Petroleum coke feedstock processing method and system

Abstract

The application relates to the field of petroleum coke, and discloses a petroleum coke raw material treatment method and system, which comprises the following steps: (1) mixing petroleum coke raw material, a solvent and a surfactant, and then contacting the mixture with water in a fiber liquid membrane contactor; (2) separating the material obtained in the step (1); (3) mixing the oil phase obtained in the step (2) with hydrogen, and feeding the mixture into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction; the mixed product of the oil phase and the hydrogen is fed into the multi-bed liquid phase hydrogenation reactor through multiple feeding ports, the multi-bed liquid phase hydrogenation reactor has multiple reaction zones, and any feeding port is arranged between two adjacent reaction zones; (4) mixing the hydrogenation product obtained in the step (3) with hydrogen, and feeding the mixture into a tubular reactor for hydrogenation reaction; and (5) extracting and distilling the hydrogenation product obtained in the step (4), and producing petroleum coke based on heavy oil fractions obtained through the distillation. Therefore, the quality of the petroleum coke raw material can be effectively improved.

Description

Technical Field

[0001] This invention relates to the field of petroleum coke technology, and more specifically to a method and system for processing petroleum coke raw materials. Background Technology

[0002] Petroleum coke is a solid product produced from heavy oil through a thermal cracking-condensation process. High-quality petroleum coke requires low sulfur content, low heavy metal content, and low ash content. However, for economic reasons, inferior oil products with high sulfur and metal content, such as vacuum residue and deoiled bitumen, are often used as raw materials for petroleum coke production, making it difficult to obtain high-quality petroleum coke.

[0003] To balance economic efficiency and obtain high-quality petroleum coke, pretreatment of the feedstock before production is a common technical approach; that is, improving the quality of the feedstock to improve the quality of the petroleum coke. For example, CN1309164A discloses a combined process of residue oil hydrotreating and delayed coking. Residue oil, coking gas oil, and hydrogen are mixed together and reacted in a hydrotreating unit in the presence of a catalyst. The hydrotreating products are separated, and the hydrotreated residue oil, either alone or together with other conventional feedstocks for needle coke production, undergoes delayed coking to separate the coking products. The coking gas oil is recycled back to the hydrotreating unit. A drawback of this method is that solid impurities in the feedstock are not effectively removed, which can affect the catalyst's lifespan. For example, CN1676574A discloses an improved delayed coking method. The coking feedstock and optional coking circulating oil are pressurized by a radiant feed pump, then contacted with hydrogen and a catalyst. After being heated to coking temperature in a coking furnace, the hydrogenated product oil is depressurized by a throttling device and enters a coking tower. The generated coke remains in the coking tower. The coking oil and gas are separated to obtain coking gas, coking gasoline, coking diesel, and coking wax oil. The disadvantage of this method is the lack of a feedstock desolidification pretreatment step.

[0004] It is evident that existing processing methods are not ideal for treating petroleum coke feedstocks and cannot effectively improve their quality. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of unsatisfactory processing effect and inability to effectively improve the quality of petroleum coke raw materials in the existing technology, and to provide a method and system for processing petroleum coke raw materials.

[0006] To achieve the above objectives, the present invention provides a method for processing petroleum coke feedstock, comprising:

[0007] (1) Mix petroleum coke raw material, solvent and surfactant to obtain mixed oil, and place the mixed oil and water in a fiber liquid film contactor for contact;

[0008] (2) Perform three-phase separation of oil, water and solid on the material obtained in step (1);

[0009] (3) The oil phase obtained in step (2) is mixed with hydrogen to obtain a first hydrogen-containing mixed oil. The first hydrogen-containing mixed oil is fed into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction. The multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed ports. Any feed port is located between two adjacent reaction zones. The first hydrogen-containing mixed oil is fed into the multi-bed liquid phase hydrogenation reactor through the multiple feed ports.

[0010] (4) The hydrogenation product obtained in step (3) is mixed with hydrogen to obtain a second hydrogen-containing mixed oil. The second hydrogen-containing mixed oil is then fed into a tubular reactor for hydrogenation reaction.

[0011] (5) Extract and distill the hydrogenation product obtained in step (4) and produce petroleum coke based on the heavy oil fraction obtained from the distillation.

[0012] In the embodiments of this application, the solvent is a heavy aromatic hydrocarbon.

[0013] In the embodiments of this application, the surfactant includes at least one of amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants.

[0014] In the embodiments of this application, in step (1), the weight ratio of petroleum coke raw material, solvent and surfactant is 1:(0.2~3.0):(0.00005~0.0005).

[0015] In this embodiment of the application, in step (1), the weight ratio of the mixed oil to water is 1:(0.05~0.3);

[0016] In step (1), the conditions for the mixed oil to contact with water include: a temperature of 60℃ to 200℃, a pressure of 0.3MPa to 3MPa, and a liquid hourly space velocity (LHSV) of 5h based on the volume of the fibers in the fiber liquid film contactor. -1 ~60h -1 .

[0017] In this embodiment of the application, mixing the oil phase obtained in step (2) with hydrogen includes:

[0018] The oil phase obtained in step (2) is heated to obtain a treated oil phase with a temperature of 200℃~450℃ and a pressure of 3.0MPa~20.0MPa;

[0019] The treated oil phase is mixed with hydrogen.

[0020] The second aspect of this application provides a petroleum coke feedstock processing system, the processing system comprising a mixing tank, a fiber liquid membrane contactor, a separation device, a primary hydrogen mixer, a multi-bed liquid phase hydrogenation reactor, a secondary hydrogen mixer, a tubular reactor, an extraction distillation device, and a delayed coking device.

[0021] The multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed inlets, with any feed inlet located between two adjacent reaction zones;

[0022] The outlet of the mixing tank is connected to the inlet of the fiber liquid membrane contactor, the outlet of the fiber liquid membrane contactor is connected to the inlet of the separation device, the oil phase outlet of the separation device is connected to the inlet of the first-stage hydrogen mixer, the outlet of the first-stage hydrogen mixer is connected to multiple inlets of the multi-bed liquid phase hydrogenation reactor, the outlet of the multi-bed liquid phase hydrogenation reactor is connected to the inlet of the second-stage hydrogen mixer, the outlet of the second-stage hydrogen mixer is connected to the inlet of the tubular reactor, the outlet of the tubular reactor is connected to the inlet of the extraction distillation device, and the heavy oil outlet of the extraction distillation device is connected to the inlet of the delayed coking device.

[0023] In this embodiment of the application, each inlet and outlet of the multi-bed liquid phase hydrogenation reactor is equipped with a pressure detection device.

[0024] In this embodiment of the application, the extraction distillation apparatus includes a high-pressure separator and a stripping tower;

[0025] The outlet of the tubular reactor is connected to the inlet of the high-pressure separator, the outlet of the target component of the high-pressure separator is connected to the inlet of the stripping tower, and the outlet of the heavy oil of the stripping tower is connected to the inlet of the delayed coking unit.

[0026] The target component is the component from which hydrogen sulfide has been removed.

[0027] In this embodiment of the application, the solvent outlet of the stripping tower is connected to the feed inlet of the mixing tank.

[0028] The above technical solution includes: (1) mixing petroleum coke raw material, solvent and surfactant to obtain mixed oil, and placing the mixed oil and water in a fiber liquid membrane contactor for contact; (2) separating the material obtained in step (1) into three phases: oil, water and solid; (3) mixing the oil phase obtained in step (2) with hydrogen to obtain a first hydrogen-containing mixed oil, and feeding the first hydrogen-containing mixed oil into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction; wherein the multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed ports, any feed port is set between two adjacent reaction zones, and the first hydrogen-containing mixed oil is fed into the multi-bed liquid phase hydrogenation reactor through the multiple feed ports; (4) mixing the hydrogenation product obtained in step (3) with hydrogen to obtain a second hydrogen-containing mixed oil, and feeding the second hydrogen-containing mixed oil into a tubular reactor for hydrogenation reaction; (5) extracting and distilling the hydrogenation product obtained in step (4), and producing petroleum coke based on the heavy oil fraction obtained by distillation. Based on the solutions provided in the embodiments of this application, solid impurities in petroleum coke raw materials can be effectively removed and the sulfur content in petroleum coke raw materials can be reduced, thereby greatly improving the quality of petroleum coke raw materials.

