Petroleum coke raw material treatment method and system

Abstract

The invention relates to the field of petroleum coke, and discloses a petroleum coke raw material treatment method and system.The petroleum coke raw material treatment method comprises the steps that 1, a petroleum coke raw material, a solvent and a surfactant are mixed, and then the mixture and water are placed in a fiber liquid membrane contactor to make contact; (2) separating the material obtained in the step (1); (3) mixing the oil phase obtained in the step (2) with hydrogen, and introducing the mixture into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction; a mixed product of an oil phase and hydrogen enters the multi-bed liquid phase hydrogenation reactor through a plurality of feed ports, the multi-bed liquid phase hydrogenation reactor is provided with a plurality of reaction zones, and any feed port is arranged between two adjacent reaction zones; (4) mixing the hydrogenation product obtained in the step (3) with hydrogen, and introducing 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 the heavy oil fraction obtained by distillation. Therefore, the quality of the petroleum coke raw material can be effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of petroleum coke, and in particular to a petroleum coke raw material processing method and a petroleum coke raw material processing system. Background Art

[0002] Petroleum coke is a solid product converted 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 benefits, low-quality oil products with high sulfur and metal content, such as vacuum residue and deoiled asphalt, are usually used as raw materials for producing petroleum coke, making it difficult to obtain high-quality petroleum coke.

[0003] In order to take into account both economic benefits and high-quality petroleum coke, it is currently a common technical means to treat the petroleum coke raw materials before producing petroleum coke; that is, to improve the quality of petroleum coke by improving the quality of petroleum coke raw materials. For example, CN1309164A discloses a combined process of residual oil hydroprocessing-delayed coking, in which residual oil, coking gas oil and hydrogen are mixed together, and enter a hydroprocessing unit in the presence of a catalyst to react, and the hydrogenation reaction product is separated, wherein the hydrogenated residual oil is delayed coking alone or together with other conventional raw materials for producing needle coke, and the coking product is separated, wherein the coking gas oil is recycled to the hydroprocessing. The disadvantage of this method is that the solid impurities in the raw materials are not effectively removed, which will affect the service life of the catalyst. For example, CN1676574A discloses an improved delayed coking method, wherein the coking raw material and the optional coking circulating oil are pressurized by a radiation feed pump, contacted with hydrogen and a catalyst, and then enter a coking heating furnace to be heated to the coking temperature. The hydrogenated oil is then depressurized by a throttling device and enters a coke tower, and the generated coke remains in the coke tower. The coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel, and coking wax oil. The disadvantage of this method is that there is no pretreatment step for desolidification of the raw material.

[0004] It can be seen that the existing treatment methods are not ideal for the treatment of petroleum coke raw materials and cannot effectively improve the quality of petroleum coke raw materials. Summary of the invention

[0005] The purpose of the present invention is to overcome the problem that the processing effect of petroleum coke raw materials in the prior art is not ideal and the quality cannot be effectively improved, and to provide a petroleum coke raw material processing method and a petroleum coke raw material processing system.

[0006] In order to achieve the above object, the present invention provides a petroleum coke raw material processing method, comprising:

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

[0008] (2) separating the material obtained in step (1) into three phases of oil, water and solid;

[0009] (3) mixing the oil phase obtained in step (2) with hydrogen to obtain a first hydrogenated mixed oil, and passing the first hydrogenated mixed oil into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction; wherein the multi-bed liquid phase hydrogenation reactor has a plurality of reaction zones and a plurality of feed ports, any one of the feed ports is arranged between two adjacent reaction zones, and the first hydrogenated mixed oil is passed into the multi-bed liquid phase hydrogenation reactor via the plurality of feed ports;

[0010] (4) mixing the hydrogenated product obtained in step (3) with hydrogen to obtain a second hydrogenated mixed oil, and passing the second hydrogenated mixed oil into a tubular reactor for a hydrogenation reaction;

[0011] (5) extracting and distilling the hydrogenated product obtained in step (4), and producing petroleum coke based on the heavy oil fraction obtained by the distillation.

[0012] In the examples of the present application, the solvent is a heavy aromatic hydrocarbon.

[0013] In an embodiment of the present application, the surfactant includes at least one of an amino acid type amphoteric surfactant, a betaine type amphoteric surfactant and an imidazoline type amphoteric surfactant.

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

[0015] In the embodiment of the present 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 contacting the mixed oil with water include: a temperature of 60°C to 200°C, a pressure of 0.3MPa to 3MPa, and a liquid hourly volume space velocity of 5h-100 of the mixed oil based on the volume of the fiber filaments in the fiber liquid membrane contactor. -1 ~60h -1 .

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

[0018] The oil phase obtained in step (2) is subjected to a heating treatment to obtain a treated oil phase having a temperature of 200° C. to 450° C. and a pressure of 3.0 MPa to 20.0 MPa;

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

[0020] The second aspect of the present application provides a petroleum coke raw material 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 extractive distillation device and a delayed coking device;

[0021] Wherein, the multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed inlets, and any feed inlet is arranged between two adjacent reaction zones;

[0022] The discharge port of the mixing tank is communicated with the feed port of the fiber liquid membrane contactor, the discharge port of the fiber liquid membrane contactor is communicated with the feed port of the separation device, the oil phase outlet of the separation device is communicated with the feed port of the primary hydrogen mixer, the discharge port of the primary hydrogen mixer is respectively communicated with multiple feed ports of the multi-bed liquid phase hydrogenation reactor, the discharge port of the multi-bed liquid phase hydrogenation reactor is communicated with the feed port of the secondary hydrogen mixer, the discharge port of the secondary hydrogen mixer is communicated with the feed port of the tubular reactor, the discharge port of the tubular reactor is communicated with the feed port of the extractive distillation device, and the heavy oil outlet of the extractive distillation device is communicated with the feed port of the delayed coking device.

[0023] In the embodiment of the present application, each feed port of the multi-bed liquid phase hydrogenation reactor and each discharge port of the multi-bed liquid phase hydrogenation reactor are provided with a pressure detection device.

[0024] In the embodiment of the present application, the extractive distillation apparatus comprises a high-pressure separator and a stripping tower;

[0025] The discharge port of the tubular reactor is communicated with the feed port of the high-pressure separator, the target component outlet of the high-pressure separator is communicated with the feed port of the stripping tower, and the heavy oil outlet of the stripping tower is communicated with the feed port of the delayed coking device;

[0026] Wherein, the target component is the component from which hydrogen sulfide is removed.

