Petroleum coke processing device, processing method and processing system

Abstract

A petroleum coke processing apparatus, processing method and processing system, the processing apparatus including an activation unit which is a ring furnace reactor, the processing system including a first reactor, the processing apparatus used as a second reactor, a washing and separation unit, a cooling unit, a melting and separation unit, a washing and drying unit, optionally a regeneration unit, optionally a drying and roasting unit, and optionally an evaporative crystallization unit. Also provided is a method for producing carbon materials using the processing system for processing petroleum coke.

Description

Detailed Description of the Invention

[0001] [Technical Field] The present disclosure relates to a petroleum coke processing apparatus, method, and system, and more particularly to an apparatus, method, and system for preparing porous carbon materials by using petroleum coke as a raw material.

[0002] [Background technology] Petroleum coke is a product of delayed coking units. Its properties include high calorific value, high moisture content, and low volatility. Petroleum coke is obtained at a yield of approximately 25% to 30% of the feedstock oil added to the coking unit. With the further development of delayed coking technology, the industry is currently facing the challenge of effectively utilizing petroleum coke and increasing its added value. Using petroleum coke as a raw material for preparing porous carbon materials has become one of the effective ways to improve the value of petroleum coke in recent years.

[0003] Petroleum coke-derived porous carbon materials have properties such as low impurity content, large specific surface area, and stable physical and chemical properties. Petroleum coke-derived porous carbon materials are widely used in fields such as industry, agriculture, national defense, and science and technology. Compared with raw materials such as biomass, coal, and asphalt, petroleum coke has a high degree of graphitization and is relatively difficult to activate. Activation of petroleum coke generally requires the use of an alkali metal hydroxide, such as potassium hydroxide, as an activator. Activation presents challenges such as severe corrosion of the equipment and unstable product properties.

[0004] US 4,082,694 A discloses activated carbon and a method for preparing it. The method includes the steps of agitating a feed of pulverized coal, coal coke, petroleum coke, or a mixture thereof in the presence of a substantial weight ratio of aqueous potassium hydroxide and heating at a lower first temperature to dehydrate the feed; activating the dehydrated feed by heating to a higher second temperature; and then cooling and removing inorganic materials from the feed by a washing process to form activated carbon with a higher specific surface area. The prepared activated carbon has a cage-like structure, microporosity, and good bulk density and total organic carbon index. For example, the preparation method includes mixing petroleum coke with three times its weight of potassium hydroxide, dehydrating at a temperature of 300-500°C, activating at a temperature of 700-800°C, washing the activated mixture with water, and producing activated carbon with a specific surface area of ​​2600 m². 2 / g of activated carbon.

[0005] JP95-215711 describes a method for activating petroleum coke with three times its weight of potassium hydroxide at 800°C under reduced pressure to produce a pulverized ... 2 A method for producing activated carbon with a yield of 1000 kJ / g or more is disclosed. This method uses a tunnel kiln activation furnace.

[0006] In CN1304788A, KOH and petroleum coke are mixed in a weight ratio of 5:1 and activated at high temperature to produce a specific surface area of ​​3500m 2 / g or more of activated carbon can be prepared.

[0007] Currently, prior art processes for activating petroleum coke employ a relatively high ratio of base to petroleum coke, which can result in severe corrosion of the activation equipment. Generally, rotary kilns or tunnel kilns are used as equipment for activating petroleum coke with base. When rotary kilns are used for high-temperature activation, the physical state of the material therein changes with temperature, causing some of the material to liquefy and adhere to the walls of the rotary kiln reactor during rotation, forming a dense layer of material, which can adversely affect heat transfer and cause uneven heating of the material. This can affect activation and lead to instability in product properties. When tunnel kilns are used, the feed is transported on a conveyor belt. During its passage through the tunnel kiln, the feed is activated at high temperatures. Tunnel kilns typically use long, flexible conveyor belts and support structures. Under the high temperature and alkaline conditions during activation, the conveyor belt and its support structure are susceptible to structural collapse and corrosion, which can lead to malfunctions of the activation equipment. Although industrial production of activated carbon from petroleum coke has been realized at present, there are still problems such as high cost of activators, unstable properties of the product, etc. Therefore, there is still a need for further development of methods, apparatuses, and systems for preparing porous carbon materials from petroleum coke.

[0008] Summary of the Invention The present disclosure provides a method, apparatus, and system for processing petroleum coke that overcomes the shortcomings of the prior art. The method, apparatus, and system according to the present disclosure can achieve continuous production. The method, apparatus, and system according to the present disclosure also have the advantages of high activation efficiency and stable properties of the resulting carbonaceous material product.