[0029] Other features and advantages of the embodiments of this application will be described in detail in the following detailed description section. Attached Figure Description

[0030] The accompanying drawings are provided to further illustrate the embodiments of this application and form part of the specification. They are used together with the following detailed description to explain the embodiments of this application, but do not constitute a limitation on the embodiments of this application. In the drawings:

[0031] Figure 1 The schematic diagram illustrates the structure of a petroleum coke feedstock processing system according to an embodiment of this application.

[0032] Explanation of reference numerals in the attached figures:

[0033] 201—Mixing tank; 202—Fiber liquid film contactor; 203—Separation unit; 204—First-stage hydrogen mixer; 205—Multi-bed liquid phase hydrogenation reactor; 2051—First-stage feed chamber; 2052—Second-stage feed chamber; 2053—Third-stage feed chamber; 2054—Fourth-stage feed chamber; 2055—First-stage reaction zone; 2056—Second-stage reaction zone; 2057—Third-stage reaction zone; 2058—Fourth-stage reaction zone; 206—Second-stage hydrogen mixer; 207—Tubular reactor; 2081—High-pressure separator; 2082—Stripping tower; 209—Delayed coking unit. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only for illustration and explanation of the embodiments of this application and are not intended to limit the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0035] If the embodiments of this application involve descriptions such as "first" or "second," these descriptions are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" or "second" may explicitly or implicitly include at least one of those features. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. If the combination of technical solutions is contradictory or impossible to implement, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed in this application.

[0036] As described in the background art, in order to balance economic benefits and obtain high-quality petroleum coke, processing the raw materials for petroleum coke production is a common technical means; that is, improving the quality of the raw materials to improve the quality of the petroleum coke. However, existing processing methods are not ideal for processing the raw materials and cannot effectively improve their quality.

[0037] To address this, one embodiment of this application provides a method for processing petroleum coke raw materials. This method can be used to pretreat raw materials for producing petroleum coke, and can pretreat petroleum coke raw materials from various sources. For example... Figure 1 As shown, the method may include steps (1), (2), (3), (4), and (5), as detailed below:

[0038] (1) The petroleum coke raw material, solvent and surfactant are mixed to obtain a mixed oil, and the mixed oil and water are placed in a fiber liquid film contactor for contact.

[0039] The petroleum coke feedstock can also be referred to as coking feedstock, delayed coking feedstock, etc. Specifically, the petroleum coke feedstock can be vacuum residue, deoiled bitumen, or other petroleum products.

[0040] In this embodiment, the solvent can be used to dilute the petroleum coke feedstock, making the diluted oil less dense than water, thus facilitating subsequent oil-water separation. On the other hand, the solvent can also dissolve the gums and asphaltenes in the petroleum coke feedstock, disrupting the coating of the petroleum coke feedstock on solid impurities and the interaction forces between the petroleum coke feedstock and the solid impurities, thereby facilitating the subsequent separation of solid impurities from the petroleum coke feedstock and achieving better desolvation. Furthermore, the solvent can reduce the viscosity and density of the petroleum coke feedstock, contributing to better mass transfer when the solid-containing petroleum coke feedstock is processed in a fiber liquid membrane contactor.

[0041] In specific implementations, the solvent can be a heavy aromatic hydrocarbon, i.e., a mixture of aromatic hydrocarbons with a molecular weight greater than xylene. More preferably, the mass fraction of C9 aromatic hydrocarbons in the solvent is 10-90%.

[0042] In the embodiments of this application, the surfactant may be an amphoteric surfactant. Specifically, the surfactant may include at least one of amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. More preferably, the surfactant may include at least one of sodium lauryl iminodipropionate, lauryl betaine, and imidazoline quaternary ammonium salt of lauryl acid.

[0043] The amounts of solvent and surfactant can be selected based on the processing volume of the petroleum coke feedstock. In specific implementations, to improve the desolidification effect of the petroleum coke feedstock and the effectiveness of subsequent processing steps, the weight ratio of petroleum coke feedstock, solvent, and surfactant can be 1:(0.2-3.0):(0.00005-0.0005). More preferably, the weight ratio of petroleum coke feedstock, solvent, and surfactant can be 1:(0.3-1.5):(0.0001-0.0004).

[0044] The fiber liquid membrane contactor is a high-efficiency mass transfer device. The fiber liquid membrane contactor can be a device with two open ends, namely the feed end and the discharge end. The feed end has two feed ports, and the discharge port of the discharge end is connected to the device used for oil, water and solid separation in the subsequent step (2).

[0045] The fiber liquid film contactor can be equipped with a fluid distributor and a mass transfer space cylinder from the feed end to the discharge end. Within the mass transfer space cylinder, a fluid redistributor and fiber filaments can be sequentially arranged along the direction from the feed end to the discharge end. Based on the fluid distributor and fluid redistributor, the solid-containing fluid entering the fiber liquid film contactor can be well distributed across the cross-section of the fiber filaments, thereby improving the mass transfer effect of the fluid in the fiber liquid film contactor.

[0046] The fiber filaments are installed inside the mass transfer space cylinder of the fiber liquid membrane reactor. The fluid is evenly distributed through the fiber filaments by the distributor. Utilizing capillary action and the difference in surface tension between the aqueous phase and the solid-containing oil phase on the fiber filaments, the aqueous phase and the oil phase added to the fiber liquid membrane contactor form a liquid film on the surface of the fiber filaments. This increases the surface area of ​​contact between the two phases, which greatly improves the mass transfer efficiency. The improved mass transfer efficiency can promote more effective contact between the aqueous phase and solid impurities in the oil, and can better play the role of solidification removal.

[0047] In practical applications, fiber liquid film contactors can be of various shapes, as long as they can achieve the effect of deconsolidation through the fiber filaments. Preferably, the fiber liquid film contactor is cylindrical. Cylindrical fiber liquid film contactors can make full use of the material flow direction and the weight of the droplets themselves for deconsolidation, thus achieving a better deconsolidation effect.

[0048] The fluid distributor can be one of the following: orifice plate, overflow, or plate type. The fluid redistributor can also be one of the following: orifice plate, overflow, or plate type. Multiple fluid redistributors can be installed within the mass transfer space cylinder.

[0049] The fiber filaments can be hydrophilic fibrous materials, and can be metal wires and / or non-metal wires. Preferably, the fiber filaments can include at least one of stainless steel wire, carbon steel wire, glass fiber filaments, polyamide fiber filaments, and polyester fiber filaments. More preferably, the fiber filaments can include at least one of stainless steel wire, glass fiber filaments, and polyester fiber filaments. To further improve the deconsolidation effect of petroleum coke feedstock, the diameter of the fiber filaments can be 0.05 mm to 0.5 mm. In practical applications, the fiber filaments can be industrially produced products, for example, commercially available 316 series stainless steel wire, 0.05 mm glass fiber filaments, and 0.05 mm polyester fiber filaments.

[0050] To further improve the deconsolidation effect, the aspect ratio of the mass transfer space in the fiber liquid film contactor can be (10-6)0:1, and the filling rate of the fiber filaments in the mass transfer space can be 2% to 30% of the volume of the mass transfer space.