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

[0028] According to the above technical scheme, the technical scheme comprises: (1) mixing petroleum coke raw material, solvent and surfactant to obtain a mixed oil, placing the mixed oil and water in a fiber liquid membrane contactor for contact; (2) performing oil, water and solid three-phase separation on the material obtained in step (1); (3) mixing the oil phase obtained in step (2) with hydrogen to obtain a first hydrogenated mixed oil, and passing the first hydrogenated mixed oil into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction; wherein the multi-bed liquid phase hydrogenation reactor has a plurality of reaction zones and a plurality of feed ports, any feed port being arranged between two adjacent reaction zones, and the first hydrogenated mixed oil is passed into the multi-bed liquid phase hydrogenation reactor via the plurality of feed ports; (4) mixing the hydrogenated product obtained in step (3) with hydrogen to obtain a second hydrogenated mixed oil, and passing the second hydrogenated mixed oil into a tubular reactor for hydrogenation reaction; (5) extracting and distilling the hydrogenated product obtained in step (4), and producing petroleum coke based on the heavy oil fraction obtained by the distillation. Based on the solution provided in the embodiments of the present application, solid impurities in the petroleum coke raw material can be effectively removed and the sulfur content in the petroleum coke raw material can be reduced, thereby greatly improving the quality of the petroleum coke raw material.

[0029] Other features and advantages of the embodiments of the present application will be described in detail in the subsequent specific implementation section. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The accompanying drawings are used to provide a further understanding of the embodiments of the present application and constitute a part of the specification. Together with the following specific implementations, they are used to explain the embodiments of the present application, but do not constitute a limitation on the embodiments of the present application. In the accompanying drawings:

[0031] Figure 1 The schematic diagram shows the structure of a petroleum coke raw material processing system according to an embodiment of the present application.

[0032] Description of reference numerals:

[0033] 201—mixing tank; 202—fiber liquid membrane contactor; 203—separation device; 204—primary hydrogen mixer; 205—multi-bed liquid phase hydrogenation reactor; 2051—primary feed chamber; 2052—secondary feed chamber; 2053—third-level feed chamber; 2054—fourth-level feed chamber; 2055—primary reaction zone; 2056—secondary reaction zone; 2057—third-level reaction zone; 2058—fourth-level reaction zone; 206—secondary hydrogen mixer; 207—tubular reactor; 2081—high-pressure separator; 2082—stripping tower; 209—delayed coking unit. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. It should be understood that the specific implementation methods described herein are only used to illustrate and explain the embodiments of the present application, and are not used to limit the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0035] If there are descriptions involving "first", "second", etc. in the embodiments of the present application, the descriptions of "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or suggesting their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in the field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by this application.

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

[0037] In view of this, in one embodiment of the present application, a method for processing petroleum coke raw materials is provided, which can be used to pre-process raw materials for producing petroleum coke, and can pre-process petroleum coke raw materials from various sources. Figure 1 As shown, the method may include step (1), step (2), step (3), step (4) and step (5), which are specifically as follows:

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

[0039] The petroleum coke raw material may also be referred to as coking raw material, delayed coking raw material, etc. The petroleum coke raw material may specifically be vacuum residue oil, deoiled asphalt and other oil products.

[0040] In the embodiments of the present application, the solvent can be used to dilute the petroleum coke raw material, so that the density of the diluted oil is less than that of water, which is conducive to the subsequent oil-water separation. On the other hand, the solvent can also be used to dissolve the colloid and asphaltene in the petroleum coke raw material, destroy the coating layer of the petroleum coke raw material on the solid impurities and the interaction force with the solid impurities, which is conducive to the subsequent separation of solid impurities from the petroleum coke raw material, and has a better desolidification effect. In addition, the solvent can also reduce the viscosity and density of the petroleum coke raw material, which helps to have a better mass transfer effect when the solid-containing petroleum coke raw material is processed in the fiber liquid membrane contactor.

[0041] In specific implementation, the solvent may be heavy aromatics, that is, mixed aromatics with a molecular weight greater than that of xylene. More preferably, in the solvent, the mass fraction of carbon nine (C9) aromatics is 10 to 90%.

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

[0043] The amount of the solvent and the surfactant can be selected according to the processing amount of the petroleum coke raw material. In the specific implementation, in order to achieve a better desolidification effect of the petroleum coke raw material and a better effect of the subsequent processing steps, the weight ratio of the amount of the petroleum coke raw material, the solvent and the surfactant can be 1: (0.2-3.0): (0.00005-0.0005). More preferably, the weight ratio of the amount of the petroleum coke raw material, the solvent and the surfactant can be 1: (0.3-1.5): (0.0001-0.0004).

[0044] The fiber liquid membrane contactor is a highly efficient mass transfer device. The fiber liquid membrane contactor can be a device with two openings at both ends, the two ends are respectively a feed end and a discharge end, the feed end has two feed ports, and the discharge port of the discharge end is connected to the device for oil, water and solid separation in the subsequent step (2).

[0045] A fluid distributor and a mass transfer space cylinder can be arranged in the fiber liquid membrane contactor from the feed end to the discharge end, and a fluid redistributor and fiber filaments can be arranged in sequence in the mass transfer space cylinder from the feed end to the discharge end. Based on the fluid distributor and the fluid redistributor, the solid-containing fluid entering the fiber liquid membrane contactor can be well distributed on the cross section of the fiber filament, so that the mass transfer effect of the fluid in the fiber liquid membrane contactor is better.

[0046] The fiber filaments are installed in the mass transfer space cylinder of the fiber liquid membrane reactor. The fluid evenly distributed through the distributor flows through the fiber filaments. By utilizing capillary action and the difference in surface tension between the water phase and the solid-oil phase on the fiber filaments, the water phase and the oil phase added to the fiber liquid membrane contactor form a liquid film on the surface of the fiber filaments, thereby increasing the surface area of ​​contact between the two phases and greatly improving the mass transfer efficiency. The improved mass transfer efficiency can promote more effective contact between the water phase and the solid impurities in the oil, and can better play the role of desolidification.

[0047] In practical applications, the fiber liquid membrane contactor can be in various shapes as long as it can achieve the effect of desolidification through fiber filaments. Preferably, the fiber liquid membrane contactor is a cylinder. The cylindrical fiber liquid membrane contactor can make full use of the direction of logistics and the effect of the weight of the droplets themselves to desolidify, thereby achieving a better desolidification effect.

