation zone inside the electrostatic precipitator is equipped with six layers of coalescing separation balls. The diameters of the coalescing separation balls from the first to the sixth layer (from top to bottom) are 20mm, 20mm, 40mm, 40mm, 60mm, and 60mm, respectively. The height of each layer of coalescing separation balls is 120mm. The coalescing separation balls are wrapped with coalescing packing made of polypropylene fiber filaments, acrylic fiber, and 1mm circular support steel wire. The weight ratio of polypropylene fiber filaments to acrylic fiber is 10:1. The inorganic ceramic membrane tube bundle has a 37-channel structure with a surface pore size of 5nm.

[0086] Light phase adsorption desiliconizer: The two adsorption columns are filled with the same type and quantity of adsorbent, and both are filled with polyvinylbenzene resin adsorbent; the operating conditions are as follows: temperature is 30℃, pressure is 0.8MPa, and residence time is 25min.

[0087] Heavy phase adsorption silica remover: The two adsorption columns are filled with the same type and quantity of adsorbent. Each adsorption column is filled with a combination of φ3 macroporous alumina and styrene macroporous resin. The desorbent is a mixed solution of 0.1% HF aqueous solution and ethanol at a volume ratio of 8:1. The adsorption process operating conditions are as follows: temperature 30℃, pressure 0.8MPa, residence time 40min. The regeneration process operating conditions are as follows: temperature 50℃, pressure 0.5MPa, residence time 65min.

[0088] The effects of deep desilication technology on high-silicon content hydrocarbon liquids after treatment using the above methods are shown in Table 3.

[0089] Example 3: The high-silicon content liquid hydrocarbons in Table 1 were subjected to deep desiliconization using the deep desiliconization treatment device of Example 1 and the composite desiliconizing agent in Table 2. The deep desiliconization method was similar to that of Example 2.

[0090] Preparation conditions for highly emulsifiable mixtures: The temperature is 25℃ and the pressure is 1.0 MPaG; The stability time of the highly emulsified mixture is 4 hours. The mass ratio of the composite desilication agent to the liquid containing high silicon hydrocarbons to be treated is 1:40; The mixer employs a series connection of a stirred tank and a microchannel mixer. First, the stirred tank is used for premixing, then the premixed material is introduced into the microchannel mixer for secondary mixing. The microchannel mixer uses channels with an equivalent characteristic size of 10 μm. The resulting highly emulsified mixture has a natural settling time of approximately 38 hours. High-frequency camera images show that the composite desilication agent droplet size is 400 μm–900 μm (≥90%).

[0091] Electrostatic precipitator: The operating conditions for the electrostatic precipitator are as follows: temperature 55℃, pressure 1.5MPaG; residence time 45min; A circular hole is made on the surface of the electrode plate of the electric sedimentation device, and an alternating current with a frequency of 50Hz is applied to the electrode plate. The slurry separation zone inside the electrostatic precipitator is equipped with 12 layers of coalescing separation balls. From the first to the twelfth layer (from top to bottom), the diameters of the coalescing separation balls are 10mm (two layers), 20mm (two layers), 40mm (two layers), 60mm (two layers), and 80mm (four layers), respectively. The height of each coalescing separation ball in layers 1-8 is 120mm, and the height of each coalescing separation ball in layers 9-12 is 160mm. The coalescing separation balls are wrapped with coalescing packing made of polypropylene fiber filaments, acrylic fiber, and 1mm circular support steel wire, with the weight ratio of polypropylene fiber filaments to acrylic fiber filaments being 8:1. The inorganic ceramic membrane tube bundle has a 37-channel structure with a surface pore size of 5nm.

[0092] Light phase adsorption desiliconizer: The two adsorption columns are filled with the same type and quantity of adsorbent, and both are filled with polyvinylbenzene resin adsorbent; the operating conditions are as follows: temperature is 30℃, pressure is 0.8MPa, and residence time is 20min.

[0093] Heavy phase adsorption silica remover: The two adsorption columns are filled with the same type and quantity of adsorbent. Each adsorption column is filled with a combination of φ3 macroporous alumina and styrene macroporous resin. The desorbent is a mixed solution of 0.1% HF aqueous solution and ethanol at a volume ratio of 1:1. The adsorption process operating conditions are as follows: temperature 30℃, pressure 0.8MPa, residence time 40min. The regeneration process operating conditions are as follows: temperature 50℃, pressure 0.5MPa, residence time 65min.

[0094] The effects of deep desilication technology on high-silicon content hydrocarbon liquids after treatment using the above methods are shown in Table 3.