[0051] In this embodiment, based on the fiber liquid film contactor, when the mixed oil and water come into contact in the fiber liquid film contactor, the fiber filaments with good hydrophilicity can capture the encapsulation formed by the amphoteric surfactant and solid impurities, as well as the water. Then, the solid impurities in the petroleum coke feedstock enter the water under the action of the hydrophilic amphoteric surfactant, thereby desolidifying the petroleum coke feedstock.

[0052] Specifically, amphoteric surfactants carry both positive and negative charges and have an isoelectric point. When the amphoteric surfactants are dispersed onto water-containing fiber filaments, the electron-rich colloids and asphaltenes in the oil phase are not easily aggregated on the fiber filaments, thus avoiding blockage. The liquid film containing solid impurities moves along the fiber filaments, continuously agglomerating to form large droplets, which then fall off under their own gravity. Finally, through the separation of oil, water, and solid phases, the desolidified petroleum coke feedstock is obtained.

[0053] To achieve better deconsolidation, the weight ratio of the mixed oil to water can be 1:(0.05-0.3). More preferably, the weight ratio of the mixed oil to water can be 1:(0.07-0.2).

[0054] To further improve the desolidification effect of petroleum coke feedstock, the conditions for contact between the mixed oil and water may include: a temperature of 60℃~200℃, a pressure of 0.3MPa~3MPa, and a liquid hourly space velocity (LHSV) of 5h based on the volume of the fibers in the fiber liquid film contactor. -1 ~60h -1 More preferably, the temperature is 130℃~150℃, the pressure is 1MPa~1.8MPa, and the liquid hourly space velocity of the mixed oil is 10h⁻¹. -1 ~20h -1 The temperature is the operating temperature of the fiber liquid film contactor, the pressure is the working pressure of the fiber liquid film contactor, specifically the gauge pressure, and the liquid hourly space velocity reflects the feed rate of the mixed oil into the fiber liquid film contactor.

[0055] In practical applications, after obtaining the mixed oil, it can be preheated before being contacted with water in a fiber liquid film contactor. Preheating the mixed oil allows the petroleum coke feedstock to further dissolve in the solvent, thereby improving the contact and desolidification effect between the mixed oil and water. The preheating temperature can be 50℃~150℃, preferably 60℃~100℃.

[0056] (2) The material obtained in step (1) is subjected to three-phase separation of oil, water and solid.

[0057] In this embodiment, the separation of the oil, water, and solid phases can be achieved through sedimentation and filtration. In practice, the material obtained in step (1) can be placed in an oil-water separator for settling. After settling, the upper layer is the oil phase, and the lower layer is water containing solid impurities. Then, the lower layer is discharged from the oil-water separator, and after sedimentation and filtration, the water and solid phases are obtained; the separated water phase can be recycled. In practical applications, the sedimentation time can be selected based on the actual separation effect of the oil and water layers in the material obtained in step (1). For example, the sedimentation time can be 0.5h to 3h, more preferably 1h to 2h.

[0058] (3) The oil phase obtained in step (2) is mixed with hydrogen to obtain a first hydrogen-containing mixed oil. The first hydrogen-containing mixed oil is fed into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction. The multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed ports. Any feed port is located between two adjacent reaction zones. The first hydrogen-containing mixed oil is fed into the multi-bed liquid phase hydrogenation reactor through the multiple feed ports.

[0059] In this embodiment of the application, the oil phase obtained in step (2) can be mixed with hydrogen in a membrane mixer.

[0060] The membrane mixer includes a housing and a membrane module. At least one membrane module is placed within the housing, with a space between the outer wall of the membrane module and the inner wall of the housing. In the membrane mixer, the channels on the membrane module serve as liquid channels for containing the oil phase obtained in step (2), and the space formed between the outer wall of the membrane module and the inner wall of the housing serves as a gas channel for containing hydrogen. Alternatively, the channels on the membrane module serve as gas channels for containing hydrogen, and the space formed between the outer wall of the membrane module and the inner wall of the housing serves as a liquid channel for containing the oil phase obtained in step (2).

[0061] In practical applications, the channels on the membrane module are preferably used as liquid channels for containing the oil phase obtained in step (2), and the space formed by the outer wall of the membrane module and the inner wall of the housing is preferably used as a gas channel for containing hydrogen. When the channels on the membrane module are used as liquid channels for containing the oil phase obtained in step (2), and the space formed by the outer wall of the membrane module and the inner wall of the housing is used as a gas channel for containing hydrogen, hydrogen is introduced into the housing through the gas inlet, and the oil phase obtained in step (2) is introduced into the channels of the membrane module. Under the action of pressure difference, hydrogen enters the oil phase obtained in step (2) through the holes on the tube wall, thereby causing the hydrogen and the oil phase obtained in step (2) to cross-flow and mix, resulting in a better mixing effect.

[0062] In the above-mentioned membrane mixer, the material forming the membrane module can be an inorganic material (such as inorganic ceramics) or an organic material, as long as the material forming the membrane module does not chemically interact with hydrogen and the oil phase obtained in step (2). The membrane module is formed of a porous material with an average pore size of nanometers. The membrane module may also include a substrate and a porous membrane attached to the substrate. The substrate has through-pores, and the porous membrane can be located on the surface of the substrate that reacts with the oil phase obtained in step (2) or on the surface of the substrate that reacts with hydrogen. Preferably, the porous membrane is located on the surface of the substrate that reacts with the oil phase obtained in step (2). The average pore size of the porous membrane is nanometers. The average pore size of the through-pores on the substrate is not particularly limited, as long as gas can pass through. Preferably, the average pore size of the through-pores on the substrate is 1 nm to 1000 μm (e.g., 50 μm to 200 μm). The filling rate of the membrane module in the housing can be 10% to 90%, such as 50% to 70%. The fill rate refers to the percentage of space occupied by the membrane module relative to the total volume of the housing.

[0063] The average pore size of the membrane module can be 1 nm to 1000 nm, preferably 30 nm to 1000 nm, more preferably 30 nm to 800 nm, and even more preferably 50 nm to 500 nm, thereby further improving the dispersion and mixing effect of hydrogen in the oil phase obtained in step (2). To further improve the dispersion and mixing effect, so that hydrogen can be dispersed more quickly and uniformly in the oil phase obtained in step (2), in the membrane module, the proportion of pores with a pore size in the range of 50 nm to 500 nm to the total number of pores is more than 95%, for example 95% to 98%.

[0064] In this embodiment, hydrogen can be injected into the oil phase obtained in step (2) which is in a static state, or hydrogen can be injected into the oil phase obtained in step (2) which is in a flowing state. It is preferable to inject hydrogen into the oil phase obtained in step (2) which is in a flowing state, so as to obtain not only better hydrogen dispersion and dissolution effect, but also higher production efficiency.

[0065] In specific implementation, the amount of hydrogen mixed with the oil phase obtained in step (2) can be selected based on the impurity content in the oil phase obtained in step (2). In existing heavy oil hydrogenation processes, the amount of hydrogen used is large, and the volume ratio of hydrogen to heavy oil feedstock is generally above 700. However, the solution provided in this application embodiment is to introduce hydrogen into the oil phase obtained in step (2) through pores with an average pore size of nanometers, which can highly disperse and dissolve the hydrogen in the oil phase obtained in step (2), providing sufficient hydrogen source for subsequent hydrogenation reactions. Therefore, even if the amount of hydrogen introduced into the oil phase obtained in step (2) is reduced, a good hydrogenation treatment effect can still be obtained.

[0066] In the above embodiments, the amount of hydrogen mixed with the oil phase obtained in step (2) is 1 to 2 times the amount of hydrogen consumed in the hydrogenation reaction. That is, the amount of hydrogen mixed with the oil phase obtained in step (2) is 0.3 m% to 3.0 m% of the petroleum coke feedstock, preferably 0.5 m% to 3.5 m%. m% can be a mass percentage.