[0048] The fluid distributor can be selected from one of the orifice plate type, overflow type and plate type fluid distributors, and the fluid redistributor can be selected from one of the orifice plate type, overflow type and plate type fluid distributors. Multiple sets of fluid redistributors can be arranged in the mass transfer space cylinder.

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

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

[0051] In the embodiment of the present application, based on the fiber liquid membrane contactor, when the mixed oil and water are in contact in the fiber liquid membrane contactor, the fiber filaments with good hydrophilicity can capture the inclusions formed by the amphoteric surfactant and the solid impurities and the water, and then the solid impurities in the petroleum coke raw material enter the water under the action of the amphoteric surfactant with hydrophilic properties, thereby desolidifying the petroleum coke raw material.

[0052] Specifically, the amphoteric surfactant carries both positive and negative charges and has an isoelectric point. When the amphoteric surfactant is dispersed on the water-carrying fiber filaments, the electron-rich colloids and asphaltene in the oil phase are not easy to gather on the fiber filaments to avoid blockage. The liquid film containing solid impurities moves along the fiber filaments, continuously coalescing to form large droplets, which fall off under the action of their own gravity. Finally, the desolidified petroleum coke raw material is obtained through the separation of oil, water and solid phases.

[0053] In order to achieve a better desolidification effect, 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] In order to further improve the desolidification effect of petroleum coke raw materials, the conditions for the contact between the mixed oil and water may include: a temperature of 60°C to 200°C, a pressure of 0.3MPa to 3MPa, and a liquid hourly volume space velocity of the mixed oil of 5h -1 ~60h -1 More preferably, the temperature is 130°C to 150°C, the pressure is 1MPa to 1.8MPa, and the liquid hourly volume space velocity of the mixed oil is 10h -1 ~20h -1 The temperature is the operating temperature of the fiber liquid membrane contactor, the pressure is the working pressure of the fiber liquid membrane contactor, the pressure is specifically the gauge pressure, and the liquid hourly volume space velocity reflects the feed rate of the mixed oil to the fiber liquid membrane contactor.

[0055] In practical applications, after obtaining the mixed oil, the mixed oil can be preheated and then contacted with water in a fiber liquid membrane contactor. Preheating the mixed oil can further dissolve the petroleum coke raw material in the solvent, thereby improving the contact desolidification effect of the mixed oil and water. The preheating temperature can be 50°C to 150°C, preferably 60°C to 100°C.

[0056] (2) Separating the material obtained in step (1) into three phases of oil, water and solid.

[0057] In the embodiment of the present application, the separation of the three phases of oil, water and solid can be achieved by sedimentation and filtration. In the specific implementation, the material obtained in step (1) can be placed in an oil-water separation tank for standing. After standing, the upper layer is the oil phase and the lower layer is water containing solid impurities. Then, the lower layer in the oil-water separation tank is discharged, and after sedimentation and filtration, an aqueous phase and a solid phase are obtained; the separated aqueous phase can be recycled. In practical applications, the sedimentation time can be selected according to the actual separation effect of the oil-water layer 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) mixing the oil phase obtained in step (2) with hydrogen to obtain a first hydrogenated mixed oil, and passing the first hydrogenated mixed oil into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction; wherein the multi-bed liquid phase hydrogenation reactor has a plurality of reaction zones and a plurality of feed ports, any one of the feed ports being arranged between two adjacent reaction zones, and the first hydrogenated mixed oil is passed into the multi-bed liquid phase hydrogenation reactor via the plurality of feed ports.

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

[0060] The membrane mixer comprises a shell and a membrane assembly. The membrane mixer is a shell in which at least one membrane assembly is placed, and a space is provided between the outer wall of the membrane assembly and the inner wall of the shell. In the membrane mixer, the channel on the membrane assembly serves as a liquid channel for accommodating the oil phase obtained in step (2), and the space formed by the outer wall of the membrane assembly and the inner wall of the shell serves as a gas channel for accommodating hydrogen. Alternatively, the channel on the membrane assembly serves as a gas channel for accommodating hydrogen, and the space formed by the outer wall of the membrane assembly and the inner wall of the shell serves as a liquid channel for accommodating the oil phase obtained in step (2).

[0061] In practical applications, the channel on the membrane assembly is preferably used as a liquid channel for accommodating the oil phase obtained in step (2), and the space formed by the outer wall of the membrane assembly and the inner wall of the shell is preferably used as a gas channel for accommodating hydrogen. When the channel on the membrane assembly is used as a liquid channel for accommodating the oil phase obtained in step (2), and the space formed by the outer wall of the membrane assembly and the inner wall of the shell is used as a gas channel for accommodating hydrogen, hydrogen is fed into the shell through the gas inlet, and the oil phase obtained in step (2) is fed into the channel of the membrane assembly. Under the action of the pressure difference, the hydrogen enters the oil phase obtained in step (2) through the holes on the tube wall, so that the hydrogen and the oil phase obtained in step (2) are cross-flow mixed, so that the mixing effect is better.

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

[0063] The average pore size of the pores of the membrane assembly 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, so as to further improve the dispersion and mixing effect of hydrogen in the oil phase obtained in step (2). In order to further improve the dispersion and mixing effect, so that hydrogen can be dispersed in the oil phase obtained in step (2) more quickly and evenly, in the membrane assembly, the number of pores with a pore size in the range of 50 nm to 500 nm accounts for more than 95% of the total number of pores, for example, 95 to 98%.

[0064] In the embodiment of the present application, hydrogen can be injected into the oil phase obtained in step (2) in a static state, or can be injected into the oil phase obtained in step (2) in a flowing state. Preferably, hydrogen is injected into the oil phase obtained in step (2) in a flowing state, which can not only obtain a better hydrogen dispersion and dissolution effect, but also obtain a higher production efficiency.

[0065] In the specific implementation, the amount of hydrogen mixed with the oil phase obtained in step (2) can be selected according to the impurity content in the oil phase obtained in step (2). In the existing heavy oil hydrogenation process, the amount of hydrogen used is large, and the volume ratio of hydrogen to heavy oil feedstock is generally above 700. The solution provided in the embodiment of the present application is to feed hydrogen into the oil phase obtained in step (2) through holes with an average pore size of nanometers, so that the hydrogen can be highly dispersed and dissolved in the oil phase obtained in step (2), which can provide sufficient hydrogen source for subsequent hydrogenation reactions. Therefore, even if the amount of hydrogen fed into the oil phase obtained in step (2) is reduced, a good hydrogenation treatment effect can be obtained.