[0095] Example 4: The high-silicon content liquid hydrocarbons in Table 1 were subjected to deep desiliconization using the deep desiliconization treatment device of Example 1 and the composite desiliconizing agent in Table 2. The deep desiliconization method was similar to that of Example 2.

[0096] Preparation conditions for highly emulsifiable mixtures: The temperature is 25℃ and the pressure is 3.0 MPaG; The stability time of the highly emulsified mixture is 5 hours. The mass ratio of the composite desilication agent to the liquid containing high silicon hydrocarbons to be treated is 1:20; The mixer employs a two-stage metal membrane mixer. The first-stage metal membrane mixer has a pore size of 10 μm, and the second-stage metal membrane mixer has a pore size of 5 μm. 50% of the composite desilication agent is first mixed with the high-silica hydrocarbon liquid to be treated in the first-stage metal membrane mixer. The remaining 50% of the composite desilication agent is then mixed with the effluent from the first-stage metal membrane mixer. The resulting highly emulsified mixture has a natural settling time of approximately 43 hours. High-frequency camera images show that the composite desilication agent droplet size ranges from 50 μm to 400 μm (≥90%).

[0097] Electrostatic precipitator: The operating conditions for the electrostatic precipitator are as follows: temperature 60℃, pressure 1.8 MPaG; residence time 55 min; A circular hole is made on the surface of the electrode plate of the electric sedimentation device, and an alternating current with a frequency of 50Hz is applied to the electrode plate. The slurry separation zone inside the electrostatic precipitator is equipped with 16 layers of coalescing separation balls. From the first to the sixteenth layer (from top to bottom), the diameters of the coalescing separation balls are 20mm (four layers), 40mm (four layers), 60mm (four layers), and 120mm (four layers). The height of each coalescing separation ball in the first to sixteenth layers is 120mm. The coalescing separation balls are wrapped with coalescing packing made of polypropylene fiber filaments, acrylic fiber, and 1mm circular support steel wire. The weight ratio of polypropylene fiber filaments to acrylic fiber is 4:1. The inorganic ceramic membrane tube bundle has a 37-channel structure with a surface pore size of 5nm.

[0098] Light phase adsorption desiliconizer: The two adsorption columns are filled with the same type and quantity of adsorbent, and both are filled with polyvinylbenzene resin adsorbent; the operating conditions are as follows: temperature is 30℃, pressure is 0.8MPa, and residence time is 32min.

[0099] Heavy phase adsorption silica remover: The two adsorption columns are filled with the same type and quantity of adsorbent. Each adsorption column is filled with a combination of φ3 macroporous alumina and styrene macroporous resin. The desorbent is a mixed solution of 0.1% HF aqueous solution and ethanol at a volume ratio of 1:5. The adsorption process operating conditions are as follows: temperature 30℃, pressure 0.8MPa, residence time 60min. The regeneration process operating conditions are as follows: temperature 50℃, pressure 0.5MPa, residence time 90min.

[0100] The effects of deep desilication technology on high-silicon content hydrocarbon liquids after treatment using the above methods are shown in Table 3.

[0101] Table 3 As shown in Table 3, Examples 2-4 employ the hydrocarbon liquid deep desilication device and method of the present invention. First, the hydrocarbon liquid and composite desilication agent are prepared into a highly emulsified mixture to enhance mass transfer, thereby enhancing the two-phase contact mass transfer effect. Then, the highly emulsified mixture is introduced into an electrostatic precipitator to achieve efficient separation of the light phase, heavy phase, and slurry phase. Finally, the separated light phase material and heavy phase material are introduced into the light phase adsorption desilication device and the heavy phase adsorption desilication device, respectively, for deep adsorption desilication. Ultimately, the content of inorganic silicon compounds and organic silicon compounds in the hydrocarbon liquid is removed to ≤5ppm, that is, the total silicon content in the hydrocarbon liquid is removed to ≤10ppm, with a desilication rate of over 98%. This achieves a low-cost and highly efficient ultra-deep desilication technology effect under relatively mild process conditions.