[0067] In practical applications, before mixing with hydrogen, the oil phase obtained in step (2) can be pressurized to the pressure required for the subsequent hydrogenation reaction and heated to the temperature required for the subsequent hydrogenation reaction before being mixed with hydrogen. This allows hydrogen to be better dissolved and dispersed in the oil phase obtained in step (2), reducing the tendency for hydrogen to escape from the oil phase. Specifically, the oil phase obtained in step (2) can be pressurized to 3.0 MPa to 20.0 MPa and heated to 200°C to 450°C.

[0068] In this embodiment, the multi-bed liquid-phase hydrogenation reactor is filled with a hydrogenation catalyst, which is a protective catalyst with large pores and strong scale-holding capacity. After the oil phase obtained in step (2) is mixed with hydrogen to obtain the first hydrogen-containing mixed oil, the first hydrogen-containing mixed oil can be fed into the multi-bed liquid-phase hydrogenation reactor in an upward flow manner. Thus, during the reaction process, the hydrogen dissolved and dispersed in the oil phase will not accumulate to form large bubbles and escape, which can replenish the hydrogen consumed in the reaction process in time, providing sufficient "reaction hydrogen driving force" for the hydrogenation reaction, thereby obtaining a better hydrogenation treatment effect. At the same time, during the reaction process, the hydrogenation catalyst is completely immersed in the first hydrogen-containing mixed oil, that is, the hydrogenation reaction is carried out in the liquid phase without reaction dead zones, so that the hydrogenation catalyst maintains high catalytic activity. In addition, the liquid-phase hydrogenation reaction is uniformly exothermic, which can carry out the reaction heat in time, and the specific heat capacity of the liquid is large, which can reduce the tendency of the hydrogenation catalyst to coke, extend the service life of the hydrogenation catalyst, and further extend the stable operation cycle of the multi-bed liquid-phase hydrogenation reactor.

[0069] In the above embodiments, the multi-bed liquid-phase hydrogenation reactor has multiple reaction zones, each filled with a hydrogenation catalyst. The multiple reaction zones are arranged sequentially from bottom to top at intervals. A feed chamber is provided between any two adjacent reaction zones. Multiple feed inlets of the multi-bed liquid-phase hydrogenation reactor are correspondingly arranged with multiple feed chambers. Material input through a feed inlet first enters the feed chamber corresponding to that inlet, and then enters the reaction zone above that feed chamber. For example, the multi-bed liquid-phase hydrogenation reactor has a primary reaction zone, a secondary reaction zone, a tertiary reaction zone, and a quaternary reaction zone, and also has primary, secondary, tertiary, and quaternary feed chambers, as well as primary, secondary, tertiary, and quaternary feed inlets. The multi-bed liquid-phase hydrogenation reactor is configured from bottom to top with the following components: primary feed chamber, primary reaction zone, secondary feed chamber, secondary reaction zone, tertiary feed chamber, tertiary reaction zone, quaternary feed chamber, and quaternary reaction zone. The primary feed inlet is connected to the primary feed chamber, the secondary feed inlet to the secondary feed chamber, the tertiary feed inlet to the tertiary feed chamber, and the quaternary feed inlet to the quaternary feed chamber. This multi-bed liquid-phase hydrogenation reactor allows for flexible switching of feed inlets, reducing bed pressure drop and ensuring the stability of petroleum coke feedstock processing.

[0070] For example, in the initial stage of operation, the first hydrogen-containing mixed oil can be fed into the primary feed inlet of the multi-bed liquid-phase hydrogenation reactor. When there is excessive fouling and a high pressure drop in the primary reaction zone (i.e., the detected pressure drop does not meet the preset value), the primary reaction zone can be shut out, and the feed can be introduced from the secondary feed inlet. Similarly, when there is excessive fouling and a high pressure drop in the secondary reaction zone (i.e., the detected pressure drop does not meet the preset value), the secondary reaction zone can be shut out, and the feed can be introduced from the tertiary feed inlet. Likewise, when there is excessive fouling and a high pressure drop in the tertiary reaction zone (i.e., the detected pressure drop does not meet the preset value), the tertiary reaction zone can be shut out, and the feed can be introduced from the quaternary feed inlet. This significantly extends the operating cycle of the multi-bed liquid-phase hydrogenation reactor, making the high-value utilization of petroleum coke feedstock more economical. Preferably, the first hydrogen-containing mixed oil passes through at least two reaction zones after entering the multi-bed liquid-phase hydrogenation reactor.

[0071] In practical applications, differential pressure interlocks can be set at each feed inlet and the outlet of the multi-bed liquid-phase hydrogenation reactor to achieve the above-mentioned feed switching process. For example, pressure detection devices are installed at each feed inlet (such as the primary feed inlet, secondary feed inlet, tertiary feed inlet, and quaternary feed inlet) and the outlet of the multi-bed liquid-phase hydrogenation reactor to monitor the pressure drop; the feed inlet is switched according to the pressure drop.

[0072] In the embodiments of this application, the reaction temperature of the first hydrogen-containing mixed oil and the hydrogenation catalyst can be 200℃~450℃, and the reaction pressure can be 3MPa.0~20.0MPa (e.g., 10.0~20.0MPa). The volume hourly space velocity of the first hydrogen-containing mixed oil can be 0.2h. -1 ~5.0h -1 (e.g., 1h) -1 ~4h -1 ).

[0073] (4) The hydrogenation product obtained in step (3) is mixed with hydrogen to obtain a second hydrogen-containing mixed oil. The second hydrogen-containing mixed oil is then fed into a tubular reactor for hydrogenation reaction.

[0074] The hydrogenation product obtained in step (3) can be mixed with hydrogen gas in a membrane mixer. The specific structure of the membrane mixer can be found in the foregoing description and will not be repeated here.

[0075] In this embodiment, the tubular reactor has a large length-to-diameter ratio. Specifically, the ratio of the length to the inner diameter of the tubular reactor can be (5-200):1, for example (10-20):1. The inner diameter of the tubular reactor can be 20mm-2000mm (e.g., 50-500mm). Compared with a batch reactor, using a tubular reactor can reduce the reactor volume, and when using the membrane mixer described above, the membrane mixer can be directly installed on the material inlet pipe of the tubular reactor, making operation flexible and convenient.

[0076] The tubular reactor is filled with a hydrogenation catalyst, which is a selective hydrogenation desulfurization catalyst with the function of inhibiting aromatic saturation, in order to ensure the stability of the properties of heavy aromatic solvents before and after hydrogenation. After the hydrogenation product obtained in step (3) is mixed with hydrogen to obtain a second hydrogen-containing mixed oil, the second hydrogen-containing mixed oil can be fed into the tubular reactor in an upward flow manner. Thus, during the reaction process, the hydrogen dissolved and dispersed in the hydrogenation product will not accumulate to form large bubbles and escape, which can replenish the hydrogen consumed in the reaction process in time, providing sufficient "reaction hydrogen driving force" for the hydrogenation reaction, thereby obtaining a better hydrogenation treatment effect. At the same time, during the reaction process, the hydrogenation catalyst is completely immersed in the second hydrogen-containing mixed oil, that is, the hydrogenation reaction is carried out in the liquid phase, without reaction dead zone, so that the hydrogenation catalyst maintains high catalytic activity. In addition, the liquid phase hydrogenation reaction is uniformly exothermic, which can carry out the reaction heat in time, and the liquid has a large specific heat capacity, which can reduce the tendency of the hydrogenation catalyst to coke, extend the service life of the hydrogenation catalyst, and further extend the stable operation cycle of the tubular reactor.