[0066] In the above embodiment, 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 0.3m%-3.0m%, preferably 0.5m%-3.5m% of the petroleum coke raw material. 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 heat exchanged to the temperature required for the subsequent hydrogenation reaction, and then mixed with hydrogen. In this way, hydrogen can be better dissolved and dispersed in the oil phase obtained in step (2), reducing the tendency of 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 the embodiment of the present application, the multi-bed liquid phase hydrogenation reactor is filled with a hydrogenation catalyst, which is a protective catalyst with large pores and strong fouling capacity. After the oil phase obtained in step (2) is mixed with hydrogen to obtain the first hydrogenated mixed oil, the first hydrogenated mixed oil can be input 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 basically not gather to form large bubbles and escape, and the hydrogen consumed in the reaction process can be replenished 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 hydrogenated mixed oil, that is, the hydrogenation reaction is carried out in the liquid phase, without a reaction dead zone, so that the hydrogenation catalyst maintains a high catalytic activity. In addition, the liquid phase hydrogenation reaction is uniformly exothermic, and the reaction heat can be taken out in time, and the specific heat capacity of the liquid is large, thereby reducing the tendency of the hydrogenation catalyst to form coke, extending the service life of the hydrogenation catalyst, and further extending the stable operation cycle of the multi-bed liquid phase hydrogenation reactor.

[0069] In the above embodiment, the multi-bed liquid phase hydrogenation reactor has multiple reaction zones, each of which is filled with hydrogenation catalyst. The multiple reaction zones are arranged in sequence from bottom to top. There is a feed cavity between any two adjacent reaction zones, and the multiple feed ports of the multi-bed liquid phase hydrogenation reactor are arranged in one-to-one correspondence with the multiple feed cavities. The material input from the feed port first enters the feed cavity corresponding to the feed port, and then enters the reaction zone above the feed cavity from the feed cavity. 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 has a primary feed cavity, a secondary feed cavity, a tertiary feed cavity and a quaternary feed cavity, and also has a primary feed port, a secondary feed port, a tertiary feed port and a quaternary feed port. Among them, the primary feed cavity, the primary reaction zone, the secondary feed cavity, the secondary reaction zone, the tertiary feed cavity, the tertiary reaction zone, the quaternary feed cavity and the quaternary reaction zone are arranged in sequence from bottom to top in the multi-bed liquid phase hydrogenation reactor; the primary feed port is connected to the primary feed cavity, the secondary feed port is connected to the secondary feed cavity, the tertiary feed port is connected to the tertiary feed cavity, and the quaternary feed port is connected to the quaternary feed cavity. By adopting the above-mentioned multi-bed liquid phase hydrogenation reactor, the feed port can be flexibly switched to reduce the bed pressure drop, thereby ensuring the stability of the petroleum coke raw material processing effect.

[0070] For example, in the initial stage of operation, the first hydrogenated mixed oil can be fed from the primary feed port of the multi-bed liquid phase hydrogenation reactor. When the primary reaction zone has a large amount of scale and a high pressure drop, that is, the detected pressure drop does not meet the preset value, the primary reaction zone can be cut out and fed from the secondary feed port; when the secondary reaction zone has a large amount of scale and a high pressure drop, that is, the detected pressure drop does not meet the preset value, the secondary reaction zone can be cut out and fed from the tertiary feed port; when the tertiary reaction zone has a large amount of scale and a high pressure drop, that is, the detected pressure drop does not meet the preset value, the tertiary reaction zone can be cut out and fed from the quaternary feed port. In this way, the operation cycle of the multi-bed liquid phase hydrogenation reactor can be greatly extended, thereby making the high value-added utilization of petroleum coke raw material resources more economical. Preferably, after the first hydrogenated mixed oil enters the multi-bed liquid phase hydrogenation reactor, it passes through at least two reaction zones.

[0071] In practical applications, each feed port and the discharge port of the multi-bed liquid phase hydrogenation reactor can be set up with a pressure difference interlock to achieve the above feed switching process. For example, a pressure detection device is set up at each feed port (such as the primary feed port, the secondary feed port, the tertiary feed port and the quaternary feed port) and the discharge port of the multi-bed liquid phase hydrogenation reactor to monitor the pressure drop; the feed port is switched according to the pressure drop.

[0072] In the embodiment of the present application, the reaction temperature of the first hydrogenated mixed oil and the hydrogenation catalyst can be 200°C to 450°C, and the reaction pressure can be 3MPa.0 to 20.0MPa (e.g., 10.0 to 20.0MPa). The volumetric space velocity of the first hydrogenated mixed oil can be 0.2h -1 ~5.0h -1 (e.g. 1h -1 ~4h -1 ).

[0073] (4) The hydrogenated product obtained in step (3) is mixed with hydrogen to obtain a second hydrogenated mixed oil, and the second hydrogenated mixed oil is introduced into a tubular reactor for a hydrogenation reaction.

[0074] The hydrogenation product obtained in step (3) can be mixed with hydrogen in a membrane mixer. The specific structure of the membrane mixer can refer to the above content and will not be described here.

[0075] In the embodiment of the present application, the tubular reactor has a large aspect 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 (such as 50-500mm). Compared with the kettle reactor, the use of a tubular reactor can reduce the volume of the reactor on the one hand, and on the other hand, when passing through the membrane mixer described above, the membrane mixer can be directly set on the material inlet pipeline of the tubular reactor, which is flexible and convenient to operate.

[0076] The tubular reactor is filled with a hydrogenation catalyst, which is a selective hydrodesulfurization catalyst with the function of inhibiting aromatic saturation, and the purpose is to ensure the stability of the properties of the heavy aromatic solvent before and after hydrogenation. After the hydrogenation product obtained in step (3) is mixed with hydrogen to obtain a second hydrogenated mixed oil, the second hydrogenated mixed oil can be input into the tubular reactor in an upward flow manner. As a result, during the reaction process, the hydrogen dissolved and dispersed in the hydrogenation product will basically not gather to form large bubbles and escape, and the hydrogen consumed in the reaction process can be replenished 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 hydrogenated mixed oil, that is, the hydrogenation reaction is carried out in the liquid phase, without a reaction dead zone, so that the hydrogenation catalyst maintains a high catalytic activity. In addition, the liquid phase hydrogenation reaction is uniformly exothermic, and the reaction heat can be taken out in time, and the specific heat capacity of the liquid is large, thereby reducing the tendency of the hydrogenation catalyst to form coke, extending the service life of the hydrogenation catalyst, and further extending the stable operation cycle of the tubular reactor.