[0009] In a first aspect, provided herein is a method for processing petroleum coke, comprising: (1) adding a feed of petroleum coke and an activator into a first reactor and subjecting the feed to a first treatment under a non-reactive atmosphere to obtain a first gas phase material and a first solid phase material; (2) adding the first solid-phase material and the first gas-phase material obtained in step (1) into a second reactor and subjecting them to a second heat treatment to obtain a second gas-phase material and a second solid-phase material; (3) subjecting the second solid phase material obtained in step (2) to a cooling treatment, a mixing treatment with water, and a liquid-solid separation treatment to obtain a first liquid phase material and a third solid phase material, wherein the third solid phase material is further subjected to a washing treatment and a drying treatment to obtain a porous carbon material. The method includes:

[0010] Preferably, the method for treating petroleum coke comprises: (4) contacting and reacting the first liquid phase material obtained in step (3) with a precipitating agent, wherein the effluent of the reaction is subjected to liquid-solid separation to obtain a second liquid phase material and a fourth solid phase material, and the fourth solid phase material is dried, calcined, and then recycled as the precipitating agent. Further includes:

[0011] More preferably, the method for treating petroleum coke comprises: (5) subjecting the second liquid phase material obtained in step (4) to evaporation-crystallization to obtain a third gas phase material and a fifth solid phase material, wherein the fifth solid phase material is reused as the activator. Further includes:

[0012] In the petroleum coke processing method according to the present disclosure, the petroleum coke feed may preferably be subjected to a drying and pulverization process before being added into the first reactor together with the activator in step (1). The drying process may be carried out according to methods well known in the art. Generally, the dried petroleum coke feed may have a moisture content of 2 wt.% or less, preferably 1 wt.% or less. The pulverization process may be carried out according to methods well known in the art. The pulverized petroleum coke feed may have a particle size of 200 μm or less, preferably 150 μm or less.

[0013] In the method for treating petroleum coke according to the present disclosure, the first treatment in step (1) may be carried out at a temperature of 200 to 500°C, preferably 350 to 450°C.

[0014] In the method for treating petroleum coke according to the present disclosure, the activator and the feed of petroleum coke in step (1) may be in a mass ratio of 0.5:1 to 8:1, preferably 1:1 to 5:1.

[0015] In the method for treating petroleum coke according to the present disclosure, the activator in step (1) may be an alkali metal compound, preferably one or more alkali metal compounds selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate, more preferably a mixture of one or two of potassium hydroxide and sodium hydroxide with one or two of potassium carbonate and sodium carbonate, and most preferably a mixture of potassium hydroxide and potassium carbonate. In one variant, the mixture of potassium hydroxide and potassium carbonate may contain a potassium carbonate content of 1 to 30% by weight, preferably 5 to 20% by weight.

[0016] In the method for treating petroleum coke according to the present disclosure, the non-reactive atmosphere in step (1) may be one or more of nitrogen or an inert gas, preferably nitrogen. The inert gas may be one or more of helium, neon, argon, krypton, and xenon. When calculated based on the mass of the petroleum coke feed, the non-reactive atmosphere may be provided in an amount of 100 to 2000 L, preferably 500 to 1000 L, per kg of the petroleum coke feed.

[0017] In the petroleum coke processing method according to the present disclosure, the first reactor in step (1) may be a rotary kiln reactor. The rotary kiln reactor may have any structure common in the art. Those skilled in the art may select it as needed. Furthermore, the rotation speed may be 0.1 to 2 rpm, preferably 0.5 to 1 rpm.

[0018] In the petroleum coke processing method according to the present disclosure, the second heat treatment in step (2) may be carried out under conditions of a pressure of 10 to 100 Pa (gauge pressure), preferably 20 to 50 Pa (gauge pressure), and a temperature of 700 to 1000°C, preferably 800 to 950°C. The second heat treatment may include a high-temperature treatment and a cooling treatment, and the high-temperature treatment may include a heating treatment and a constant-temperature maintenance treatment. The heating treatment may be continued for 30 to 300 minutes, preferably 60 to 180 minutes. The constant-temperature maintenance treatment may be continued for 10 to 120 minutes, preferably 20 to 60 minutes. Furthermore, in the cooling treatment, the material after the constant-temperature maintenance treatment step may be cooled to 300 to 500°C. The heating treatment may be carried out by fuel gas or electric thermal radiation heating. The constant-temperature maintenance treatment step may be carried out by using microwave heating. The cooling treatment may be carried out by water cooling or by passing a gas through the material to cool it after the isothermal treatment step.

[0019] In the petroleum coke processing method of the present disclosure, the second gaseous material obtained in step (2) may be subjected to a water washing treatment and then a separation treatment in a separation unit. The separation unit may employ one or more separation means to obtain various gas products (e.g., nitrogen, hydrogen, and other gases (mainly including carbon monoxide, carbon dioxide, and hydrocarbon-containing gases such as methane, etc.)). The water washing treatment may be carried out by using a venturi scrubber. The separation unit may include one or more devices, such as a cryogenic separation device, a pressure swing adsorption device, a membrane separation device, etc. The nitrogen obtained after the separation treatment may be recycled to the first reactor as the non-reactive atmosphere. The carbon dioxide and hydrogen obtained after the separation treatment may be stored as products for other uses. The hydrocarbon-containing gas and carbon monoxide obtained after the separation treatment may be used as fuel gas for heating treatment. Those skilled in the art can select an appropriate device for the separation unit based on the gas composition and actual needs, which is a basic skill required for those skilled in the art.