[0077] In the embodiments of this application, the reaction temperature between the second hydrogen-containing mixed oil and the hydrogenation catalyst can be 200℃~450℃, and the reaction pressure can be 3MPa.0~20.0MPa (e.g., 10.0~20.0MPa). The volume hourly space velocity (VHSV) of the second hydrogen-containing mixed oil can be 0.2h. -1 ~5.0h -1 (e.g., 1h) -1 ~4h -1 ).

[0078] In practical applications, two or more tubular reactors can be set up. Multiple tubular reactors can be connected in series, or they can be connected in series in pairs and then in parallel. The series connection means that the hydrogenation product output from the previous tubular reactor is the feed for the next tubular reactor; the parallel connection means that there is no material exchange between the tubular reactors.

[0079] (5) Extract and distill the hydrogenation product obtained in step (4) and produce petroleum coke based on the heavy oil fraction obtained from the distillation.

[0080] The hydrogenation product obtained in step (4) is extracted and distilled to obtain dry gas, naphtha, solvent fraction, and heavy oil fraction. Since most sulfur atoms are removed during liquid-phase hydrogenation and aromatic hydrocarbon loss is minimal, the heavy oil fraction obtained through extraction and distillation is of high quality and can be used to prepare high-quality petroleum coke. Specifically, the heavy oil fraction can be heated and fed into a delayed coking unit for reaction to produce petroleum coke.

[0081] In this embodiment, the solvent fraction obtained from extraction and distillation can be returned to step (1) for reuse. The solvent fraction has a distillation range of 120℃-230℃, and its components are mostly heavy aromatics, with a small amount of hydrotreated heavy naphtha. Using the solvent fraction obtained from the hydrotreated part of the device itself as a solvent for recycling can reduce the viscosity and density of the petroleum coke feedstock, achieve a good desoldering effect, reduce the loss of external solvent, reduce the heat release of heavy oil products during the hydrogenation process, extend the service life of the catalyst, and thus extend the stable operation cycle of the hydrogenation device (multi-bed liquid phase hydrogenation reactor and tubular reactor).

[0082] It is understood that the petroleum coke feedstock processing method provided in the embodiments of this application includes: (1) mixing petroleum coke feedstock, solvent and surfactant to obtain mixed oil, and placing the mixed oil and water in a fiber liquid membrane contactor for contact; (2) separating the material obtained in step (1) into three phases: oil, water and solid; (3) mixing the oil phase obtained in step (2) with hydrogen to obtain a first hydrogen-containing mixed oil, and feeding the first hydrogen-containing mixed oil into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction; wherein the multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed ports, any feed port is set between two adjacent reaction zones, and the hydrogen-containing mixed oil is fed into the multi-bed liquid phase hydrogenation reactor through the multiple feed ports; (4) mixing the hydrogenation product obtained in step (3) with hydrogen to obtain a second hydrogen-containing mixed oil, and feeding the second hydrogen-containing mixed oil into a tubular reactor for hydrogenation reaction; (5) extracting and distilling the hydrogenation product obtained in step (4), and producing petroleum coke based on the heavy oil fraction obtained by distillation. Based on the solutions provided in the embodiments of this application, solid impurities in petroleum coke raw materials can be effectively removed and the sulfur content in petroleum coke raw materials can be reduced, thereby greatly improving the quality of petroleum coke raw materials.

[0083] Furthermore, the solution provided in this application maximizes the high-value utilization of petroleum coke feedstock resources. The fiber liquid membrane purification and desolidification process, where the oil and water phases contact and elude on a planar membrane, offers advantages such as a large reaction area, high mass transfer efficiency, minimal risk of oil-water emulsification, effective removal of solid impurities from the oil, and continuous, large-scale operation. Simultaneously, this application's embodiment utilizes the electrostatic attraction between amphoteric surfactants and solid impurities to break the original balance of forces between the oil and the solid impurity coating, ultimately forming a hydrophilic solid impurity coating layer. Due to the excellent hydrophilicity of the amphoteric surfactants, the coating formed with the solid impurities easily disperses into the aqueous phase and is captured by the fibers along with the water, thus fully achieving desolidification of the petroleum coke feedstock. In addition, by introducing the first hydrogen-containing mixed oil through multiple inlets of the multi-bed liquid-phase hydrogenation reactor, the problems of high pressure drop and short operating cycles in existing fixed-bed heavy oil hydrogenation can be solved. This efficiently removes solid and metallic impurities from the petroleum coke feedstock, reduces its sulfur content, and allows the treated petroleum coke feedstock to be used for the production of high-quality petroleum coke.

[0084] Based on the petroleum coke feedstock processing method provided in the above embodiments of this application, this application also provides a petroleum coke feedstock processing system, such as... Figure 1As shown, the processing system includes a mixing tank 201, a fiber liquid membrane contactor 202, a separation device 203, a primary hydrogen mixer 204, a multi-bed liquid-phase hydrogenation reactor 205, a secondary hydrogen mixer 206, a tubular reactor 207, an extraction distillation device, and a delayed coking device 209. The multi-bed liquid-phase hydrogenation reactor 205 has multiple reaction zones and multiple feed inlets, with any feed inlet located between two adjacent reaction zones. The outlet of the mixing tank 201 is connected to the feed inlet of the fiber liquid membrane contactor 202, and the outlet of the fiber liquid membrane contactor 202 is connected to the feed inlet of the separation device 203. The oil phase outlet of the separation device 203 is connected to the inlet of the primary hydrogen mixer 204. The outlet of the primary hydrogen mixer 204 is connected to multiple inlets of the multi-bed liquid phase hydrogenation reactor 202. The outlet of the multi-bed liquid phase hydrogenation reactor 205 is connected to the inlet of the secondary hydrogen mixer 206. The outlet of the secondary hydrogen mixer 206 is connected to the inlet of the tubular reactor 207. The outlet of the tubular reactor 207 is connected to the inlet of the extraction distillation device. The heavy oil outlet of the extraction distillation device is connected to the inlet of the delayed coking device 209.

[0085] The mixing tank 201 can be used to mix petroleum coke feedstock, solvent, and surfactant. The inlet of the mixing tank 201 can be used to input petroleum coke feedstock A, solvent B, and surfactant C. The resulting mixed oil is conveyed from the outlet of the mixing tank 201 to the fiber liquid film contactor 202.

[0086] In the fiber liquid membrane contactor 202, the mixed oil comes into contact with the input water D, and the resulting material is input into the separation device 203. The separation device 203 may include an oil-water separator and a sedimentation filter.

[0087] After processing by separation unit 203, oil phase E, aqueous phase F, and solid phase G are obtained. Oil phase E is fed into primary hydrogen mixer 204 and mixed with input hydrogen gas H to obtain a first hydrogen-containing mixed oil. The primary hydrogen mixer 204 can be a membrane mixer.

[0088] The first hydrogen-containing mixed oil can enter through multiple feed ports of the multi-bed liquid-phase hydrogenation reactor 205. In the embodiments of this application, the multi-bed liquid-phase hydrogenation reactor 205 may have a primary feed chamber 2051, a secondary feed chamber 2052, a tertiary feed chamber 2053, and a quaternary feed chamber 2054, as well as a primary reaction zone 2055, a secondary reaction zone 2056, a tertiary reaction zone 2057, and a quaternary reaction zone 2058, and has a primary feed port, a secondary feed port, a tertiary feed port, and a quaternary feed port. The primary feed chamber 2051, primary reaction zone 2055, secondary feed chamber 2052, secondary reaction zone 2056, tertiary feed chamber 2053, tertiary reaction zone 2057, quaternary feed chamber 2054, and quaternary reaction zone 2058 are arranged sequentially from bottom to top within the multi-bed liquid-phase hydrogenation reactor 205. The primary feed inlet is connected to the primary feed chamber 2051, the secondary feed inlet is connected to the secondary feed chamber 2052, the tertiary feed inlet is connected to the tertiary feed chamber 2053, and the quaternary feed inlet is connected to the quaternary feed chamber 2054. Figure 1 As shown.