[0077] In the embodiment of the present application, the reaction temperature of the second hydrogenated mixed oil and the hydrogenation catalyst can be 200°C to 450°C, and the reaction pressure can be 3MPa.0 to 20.0MPa (e.g., 10.0 to 20.0MPa). The volumetric space velocity of the second hydrogenated 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 may be provided, and the multiple tubular reactors may be connected in series or in pairs in series 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) extracting and distilling the hydrogenated product obtained in step (4), and producing petroleum coke based on the heavy oil fraction obtained by the distillation.

[0080] Among them, after extracting and distilling the hydrogenation product obtained in step (4), dry gas, naphtha, solvent fraction and heavy oil fraction can be obtained. Since most of the sulfur atoms are removed during the liquid phase hydrogenation process, the loss of aromatics is small, so the heavy oil fraction obtained by 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 then input into a delayed coking unit for reaction to produce petroleum coke.

[0081] In the embodiment of the present application, the solvent fraction obtained by extraction and distillation can be returned to step (1) for reuse. The distillation range of the solvent fraction is 120°C-230°C, and most of its components are heavy aromatics, and there is also a small amount of heavy naphtha after hydrogenation and modification. The solvent fraction after hydrogenation and modification of the device itself is used as a solvent for recycling, which can reduce the viscosity and density of the petroleum coke raw material, achieve a good desolidification effect, and reduce the loss of the added solvent, reduce the heat release of heavy oil products during the hydrogenation process, and extend the service life of the catalyst, thereby extending the stable operation period of the hydrogenation device (multi-bed liquid phase hydrogenation reactor and tubular reactor).

[0082] It can be understood that the petroleum coke raw material processing method provided in the embodiment of the present application includes: (1) mixing the petroleum coke raw material, a solvent and a surfactant to obtain a 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 oil, water and solid phases; (3) mixing the oil phase obtained in step (2) with hydrogen to obtain a first hydrogenated mixed oil, and passing the first hydrogenated 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 arranged between two adjacent reaction zones, and the hydrogenated mixed oil is passed into the multi-bed liquid phase hydrogenation reactor through the multiple feed ports; (4) mixing the hydrogenated product obtained in step (3) with hydrogen to obtain a second hydrogenated mixed oil, and passing the second hydrogenated mixed oil into a tubular reactor for hydrogenation reaction; (5) extracting and distilling the hydrogenated product obtained in step (4), and producing petroleum coke based on the heavy oil fraction obtained by the distillation. Based on the solution provided in the embodiments of the present application, solid impurities in the petroleum coke raw material can be effectively removed and the sulfur content in the petroleum coke raw material can be reduced, thereby greatly improving the quality of the petroleum coke raw material.

[0083] In addition, based on the scheme provided by the embodiment of the present application, the high added value utilization of petroleum coke raw material resources can be maximized. The fiber liquid membrane purification and desolidification treatment is adopted. Since the oil-water two phases are contacted and eluted on the plane membrane, it has the advantages of large reaction area, high mass transfer efficiency, not easy to form oil-water emulsification, good effect of removing solid impurities in oil, and continuous large-scale operation. At the same time, the embodiment of the present application breaks the balance of the original oil-to-solid impurity wrapping oil film through the electrostatic attraction of amphoteric surfactants and solid impurities, and finally forms a hydrophilic solid impurity wrapping layer. Since the amphoteric surfactant has good hydrophilicity, the wrapping formed with the solid impurities is easily dispersed into the water phase, and is captured by the fiber filaments together with the water, thereby fully realizing the desolidification of the petroleum coke raw material. In addition, by setting the first hydrogen-containing mixed oil to enter through multiple feed ports of the multi-bed liquid phase hydrogenation reactor, the problems of high pressure drop and short operation cycle of the existing fixed bed heavy oil hydrogenation can be solved, and the solid and metal impurities in the petroleum coke raw material can be efficiently removed, and the sulfur content in the petroleum coke raw material can be reduced. The treated petroleum coke raw material can be used to produce high-quality petroleum coke.

[0084] Based on the petroleum coke raw material processing method provided in the above embodiment of the present application, the embodiment of the present application also provides a petroleum coke raw material processing system, such as Figure 1As shown, the treatment 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 extractive distillation device and a delayed coking device 209; the multi-bed liquid phase hydrogenation reactor 205 has multiple reaction zones and multiple feed ports, and any feed port is arranged between two adjacent reaction zones; the discharge port of the mixing tank 201 is connected to the feed port of the fiber liquid membrane contactor 202, and the discharge port of the fiber liquid membrane contactor 202 is connected to the feed port of the separation device 203. The oil phase outlet of the separation device 203 is connected to the feed port of the primary hydrogen mixer 204, the discharge port of the primary hydrogen mixer 204 is respectively connected to the multiple feed ports of the multi-bed liquid phase hydrogenation reactor 202, the discharge port of the multi-bed liquid phase hydrogenation reactor 205 is connected to the feed port of the secondary hydrogen mixer 206, the discharge port of the secondary hydrogen mixer 206 is connected to the feed port of the tubular reactor 207, the discharge port of the tubular reactor 207 is connected to the feed port of the extractive distillation device, and the heavy oil outlet of the extractive distillation device is connected to the feed port of the delayed coking device 209.

[0085] The mixing tank 201 can be used to mix petroleum coke raw materials, solvents and surfactants. The feed port of the mixing tank 201 can be used to input petroleum coke raw materials A, solvents B and surfactants C. The mixed oil is transported from the discharge port of the mixing tank 201 to the fiber liquid membrane contactor 202.

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

[0087] After being processed by the separation device 203, an oil phase E, a water phase F and a solid phase G are obtained. The oil phase E is input into the primary hydrogen mixer 204 and mixed with the input hydrogen H to obtain a first hydrogen-containing mixed oil. The primary hydrogen mixer 204 may 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 embodiment of the present application, the multi-bed liquid-phase hydrogenation reactor 205 can have a primary feed cavity 2051, a secondary feed cavity 2052, a tertiary feed cavity 2053, and a quaternary feed cavity 2054, and also has 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. Among them, the primary feed cavity 2051, the primary reaction zone 2055, the secondary feed cavity 2052, the secondary reaction zone 2056, the tertiary feed cavity 2053, the tertiary reaction zone 2057, the quaternary feed cavity 2054 and the quaternary reaction zone 2058 are sequentially arranged in the multi-bed liquid phase hydrogenation reactor 205 from bottom to top, the primary feed port is connected to the primary feed cavity 2051, the secondary feed port is connected to the secondary feed cavity 2052, the tertiary feed port is connected to the tertiary feed cavity 2053, and the quaternary feed port is connected to the quaternary feed cavity 2054. Figure 1 shown.