[0102] 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 deep desilication treatment device for hydrocarbon liquids, characterized in that, This includes electrostatic precipitators, membrane filters, heavy phase adsorption desiliconizers, and light phase adsorption desiliconizers; The electrostatic precipitator consists of an upper electrostatic precipitation zone and a lower slurry separation zone; The electrosettling zone is equipped with an upper electrode plate and a lower electrode plate; the area above the upper electrode plate in the electrosettling zone is a light phase storage chamber, which is connected to the light phase adsorption desiliconizer; the area below the lower electrode plate in the electrosettling zone is a heavy phase storage chamber, which is connected to the slurry separation zone; the area between the upper and lower electrode plates in the electrosettling zone is externally connected to a highly emulsified mixture containing silane hydrocarbon liquid and desiliconizing agent. The slurry separation zone is equipped with an upper grid plate and a lower grid plate, and coalescing separation balls are installed between the upper grid plate and the lower grid plate. The electrostatic precipitator is equipped with a slurry outlet at the bottom and a heavy liquid outlet on the side below the lower grid plate. The inlet of the membrane filter is connected to the heavy liquid outlet, and the membrane filtration permeate outlet is connected to the heavy phase adsorption desiliconizer.

2. The deep desilication treatment device for hydrocarbon liquids according to claim 1, characterized in that, The upper and lower electrode plates face each other to form an electric field. The electric field can be pulsed or non-pulsed, and the electric field strength is 0.15-1.0kV / cm. In actual operation, the distance between the upper and lower electrode plates is adjusted according to the separation effect to adjust the electric field strength. The electric sedimentation device has a horizontal structure, with the upper and lower electrode plates arranged horizontally along the axial direction of the device. One electrode plate is energized, and the other electrode plate is grounded. The upper and lower electrode plates are grid-shaped, with round and / or square holes on their surfaces; The upper and lower electrode plates are loaded with alternating current, direct current, or a combination of alternating current and direct current, with the alternating current frequency being 50-60Hz; The area between the upper and lower grid plates is divided into several grid spaces by transverse and longitudinal grid baffles. Each grid space contains at least one coalescing and separating sphere. The coalescing and separating sphere has room to move within the grid space and can move and flip in any direction. The grid space is a cube and / or cuboid; The coalescing separator sphere has a hollow internal structure and is wrapped with coalescing packing material on the outside. The coalescing packing is composed of oleophilic and hydrophilic fibers and supporting steel wires. The supporting steel wires are used to maintain the shape of the coalescing packing. The supporting steel wires are round stainless steel wires with a diameter of 0.5~2.5mm. The manufacturing process of coalescing filler includes: first, weaving oleophilic and hydrophilic fibers into patterned sheet-like fiber filler, then inserting supporting steel wires into its surface to make the sheet-like fiber filler rigid, and then making it into a spherical structure through a spherical mold. The weaving weight ratio of oleophilic fibers to hydrophilic fibers is 1~80:1, preferably 2~20:1; Oleophilic fibers include polyester fibers, nylon fibers, polyurethane fibers, polypropylene fibers, polyacrylonitrile fibers, polyvinyl chloride fibers, and one or more fibers selected from those whose surfaces have undergone oleophilic modification treatment by physical and / or chemical methods. The hydrophilic fiber includes at least one of the following: a high molecular weight polymer whose main chain and / or side chains contain hydrophilic groups, and a fiber filament that has been hydrophilically modified by physical and / or chemical methods. The hydrophilic groups include one or more of carboxyl groups, amide groups, amino groups, and hydroxyl groups. Further, the hydrophilic fiber includes one or more of polyamide fibers and acrylic fibers. The coalescing spheres are arranged in 1-50 layers, preferably 4-20 layers; the height of each coalescing sphere layer is 50-1000mm, preferably 80-400mm; the diameter of the coalescing spheres is 5-200mm, preferably 10-80mm; the diameters of the coalescing spheres in each layer may be the same or different. Preferably, for any two adjacent coalescing sphere layers, the diameter of the lower coalescing sphere is greater than or equal to the diameter of the upper coalescing sphere.

3. The deep desilication treatment apparatus for hydrocarbon liquids according to claim 1, characterized in that, The membrane filter has an integrated shell structure containing several inorganic ceramic membrane tube bundles; the inorganic ceramic membrane tube bundles are hollow tubes, single-channel or multi-channel, and the inner and outer surfaces of the channels have nano-micropore structures with a pore size of 1nm~1μm; The membrane filter's residual liquid outlet is connected to the side below the lower grid plate of the electrostatic precipitator.

4. The deep desilication treatment device for hydrocarbon liquids according to claim 1, characterized in that, The light phase adsorption desiliconizer includes one or more light phase adsorption columns arranged in parallel. The light phase adsorption columns are filled with light phase adsorbent for removing small molecule organosilicon. The light phase adsorbent is not regenerated. The light phase adsorption columns are in a downward fixed bed flow mode. Light phase adsorbents include one or more of the following: modified or unmodified activated carbon, molecular sieves, resins, and silica gel.