[0089] Furthermore, a differential pressure interlock can be set at each feed inlet and the outlet of the multi-bed liquid phase hydrogenation reactor 205 to achieve feed switching. For example, pressure detection devices are installed at the primary feed inlet, secondary feed inlet, tertiary feed inlet, quaternary feed inlet, and the outlet of the multi-bed liquid phase hydrogenation reactor to monitor the pressure drop; the feed inlet is switched according to the pressure drop.

[0090] The hydrogenation product output from the multi-bed liquid-phase hydrogenation reactor 205 is transported to a secondary hydrogen mixer 206, where it is mixed with the input hydrogen gas H to obtain a second hydrogen-containing mixed oil. The secondary hydrogen mixer 206 may be a membrane mixer.

[0091] The second hydrogen-containing mixed oil is fed into tubular reactor 207 for hydrogenation treatment. The hydrogenated product obtained from tubular reactor 207 is fed into an extraction distillation unit for further processing.

[0092] In this embodiment of the application, the extraction distillation apparatus may include a high-pressure separator 2081 and a stripping tower 2082. The outlet of the tubular reactor 207 is connected to the inlet of the high-pressure separator 2081, the target gas outlet of the high-pressure separator 2081 is connected to the inlet of the stripping tower 2082, and the heavy oil outlet of the stripping tower 2082 is connected to the inlet of the delayed coking unit 209.

[0093] In this process, hydrogen sulfide gas I is removed from the input hydrogenation product by the high-pressure separator 2081. The target component J, after the removal of hydrogen sulfide gas I, is then sent to the stripping tower 2082 for further processing. After processing in the stripping tower 2082, dry gas K, naphtha L, solvent fraction M, and heavy oil fraction N are obtained. The heavy oil fraction N is fed into the delayed coking unit 209 via the heavy oil outlet of the extraction distillation unit for the production of petroleum coke. The solvent fraction M can be returned to the mixing tank 201 for reuse. Therefore, in one embodiment, the solvent outlet of the stripping tower 2082 can be connected to the feed inlet of the mixing tank 201.

[0094] It is understood that the petroleum coke feedstock processing system provided in the embodiments of this application can, on the one hand, effectively remove solid impurities from the petroleum coke feedstock, reduce the sulfur content in the petroleum coke feedstock, and greatly improve the quality of the petroleum coke feedstock; on the other hand, it can solve the problems of high pressure drop and short operating cycle in existing fixed-bed heavy oil hydrotreating.

[0095] The following describes the petroleum coke feedstock processing method and system provided in this application, with reference to specific embodiments and comparative examples:

[0096] Example 1

[0097] 1) Combine petroleum coke feedstock (composition as shown in Table 1) and solvent (heavy aromatics, density 0.91 g / cm³). 3 The mixture of sodium lauryl iminodipropionate and sodium lauryl iminodipropionate at a mass ratio of 1:0.5:0.0001 is preheated to 100°C. The fibers in the mass transfer space of the fiber liquid film contactor are 316 series stainless steel wire (0.05 mm in diameter). The aspect ratio of the cylindrical mass transfer space is 60:1, the filling rate of the cylinder is 5%, and the volume of the fiber liquid film contactor is 0.3 L. The preheated mixed oil is then subjected to a liquid hourly space velocity (LHSV) of 20 h⁻¹. -1 Inject 10% by weight (relative to the mixed oil) into the fiber liquid film contactor; the contact temperature in the fiber liquid film contactor is 130°C and the contact pressure is 1 MPa.

[0098] 2) After the material obtained in step 1) is allowed to settle in the oil-water separator for 2 hours, the oil and water phases are separated. The lower water phase is precipitated and filtered, and then repeatedly injected into the fiber liquid membrane contactor for recycling, and the catalyst solid powder is recovered. The upper oil phase is mixed with hydrogen in the membrane mixer and then sequentially enters the multi-bed liquid phase hydrogenation reactor, membrane mixer and tubular reactor for processing.

[0099] 3) The hydrotreating conditions are as follows: the average pore size of the membrane mixer is 50 nm, and the proportion of pores with a diameter in the range of 50-55 nm is 98% of the total number of pores; the channels on the membrane module pipes serve as liquid channels, and the space formed by the outer wall of the pipes and the inner wall of the shell serves as a gas channel; the pipes are 60% filled in the shell. The multi-bed liquid-phase hydrotreating reactor is filled with HDD series hydrotreating protectant with large pores and strong scale-holding capacity from Hunan Changlian New Material Technology Co., Ltd.; the tubular reactor is filled with DC series hydrotreating protectant, a selective hydrodesulfurization catalyst with aromatic saturation inhibition function from Hunan Changlian New Material Technology Co., Ltd. The process conditions for hydrotreating are as follows: the hydrotreating reactants enter from the primary feed inlet of the multi-bed liquid-phase hydrotreating reactor and pass through the entire reaction zone. The temperature of the multi-bed liquid-phase hydrotreating reactor is 280℃, the temperature of the tubular reactor is 320℃, the pressure is 10.0 MPa, the hydrogen-to-oil volume ratio of a single reactor is 120:1, and the volume hourly space velocity of the multi-bed liquid-phase hydrotreating reactor is 0.35 h⁻¹. -1 The volumetric space velocity of the tubular reactor is 0.5 h⁻¹. -1 .

[0100] 4) After the hydrogenated oil is separated in a high-pressure separator and a stripping tower, dry gas, naphtha, solvent fraction and heavy oil fraction are obtained. The solvent fraction is returned to step 1) as a solvent for recycling.

[0101] Experiments showed that the system can operate stably for 8000 hours. The properties of petroleum coke feedstock, mixed oil, desolidified petroleum coke feedstock, and hydrogenated oil are shown in Table 1.

[0102] Example 2

[0103] The petroleum coke feedstock was processed according to the method in Example 1, except that the hydrogenation reactants entered through the secondary feed inlet of the multi-bed liquid phase reactor, bypassing the primary reaction zone. The temperature of the multi-bed liquid phase reactor was 280°C, the temperature of the tubular reactor was 320°C, the pressure was 10.0 MPa, the hydrogen-to-oil volume ratio in a single reactor was 120:1, and the volume hourly space velocity (VHSV) of the multi-bed liquid phase reactor was 0.4 h⁻¹. -1 The volumetric space velocity of the tubular reactor is 0.5 h⁻¹. -1 .

[0104] Example 3

[0105] The petroleum coke feedstock was processed according to the method in Example 1, except that the hydrogenation reactants entered through the tertiary feed inlet of the multi-bed liquid phase reactor, bypassing the primary and secondary reaction zones. The temperature of the multi-bed liquid phase reactor was 280°C, the temperature of the tubular reactor was 320°C, the pressure was 10.0 MPa, the hydrogen-to-oil volume ratio in a single reactor was 120:1, and the volume hourly space velocity (VHSV) of the multi-bed liquid phase reactor was 0.45 h⁻¹. -1 The volumetric space velocity of the tubular reactor is 0.5 h⁻¹. -1 .

[0106] Example 4

[0107] The petroleum coke feedstock was processed according to the method in Example 1, except that the hydrogenation reactants entered through the fourth-stage feed inlet of the multi-bed liquid phase reactor, bypassing the primary and secondary reaction zones. The temperature of the multi-bed liquid phase reactor was 280°C, the temperature of the tubular reactor was 320°C, the pressure was 10.0 MPa, the hydrogen-to-oil volume ratio in a single reactor was 120:1, and the volume hourly space velocity (VHSV) of the multi-bed liquid phase reactor was 0.5 h⁻¹. -1 The volumetric space velocity of the tubular reactor is 0.5 h⁻¹. -1 .

[0108] Table 1. Properties of petroleum coke feedstock, mixed oil, desolidified petroleum coke feedstock, and hydrogenated oil in Examples 1-4.