[0089] Furthermore, each feed port and the discharge port of the multi-bed liquid phase hydrogenation reactor 205 can be provided with a pressure differential interlock to achieve feed switching. For example, a pressure detection device is provided at the primary feed port, the secondary feed port, the tertiary feed port, the quaternary feed port and the discharge port of the multi-bed liquid phase hydrogenation reactor to monitor the pressure drop; the feed port is switched according to the pressure drop.

[0090] The hydrogenation product output from the multi-bed liquid phase hydrogenation reactor 205 is transported to the secondary hydrogen mixer 206 and mixed with the input hydrogen 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 the tubular reactor 207 for hydrogenation treatment. The hydrogenation product obtained from the tubular reactor 207 is fed into the extractive distillation device for treatment.

[0092] In an embodiment of the present application, the extractive distillation device may include a high-pressure separator 2081 and a stripping tower 2082, the discharge port of the tubular reactor 207 is connected to the feed port of the high-pressure separator 2081, the target gas outlet of the high-pressure separator 2081 is connected to the feed port of the stripping tower 2082, and the heavy oil outlet of the stripping tower 2082 is connected to the feed port of the delayed coking device 209.

[0093] Among them, after the high-pressure separator 2081, the hydrogen sulfide gas I in the input hydrogenation product is removed, and the target component J after the hydrogen sulfide gas I is removed is transported to the stripping tower 2082 for treatment. After being processed by the stripping tower 2082, dry gas K, naphtha L, solvent fraction M and heavy oil fraction N are obtained. Among them, the heavy oil fraction N is input into the delayed coking unit 209 through the heavy oil outlet of the extractive 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 port of the mixing tank 201.

[0094] It can be understood that the petroleum coke raw material processing system provided in the embodiment of the present application can, on the one hand, effectively remove solid impurities in the petroleum coke raw materials, reduce the sulfur content in the petroleum coke raw materials, and greatly improve the quality of the petroleum coke raw materials; on the other hand, it can solve the problems of high pressure drop and short operation cycle in the existing fixed bed heavy oil hydrogenation.

[0095] The following is a description of the petroleum coke raw material processing method and system provided in the embodiments of the present application in combination with specific embodiments and comparative examples:

[0096] Example 1

[0097] 1) Petroleum coke raw material (composition as shown in Table 1), solvent (heavy aromatics, density 0.91g / cm 3 ) and sodium lauryl iminodipropionate in a mass ratio of 1:0.5:0.0001, and then preheated to 100°C. The fiber filaments in the mass transfer space cylinder of the fiber liquid membrane contactor are 316 series stainless steel wires (diameter 0.05mm), 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 membrane contactor is 0.3L. The preheated mixed oil is heated at a liquid hourly volumetric space velocity of 20h -1 Inject into the fiber liquid membrane contactor, and at the same time, inject 10 wt% (relative to the mixed oil) into the fiber liquid membrane contactor; the contact temperature in the fiber liquid membrane contactor is 130°C and the contact pressure is 1MPa.

[0098] 2) The material obtained in step 1) is allowed to stand and settle in the oil-water separation tank for 2 hours, and 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 enters the multi-bed liquid phase hydrogenation reactor, membrane mixer, and tubular reactor in sequence for treatment.

[0099] 3) The conditions for hydrogenation treatment are: the average pore size of the membrane mixer is 50nm, and the number of pores with a pore size in the range of 50-55nm accounts for 98% of the total number of pores; the channel on the membrane module pipeline is used as a liquid channel, and the space formed by the outer wall of the pipeline and the inner wall of the shell is used as a gas channel, and the filling rate of the pipeline in the shell is 60%. The multi-bed liquid phase hydrogenation reactor is filled with the large-pore, scale-tolerant HDD series hydrogenation protective agent of Hunan Changlian New Materials Technology Co., Ltd.; the tubular reactor is filled with the DC series hydrogenation protective agent of Hunan Changlian New Materials Technology Co., Ltd., which has the function of inhibiting aromatic saturation. The process conditions for hydrogenation modification are: the hydrogenation reaction materials enter from the primary feed port of the multi-bed liquid phase hydrogenation reactor and pass through all reaction zones. The temperature of the multi-bed liquid phase hydrogenation reactor is 280℃, the temperature of the tubular reactor is 320℃, the pressure is 10.0MPa, the hydrogen-oil volume ratio of a single reactor is 120:1, and the volume space velocity of the multi-bed liquid phase hydrogenation reactor is 0.35h -1 , volumetric space velocity of tubular reactor 0.5h -1 .

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

[0101] According to the experiment, the system can run stably for 8000 hours. The properties of petroleum coke raw material, mixed oil, desolidified petroleum coke raw material and hydrogenated oil are shown in Table 1.

[0102] Example 2

[0103] The petroleum coke raw material was treated according to the method of Example 1, except that the hydrogenation reaction material entered from the secondary feed port of the multi-bed liquid phase reactor and did not pass through 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 of a single reactor was 120:1, and the volumetric space velocity of the multi-bed liquid phase reactor was 0.4 h -1 , volumetric space velocity of tubular reactor 0.5h -1 .

[0104] Example 3

[0105] The petroleum coke raw material was treated according to the method of Example 1, except that the hydrogenation reaction material entered from the third-stage feed port of the multi-bed liquid phase reactor without passing through 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 of a single reactor was 120:1, and the volumetric space velocity of the multi-bed liquid phase reactor was 0.45 h -1 , volumetric space velocity of tubular reactor 0.5h -1 .

[0106] Example 4

[0107] The petroleum coke raw material was treated according to the method of Example 1, except that the hydrogenation reaction material entered from the fourth-stage feed port of the multi-bed liquid phase reactor without passing through 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 of a single reactor was 120:1, and the volumetric space velocity of the multi-bed liquid phase reactor was 0.5 h -1 , volumetric space velocity of tubular reactor 0.5h -1 .