5. The deep desilication treatment apparatus for hydrocarbon liquids according to claim 1, characterized in that, The heavy phase adsorption desiliconizer includes one or more heavy phase adsorption columns arranged in parallel. The heavy phase adsorption columns are filled with heavy phase adsorbent for removing macromolecular organosilicon. The adsorption and regeneration of the heavy phase adsorption columns are countercurrent. The bottom of the heavy phase adsorption column is connected to the membrane filter permeate outlet for feeding, and the top outlet yields hydrocarbon liquid products. Heavy phase adsorbents include one or more of the following: modified or unmodified activated carbon, macroporous alumina, and macroporous resins; The heavy phase adsorption column is regenerated using a desorbent; the desorbent includes organic, inorganic and / or organic-inorganic mixtures with regeneration function, further including one or more of water, acid, alkali, salt, and alcohol, and even more specifically 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.

6. The deep desilication treatment apparatus for hydrocarbon liquids according to any one of claims 1 to 5 is used for the desilication of silicon-containing hydrocarbon liquids.

7. A method for deep desilication treatment of hydrocarbon liquids, characterized in that, The deep desilication treatment apparatus for hydrocarbon liquids as described in any one of claims 1 to 5; The deep desilication treatment method for hydrocarbon liquids includes the following steps: (1) First, the silicon-containing hydrocarbon liquid and the desiliconizing agent are prepared into a highly emulsified mixture, and after being fully stabilized and homogenized, it is introduced into the electrostatic precipitator to complete the efficient separation of light phase, heavy phase and slurry phase; (2) The heavy phase material separated by the electrodeposition device is introduced into the membrane filter for further deep treatment to remove inorganic silicon; (3) The light phase material separated by the electrostatic precipitator and the permeate of the heavy phase material that has been deeply treated by the membrane filter are introduced into the light phase adsorption desiliconizer and the heavy phase adsorption desiliconizer respectively for deep adsorption desiliconization.

8. The method for deep desilication treatment of hydrocarbon liquids according to claim 7, characterized in that, The total silicon content of the silicon-containing hydrocarbon liquid is 500-1000 ppm by mass; Steps (1) and (2) remove the inorganic silicon content in the silane-containing liquid to ≤5 ppm; Step (3) Remove the organosilicon mass content in the permeate of the light phase material and the heavy phase material to ≤5ppm; The deep desiliconization treatment method for hydrocarbon liquids ultimately removes the total silicon content in silicon-containing hydrocarbon liquids to ≤10ppm.

9. The method for deep desilication treatment of hydrocarbon liquids according to claim 7, characterized in that, In step (1): The desilicifying agent droplets in the highly emulsified mixture have a droplet size of more than 90% in the nano-micron range, with a size of 10nm-1000μm; the nano-micron droplets are formed by one or more combinations of metal film mixers, static mixers, jet mixers, mechanical shear mixers, impact mixers, nanofilm mixers, and microchannel mixers. The stabilization time is 1~10h, preferably 2~5h; The desilication agent is prepared into a microemulsion by means of an extractant, a precipitant and a flocculant using a microemulsion preparation device; The extractant includes any one or more of 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 inorganic precipitants and / or organic precipitants, and further includes any 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 any one or more of aluminum sulfate, aluminum chloride, ferric sulfate, ferric chloride, polyaluminum chloride, polyacrylamide, polyacrylic acid, sodium polyacrylate, calcium polyacrylate, and polyethylene oxide. The mass fraction of flocculant in desilication agent is 1%~25%; The mass ratio of the desilication agent to the silane-containing liquid is 1:1 to 200, preferably 1:10 to 100; Silicon-containing liquids originate 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 superposition unit; Silicon-containing hydrocarbon liquids 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 preparation conditions for the highly emulsifiable mixture include: a temperature of room temperature to 150°C, and a pressure of 0.1 to 20.0 MPa, preferably 1.0 to 5.0 MPa; The operating conditions of the electrostatic precipitator include: temperature of room temperature to 200℃, preferably 50 to 80℃; pressure of 0.1 to 5.0 MPa, preferably 0.5 to 2.0 MPa; and residence time of 1 to 180 min, preferably 10 to 60 min.

10. The method for deep desilication treatment of hydrocarbon liquids according to claim 7, characterized in that, In step (3): The operating conditions for the light phase adsorption desiliconizer 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 adsorption process of the heavy phase adsorption silica remover 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 10 to 90 min, preferably 20 to 60 min. The operating conditions for the regeneration process of the heavy phase adsorption silica remover 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 10 to 200 min, preferably 50 to 120 min.

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