[0109]

[0110] As can be seen from Table 1, the method of this application embodiment can effectively remove heavy metals from petroleum coke feedstock, reduce its sulfur content, and leave aromatics basically unsaturated.

[0111] Heavy oil fraction was used as feedstock for delayed coking. The operating conditions of the delayed coking unit were as follows: furnace outlet temperature of 500℃, coke tower top temperature of 440℃, water injection rate of 2.0% of feed weight, recirculation ratio of 0.2, tower top pressure of 0.1MPa, and catalyst-to-oil ratio of 6.0. The product distribution of coking evaluation is shown in Table 2, and the main properties of petroleum coke are shown in Table 3.

[0112] Table 2 Product Quality Distribution

[0113] project Product quality distribution, % gas 3.32 naphtha 11.34 diesel fuel 24.28 Wax oil 28.12 Petroleum coke 32.63 loss 0.31 total 100

[0114] Table 3 Properties of Petroleum Coke in Examples 1-4

[0115]

[0116] As shown in Table 3, the petroleum coke feedstock treated using the methods in Examples 1-4 can all be used to produce high-quality No. 1 petroleum coke. The results indicate that the primary, secondary, and tertiary reaction zones of the multi-bed liquid-phase hydrogenation reactor can be flexibly separated without significantly impacting the quality of the coking product. Initially, the material is fed through the primary inlet. When the primary reaction zone experiences significant fouling and a high pressure drop, it can be separated and fed through the secondary inlet. Similarly, when the secondary reaction zone experiences significant fouling and a high pressure drop, it can be separated and fed through the tertiary inlet. Finally, when the tertiary reaction zone experiences significant fouling and a high pressure drop, it can be separated and fed through the quaternary inlet.

[0117] Example 5

[0118] 1) Combine the coking feedstock (composition as shown in Table 5) and solvent (heavy aromatics, density 0.91 g / cm³). 3 The mixture was diluted with sodium lauryl iminodipropionate at a mass ratio of 1:0.8:0.0002 and preheated to 60°C. The fibers in the mass transfer space of the fiber liquid film contactor were 316 series stainless steel wire (0.05 mm in diameter). The length-to-diameter ratio of the cylindrical mass transfer space was 60:1, the filling rate of the cylinder was 5%, and the volume of the fiber liquid film contactor was 0.3 L. The preheated mixed oil was then subjected to a liquid hourly space velocity (LHSV) of 20 h⁻¹. -1 Inject 10% by weight (relative to the mixed oil) into the fiber liquid film contactor; the contact temperature in the fiber liquid film contactor is 160°C and the contact pressure is 1.5 MPa.

[0119] 2) After the material obtained in step 1) is allowed to settle in the oil-water separator for 1 hour, the oil and water phases are separated. The lower aqueous phase is precipitated and filtered, then repeatedly injected into the fiber liquid membrane contactor for recycling, and the catalyst solid powder is recovered. The upper oil phase is mixed with hydrogen in the membrane mixer and then enters the multi-bed liquid phase hydrogenation reactor, membrane mixer, and tubular reactor for processing. The system has been running stably for 8000 hours.

[0120] 3) The hydrotreating conditions are as follows: the average pore size of the membrane mixer is 50 nm, and the proportion of pores with a diameter in the range of 50-55 nm is 98% of the total number of pores; the channels on the membrane module pipes serve as liquid channels, and the space formed by the outer wall of the pipes and the inner wall of the shell serves as a gas channel; the pipes are 60% filled in the shell; the multi-bed liquid phase hydrotreating reactor is filled with HDD series hydrotreating protectant with large pores and strong scale-holding capacity from Hunan Changlian New Material Technology Co., Ltd.; the tubular reactor is filled with DC series hydrotreating protectant, a selective hydrodesulfurization catalyst with aromatic saturation inhibition function from Hunan Changlian New Material Technology Co., Ltd. The hydrotreating process conditions are as follows: the hydrotreating reactants enter from the primary feed inlet of the multi-bed liquid phase hydrotreating reactor and pass through the entire reaction zone. The temperature of the multi-bed liquid phase hydrotreating reactor is 280℃, the temperature of the tubular reactor is 320℃, the pressure is 10.0 MPa, the hydrogen-to-oil volume ratio of a single reactor is 120:1, and the volume hourly space velocity of the multi-bed liquid phase hydrotreating reactor is 0.35 h⁻¹. -1 The volumetric space velocity of the tubular reactor is 0.5 h⁻¹. -1 .

[0121] 4) After the hydrogenated oil is separated in a high-pressure separator and a stripping tower, dry gas, naphtha, solvent fraction and heavy oil fraction are obtained. The solvent fraction is returned to step 1) as a solvent for recycling.

[0122] Experiments showed that the device can operate stably for long periods of time. The properties of petroleum coke feedstock, mixed oil, desolidified petroleum coke feedstock, and hydrogenated oil are shown in Table 4.

[0123] Table 4. Properties of petroleum coke feedstock, mixed oil, desolidified petroleum coke feedstock, and hydrogenated oil in Example 5.

[0124]

[0125] As can be seen from Table 4, the method of this application embodiment can effectively remove heavy metals from petroleum coke feedstock, reduce its sulfur content, and leave aromatics basically unsaturated.

[0126] Heavy oil fraction was used as feedstock for delayed coking. The operating conditions of the delayed coking unit were as follows: furnace outlet temperature 500℃, coke tower top temperature 440℃, water injection rate 2.0% of feed weight, recirculation ratio 0.2, tower top pressure 0.1MPa, and catalyst-to-oil ratio 6.0. The distribution of coking products is shown in Table 5, and the main properties of petroleum coke are shown in Table 6.

[0127] Table 5 Quality Distribution of Coking Products

[0128] project Product quality distribution, % gas 3.27 naphtha 11.15 diesel fuel 24.53 Wax oil 28.28 Petroleum coke 32.43 loss 0.34 total 100

[0129] Table 6 Properties of petroleum coke in Example 5

[0130]

[0131] As can be seen from Table 6, the petroleum coke feedstock treated by the method in Example 5 can be used to produce high-quality No. 1 petroleum coke.

[0132] Comparative Example 1

[0133] The petroleum coke feedstock was processed according to the method in Example 1, except that a fiber liquid membrane contactor was not used for deconsolidation; instead, the mixed oil was directly subjected to tubular fixed-bed liquid-phase hydrogenation via a membrane mixer. The properties of the resulting hydrogenated oil are listed in Table 7. The test unit was clogged after 800 hours of operation.

[0134] Table 7 Properties of Hydrogenated Oil from Comparative Example 1

[0135] project Petroleum coke raw materials Mixed oil Hydrogenation produces oil Density (20℃), Kg / m3 1017.1 982.7 968.2 Viscosity (100℃), mm² / s 1446 13.57 12.73 Sulfur content, ppm 15379 10432 2553 Ash content, wt% 0.065 0.043 0.001 Four components, wt% Saturated hydrocarbons 15.19 10.13 9.36 Aromatic hydrocarbons 44.59 70.54 73.13 gelatinous 31.27 12.03 8.99 Asphalt 3.87 1.52 0.73 Metal content, μg / g Ca 85.8 61.2 51.2 Fe 93.3 63.2 42.3 Ni 83.3 56.1 44.1 V 73.8 49.4 29.7 Na 93.7 64.5 44.9

[0136] A comparison of the results of Comparative Example 1 and Example 1 shows that the petroleum coke feedstock after being desolidified by the scheme of the present invention is not suitable for direct hydrogenation.