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

[0109]

[0110] It can be seen from Table 1 that the method of the embodiment of the present application can effectively remove heavy metals in the petroleum coke raw material, reduce its sulfur content, and the aromatics are basically not saturated.

[0111] The heavy oil fraction is used as the delayed coking raw material, and the operating conditions of the delayed coking unit are: the outlet temperature of the heating furnace is 500℃, the top temperature of the coke tower is 440℃, the water injection volume accounts for 2.0% of the feed weight, the circulation ratio is 0.2, the top pressure is 0.1MPa, and the catalyst-oil ratio is 6.0. The distribution of coking evaluation products 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] It can be seen from Table 3 that the petroleum coke raw materials treated by the methods of Examples 1 to 4 can all be used to produce high-quality 1# petroleum coke. The results show that the primary, secondary, and tertiary reaction zones of the multi-bed liquid phase hydrogenation reactor can be flexibly cut out without causing a significant adverse effect on the quality of the coking product. In the initial operation, the material is fed from the primary feed port; when the primary reaction zone has a large scale capacity and a high pressure drop, the primary reaction zone can be cut out and fed from the secondary feed port; when the secondary reaction zone has a large scale capacity and a high pressure drop, the secondary reaction zone can be cut out and fed from the tertiary feed port; when the tertiary reaction zone has a large scale capacity and a high pressure drop, the tertiary reaction zone can be cut out and fed from the quaternary feed port.

[0117] Example 5

[0118] 1) Coking raw materials (composition as shown in Table 5), solvent (heavy aromatics, density 0.91g / cm 3 ) and sodium lauryl iminodipropionate were mixed and diluted in a mass ratio of 1:0.8:0.0002 and preheated to 60°C. The fiber filaments in the mass transfer space cylinder of the fiber liquid membrane contactor are 316 series stainless steel wires (diameter 0.05mm), 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 membrane contactor is 0.3L. The preheated mixed oil is heated at a liquid hourly volumetric space velocity of 20h -1 Inject into the fiber liquid membrane contactor, and at the same time, inject 10 wt% (relative to the mixed oil) into the fiber liquid membrane contactor; the contact temperature in the fiber liquid membrane contactor is 160°C and the contact pressure is 1.5 MPa.

[0119] 2) The material obtained in step 1) was placed in the oil-water separation tank for 1 hour, and the oil and water phases were separated. The lower water phase was precipitated and filtered, and then repeatedly injected into the fiber liquid membrane contactor for recycling, and the catalyst solid powder was recovered. The upper oil phase was mixed with hydrogen in the membrane mixer and then entered the multi-bed liquid phase hydrogenation reactor, membrane mixer, and tubular reactor for treatment. The system ran stably for 8,000 hours.

[0120] 3) The conditions for hydrogenation treatment are as follows: the average pore size of the membrane mixer is 50nm, and the number of pores with a pore size in the range of 50-55nm accounts for 98% of the total number of pores; the channel on the membrane module pipeline is used as a liquid channel, and the space formed by the outer wall of the pipeline and the inner wall of the shell is used as a gas channel. The filling rate of the pipeline in the shell is 60%, and the multi-bed liquid phase hydrogenation reactor is filled with the large-pore, scale-tolerant HDD series hydrogenation protective agent of Hunan Changlian New Materials Technology Co., Ltd.; the tubular reactor is filled with the DC series hydrogenation protective agent of Hunan Changlian New Materials Technology Co., Ltd., which has the function of inhibiting aromatic saturation. The process conditions for hydrogenation reforming are as follows: the hydrogenation reaction materials enter from the primary feed port of the multi-bed liquid phase hydrogenation reactor and pass through all reaction zones. The temperature of the multi-bed liquid phase hydrogenation reactor is 280℃, the temperature of the tubular reactor is 320℃, the pressure is 10.0MPa, the hydrogen-oil volume ratio of a single reactor is 120:1, and the volume space velocity of the multi-bed liquid phase hydrogenation reactor is 0.35h -1 , volumetric space velocity of tubular reactor 0.5h -1 .

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

[0122] The experiment shows that the device can operate stably for a long period of time. The properties of petroleum coke raw material, mixed oil, petroleum coke raw material after desolidification, and hydrogenated oil are shown in Table 4.

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

[0124]

[0125] It can be seen from Table 4 that the method of the embodiment of the present application can effectively remove heavy metals in the petroleum coke raw material, reduce its sulfur content, and the aromatics are basically not saturated.

[0126] The heavy oil fraction is used as the delayed coking raw material, and the operating conditions of the delayed coking unit are: the outlet temperature of the heating furnace is 500℃, the top temperature of the coke tower is 440℃, the water injection volume accounts for 2.0% of the feed weight, the circulation ratio is 0.2, the top pressure is 0.1MPa, and the catalyst-oil ratio is 6.0. The distribution of coking evaluation products is shown in Table 5, and the main properties of petroleum coke are shown in Table 6.

[0127] Table 5 Coking product quality distribution

[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 Petroleum coke properties of Example 5

[0130]

[0131] It can be seen from Table 6 that the petroleum coke raw material treated by the method of Example 5 can be used to produce high-quality 1# petroleum coke.

[0132] Comparative Example 1

[0133] The petroleum coke raw material was treated according to the method of Example 1, except that the fiber liquid membrane contactor was not used for desolidification, and the mixed oil was directly subjected to a tubular fixed bed liquid phase hydrogenation reaction through a membrane mixer. The properties of the hydrogenated oil obtained are listed in Table 7. The test device was blocked after running for 800 hours.

[0134] Table 7 Comparative Example 1 Hydrogenation Oil Properties

[0135] project Petroleum coke raw materials Mixed oil Hydrogenated 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, 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 Gel 31.27 12.03 8.99 Asphaltene 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] From the comparison of the results of Comparative Example 1 and Example 1, it can be seen that the petroleum coke raw material after the desolidification treatment according to the scheme of the present invention is not suitable for direct hydrogenation treatment.

[0137] Comparative Example 2

[0138] The petroleum coke raw material enters the delayed coking directly without any treatment. The operating conditions of the delayed coking unit are: the outlet temperature of the heating furnace is 500℃, the top temperature of the coke tower is 440℃, the water injection volume accounts for 2.0% of the feed weight, the circulation ratio is 0.2, the top pressure is 0.1MPa, and the catalyst-oil ratio is 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] It can be seen from Table 8 that by using the method of Comparative Example 2, only 3A petroleum coke can be produced from the coking raw materials without any treatment.

[0142] Comparative Example 3

[0143] The petroleum coke raw material was treated according to the method of Example 1, except that the same weight of sodium dodecylbenzene sulfonate (anionic surfactant) was used instead of sodium lauryl iminodipropionate. The properties of the coking raw material after desolidification are shown in Table 9.

[0144] Comparative Example 4

[0145] The petroleum coke raw material was treated according to the method of Example 1, except that the same weight of hexadecyltrimethylammonium bromide (cationic surfactant) was used instead of sodium lauryl iminodipropionate. The properties of the coking raw material after desolidification are shown in Table 9.

[0146] Comparative Example 5

[0147] The petroleum coke raw material was treated according to the method of Example 1, except that sodium lauryl iminodipropionate was not added. The properties of the coking raw material after desolidification are shown in Table 9.

[0148] Table 9 Properties of coking raw materials after desolidification of comparative examples 3-5

[0149]

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

[0151] In the above embodiments and comparative examples, saturated hydrocarbons include paraffins and cycloalkanes, and the saturated hydrocarbon content in heavy oil is determined using oil product analysis techniques such as SH / T0659-1998 method and four-component analysis method. The quality of 1# petroleum coke, 2A petroleum coke and 3A petroleum coke decreases in sequence.

[0152] Based on the above embodiments and comparative examples, it can be seen that the solution provided in the embodiments of the present application can effectively remove solid impurities in the petroleum coke raw material, reduce the sulfur content in the petroleum coke raw material, and greatly improve the quality of the petroleum coke raw material.

[0153] It should also be noted that the endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in this article.

[0154] The terms "include", "comprising" or any other variation thereof are intended to cover non-exclusive inclusion, so that a process, method, commodity or apparatus comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, commodity or apparatus. In the absence of more restrictions, an element defined by the phrase "comprising a ..." does not exclude the presence of other identical elements in the process, method, commodity or apparatus comprising the element.

[0155] The above are only embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included within the scope of the claims of the present application.

Claims

1. A method for processing petroleum coke raw materials, characterized in that: include: (1) mixing a petroleum coke raw material, a solvent and a surfactant to obtain a 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 of oil, water and solid; (3) mixing the oil phase obtained in step (2) with hydrogen to obtain a first hydrogenated mixed oil, and passing the first hydrogenated mixed oil into a multi-bed liquid phase hydrogenation reactor for hydrogenation reaction; wherein the multi-bed liquid phase hydrogenation reactor has a plurality of reaction zones and a plurality of feed ports, any one of the feed ports is arranged between two adjacent reaction zones, and the first hydrogenated mixed oil is passed into the multi-bed liquid phase hydrogenation reactor via the plurality of feed ports; (4) mixing the hydrogenated product obtained in step (3) with hydrogen to obtain a second hydrogenated mixed oil, and passing the second hydrogenated mixed oil into a tubular reactor for a hydrogenation reaction; (5) extracting and distilling the hydrogenated product obtained in step (4), and producing petroleum coke based on the heavy oil fraction obtained by the distillation.

2. The petroleum coke raw material processing method according to claim 1, characterized in that: The solvent is a heavy aromatic hydrocarbon.

3. The petroleum coke raw material processing method according to claim 1, characterized in that: The surfactant includes at least one of an amino acid type amphoteric surfactant, a betaine type amphoteric surfactant and an imidazoline type amphoteric surfactant.

4. The petroleum coke raw material processing method according to claim 1, characterized in that: In step (1), the weight ratio of the petroleum coke raw material, the solvent and the surfactant is 1: (0.2-3.0): (0.00005-0.0005).

5. The petroleum coke raw material processing method according to claim 1, characterized in that: In step (1), the weight ratio of the mixed oil to water is 1:(0.05-0.3); In step (1), the conditions for contacting the mixed oil with water include: a temperature of 60°C to 200°C, a pressure of 0.3MPa to 3MPa, and a liquid hourly volume space velocity of 5h-100 of the mixed oil based on the volume of the fiber filaments in the fiber liquid membrane contactor. -1 ~60h -1 .

6. The petroleum coke raw material processing method according to claim 1, characterized in that: The step of mixing the oil phase obtained in step (2) with hydrogen comprises: The oil phase obtained in step (2) is subjected to a heating treatment to obtain a treated oil phase having a temperature of 200° C. to 450° C. and a pressure of 3.0 MPa to 20.0 MPa; The treated oil phase is mixed with hydrogen.

7. A petroleum coke raw material processing system, characterized in that: The treatment system includes 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 extractive distillation device and a delayed coking device; Wherein, the multi-bed liquid phase hydrogenation reactor has multiple reaction zones and multiple feed inlets, and any feed inlet is arranged between two adjacent reaction zones; The discharge port of the mixing tank is communicated with the feed port of the fiber liquid membrane contactor, the discharge port of the fiber liquid membrane contactor is communicated with the feed port of the separation device, the oil phase outlet of the separation device is communicated with the feed port of the primary hydrogen mixer, the discharge port of the primary hydrogen mixer is respectively communicated with multiple feed ports of the multi-bed liquid phase hydrogenation reactor, the discharge port of the multi-bed liquid phase hydrogenation reactor is communicated with the feed port of the secondary hydrogen mixer, the discharge port of the secondary hydrogen mixer is communicated with the feed port of the tubular reactor, the discharge port of the tubular reactor is communicated with the feed port of the extractive distillation device, and the heavy oil outlet of the extractive distillation device is communicated with the feed port of the delayed coking device.

8. The petroleum coke raw material processing system according to claim 7, characterized in that: Each feed port of the multi-bed liquid phase hydrogenation reactor and each discharge port of the multi-bed liquid phase hydrogenation reactor are provided with a pressure detection device.

9. The petroleum coke raw material processing system according to claim 7, characterized in that: The extractive distillation device comprises a high-pressure separator and a stripping tower; The discharge port of the tubular reactor is communicated with the feed port of the high-pressure separator, the target component outlet of the high-pressure separator is communicated with the feed port of the stripping tower, and the heavy oil outlet of the stripping tower is communicated with the feed port of the delayed coking device; Wherein, the target component is the component from which hydrogen sulfide is removed.

10. The petroleum coke raw material processing system according to claim 9, characterized in that: The solvent outlet of the stripping tower is communicated with the feed inlet of the mixing tank.

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