[0137] Comparative Example 2

[0138] Petroleum coke feedstock is fed directly into delayed coking without any treatment. The operating conditions of the delayed coking unit are as follows: furnace outlet temperature 500℃, coke tower top temperature 440℃, water injection rate 2.0% of feed weight, circulation ratio 0.2, tower top pressure 0.1MPa, and catalyst-to-oil ratio 6.0. The main properties of petroleum coke are shown in Table 8.

[0139] Table 8 Properties of petroleum coke in Comparative Example 2

[0140] project Comparative Example 2: Petroleum Coke 2A petroleum coke 3A petroleum coke w(S), % 1.85 ≯1.0 ≯2.0 w (volatile matter), % -6 ≯12 ≯12 w (ash content), % 0.21 ≯0.35 ≯0.5 Ca, μg / g 380.1 ≯300 - Fe, μg / g 458.2 ≯300 - Ni, μg / g 309.8 ≯250 - V, μg / g 317.5 ≯300 - Na, μg / g 311.4 ≯200 -

[0141] As can be seen from Table 8, using the method of Comparative Example 2, the coking raw materials without any treatment can only produce 3A petroleum coke.

[0142] Comparative Example 3

[0143] The petroleum coke feedstock was processed according to the method in Example 1, except that sodium dodecylbenzenesulfonate (an anionic surfactant) was used instead of sodium lauryliminodipropionate by the same weight. The properties of the deconsolidated coking feedstock are shown in Table 9.

[0144] Comparative Example 4

[0145] The petroleum coke feedstock was processed according to the method in Example 1, except that the same weight of hexadecyltrimethylammonium bromide (a cationic surfactant) was used instead of sodium lauryliminodipropionate. The properties of the deconsolidated coking feedstock are shown in Table 9.

[0146] Comparative Example 5

[0147] The petroleum coke feedstock was processed according to the method in Example 1, except that sodium lauryl iminodipropionate was not added. The properties of the deconsolidated coking feedstock are shown in Table 9.

[0148] Table 9 Properties of coking feedstocks after deconsolidation in Comparative Examples 3-5

[0149]

[0150] Comparing the results of Comparative Examples 3-5 with those of Example 1, it can be seen that the amphoteric surfactant used in this example has a better effect on the desolidification of petroleum coke raw materials, and the sodium lauryl iminodipropionate used has an even better effect on the desolidification of petroleum coke raw materials.

[0151] In the above embodiments and comparative examples, saturated hydrocarbons include alkanes and cycloalkanes. The saturated hydrocarbon content in heavy oil was determined using oil analysis techniques such as the SH / T0659-1998 method and the four-component analysis method. The quality of No. 1 petroleum coke, No. 2A petroleum coke, and No. 3A petroleum coke decreased sequentially.

[0152] As can be seen from the above embodiments and comparative examples, the solution provided by the embodiments of this application can effectively remove solid impurities from petroleum coke raw materials, reduce the sulfur content in petroleum coke raw materials, and greatly improve the quality of petroleum coke raw materials.

[0153] It should also be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0154] The terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase “comprising one…” does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes that element.

[0155] The above are merely embodiments of this application and are not intended to limit the scope of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the scope of the claims of this application.

Claims

1. A method for treating a petroleum coke feedstock, characterized by, include: (1) Petroleum coke feedstock, solvent and surfactant are mixed to obtain mixed oil, and the mixed oil is placed in a fiber liquid film contactor for contact to obtain material; wherein, the petroleum coke feedstock is vacuum residue or deoiled asphalt, the solvent is a mixed aromatic hydrocarbon with a molecular weight greater than xylene, and the mass fraction of C9 aromatic hydrocarbons in the solvent is 10-90%; the surfactant includes at least one of amino acid amphoteric surfactant, betaine amphoteric surfactant and imidazoline amphoteric surfactant; the weight ratio of petroleum coke feedstock, solvent and surfactant is 1:(0.2~3.0):(0.00005~0.0005); (2) The material obtained in step (1) is subjected to three-phase separation of oil, water and solid to obtain the oil phase; (3) The oil phase obtained in step (2) is mixed with hydrogen to obtain a first hydrogen-containing mixed oil. The first hydrogen-containing mixed oil is fed into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction to obtain hydrogenation products. The multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed ports. Any feed port is located between two adjacent reaction zones. The first hydrogen-containing mixed oil is fed into the multi-bed liquid phase hydrogenation reactor through the multiple feed ports. The first hydrogen-containing mixed oil is fed into the multi-bed liquid phase hydrogenation reactor in an upward flow manner. After entering the multi-bed liquid phase hydrogenation reactor, the first hydrogen-containing mixed oil passes through at least four reaction zones. (4) The hydrogenation product obtained in step (3) is mixed with hydrogen to obtain a second hydrogen-containing mixed oil. The second hydrogen-containing mixed oil is fed into a tubular reactor for hydrogenation reaction to obtain hydrogenation product. The tubular reactor is filled with a hydrogenation catalyst, which is a hydrodesulfurization catalyst with selective function of inhibiting aromatic saturation. (5) Extract and distill the hydrogenated product obtained in step (4) to obtain heavy oil; The heavy oil obtained in step (5) is used for delayed coking to produce petroleum coke.

2. The petroleum coke feedstock treatment method according to claim 1, characterized by, In step (1), the weight ratio of the mixed oil to water is 1:(0.05~0.3). In step (1), the conditions under which the mixed oil is contacted with water include a temperature of 60°C to 200°C, a pressure of 0.3 MPa to 3 MPa, and a liquid hourly space velocity of the mixed oil of 5 h -1 to 60 h -1 based on the volume of the fiber filaments in the fiber liquid membrane contactor.

3. The petroleum coke feedstock treatment method according to claim 1, characterized by, The process of mixing the oil phase obtained in step (2) with hydrogen includes: The oil phase obtained in step (2) is heated to obtain a treated oil phase with a temperature of 200℃~450℃ and a pressure of 3.0MPa~20.0MPa; The treated oil phase is mixed with hydrogen.

4. The petroleum coke feedstock treatment method according to claim 1, characterized by, A processing system is used to process petroleum coke feedstock. The processing system includes a mixing tank, a fiber liquid film contactor, a separation device, a primary hydrogen mixer, a multi-bed liquid phase hydrogenation reactor, a secondary hydrogen mixer, a tubular reactor, an extraction distillation device, and a delayed coking device. The multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed inlets, with any feed inlet located between two adjacent reaction zones; The outlet of the mixing tank is connected to the inlet of the fiber liquid membrane contactor, the outlet of the fiber liquid membrane contactor is connected to the inlet of the separation device, the oil phase outlet of the separation device is connected to the inlet of the first-stage hydrogen mixer, the outlet of the first-stage hydrogen mixer is connected to multiple inlets of the multi-bed liquid phase hydrogenation reactor, the outlet of the multi-bed liquid phase hydrogenation reactor is connected to the inlet of the second-stage hydrogen mixer, the outlet of the second-stage hydrogen mixer is connected to the inlet of the tubular reactor, the outlet of the tubular reactor is connected to the inlet of the extraction distillation device, and the heavy oil outlet of the extraction distillation device is connected to the inlet of the delayed coking device.

5. The method for processing petroleum coke feedstock according to claim 4, characterized in that, Pressure detection devices are installed at each inlet and outlet of the multi-bed liquid phase hydrogenation reactor.

6. The method for processing petroleum coke feedstock according to claim 4, characterized in that, The extraction and distillation apparatus includes a high-pressure separator and a stripping tower; The outlet of the tubular reactor is connected to the inlet of the high-pressure separator, the outlet of the target component of the high-pressure separator is connected to the inlet of the stripping tower, and the outlet of the heavy oil of the stripping tower is connected to the inlet of the delayed coking unit. The target component is the component from which hydrogen sulfide has been removed.

7. The method for processing petroleum coke feedstock according to claim 6, characterized in that, The solvent outlet of the stripping tower is connected to the feed inlet of the mixing tank.

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