[0020] In the method for treating petroleum coke according to the present disclosure, the second reactor is a tube furnace reactor, which comprises: (i) a housing forming an enclosed annular space divided into an inlet / outlet zone, a high temperature zone, and a cooling zone, the high temperature zone may include a heated section and a constant temperature section; (ii) a rotary table located within the housing and arranged along the annular space of the housing, the rotary table being rotatable relative to the housing to receive the first solid phase material at the entrance / exit zone, convey the first solid phase material sequentially into the high temperature zone and the cooling zone, and then discharge the first solid phase material at the entrance / exit zone; (iii) a plurality of baffles located within the housing, fixed on the housing, and spaced apart above the rotary table, the baffles including a plurality of guide holes; Equipped with.

[0021] Further, in some of the above embodiments, the heating section may be powered by fuel gas or electric radiant heating, the heating section may be heated to a temperature of 700-1000°C in 30-300 minutes, and the constant temperature section may be powered using microwave heating at a constant temperature of 700-1000°C for 10-120 minutes.

[0022] Furthermore, in some of the above embodiments, the heating section may be heated to a temperature of 800-950°C in 60-180 minutes, and the constant temperature section may be operated using microwave heating at a constant temperature of 800-950°C for 20-60 minutes.

[0023] Furthermore, in the above embodiments, the material that has passed through the constant temperature zone may be cooled to 300 to 500° C. in the cooling zone. Preferably, the material that has passed through the constant temperature zone may be cooled to 300 to 500° C. in the cooling zone via a water-cooled coil.

[0024] Furthermore, in some of the above embodiments, the tube furnace reactor may further include one or more carrier gas inlets disposed in the inlet / outlet zone and a gas outlet disposed in the high temperature zone. There may be three carrier gas inlets, disposed at the beginning, middle, and end of the inlet / outlet zone, respectively.

[0025] Furthermore, in the above embodiments, the baffles may be perpendicular to the surface of the rotary table, the guide holes may be arranged in the upper one-third to the upper one-half of the baffles, and the guide holes may be formed with an opening ratio of 20% to 30%. The inlet side of the guide holes may have a larger hole diameter than the outlet side. The guide holes may be conical.

[0026] Furthermore, in some of the above embodiments, the gas outlet may be located in the constant temperature section of the high temperature zone.

[0027] Furthermore, in some of the above embodiments, the inlet / outlet zone may include a feeder, which may include one or more star valves for preventing gas in the housing from entering a line for the first solid phase material, and a distributor for evenly distributing the first solid phase material entering the housing onto the rotary table.

[0028] Furthermore, in some of the above embodiments, the inlet / outlet zone may include a discharge system fixed inside the housing, the discharge system including: (i) a spiral discharge device that outputs discharged material horizontally from a top of the spiral discharge device; (ii) a conveyor belt that is inclined with one end disposed on the top of the spiral discharge device and delivers the discharged material to the top of the spiral discharge device; and (iii) a lifting surface that is inclined to pick up the second solid phase material disposed on the rotating table as the discharged material and to the other end of the conveyor belt.

[0029] Further, in some of the above embodiments, the lifting surface may include a primary lifting surface that picks up particles of the second solid phase material having a particle size distribution greater than D10 onto the conveyor belt, and a secondary lifting surface that picks up particles of the second solid phase material having a particle size distribution smaller than D10 onto the conveyor belt.

[0030] Furthermore, in some of the above embodiments, the lowermost edge of the primary lifting surface may be out of contact with the surface of the rotary table, may be made of a rigid material, and may have a sawtooth shape, and the lowermost edge of the secondary lifting surface may be in contact with the surface of the rotary table and may be made of a flexible material.

[0031] In the petroleum coke processing method according to the present disclosure, in step (3), the second solid phase material is cooled to 20-100°C, preferably 50-80°C, and then mixed with water. Here, the amount of water is 2-10 times, preferably 3-5 times, the weight of the second solid phase material. The cooling treatment may be carried out in a slag cooler. The slag cooler may be any commonly used in the art.

[0032] In the petroleum coke processing method according to the present disclosure, in step (3), the third solid phase material is subjected to further washing and drying processes to obtain a porous carbon material, preferably activated carbon. The washing process may include water washing and pickling. Preferably, the water washing process is carried out until the filtrate becomes neutral. The water washing process may be carried out in a container or on a belt. The pickling process may be carried out using an acid, which may be hydrochloric acid, sulfuric acid, or a mixture thereof. Typically, the acid is used as an aqueous solution with a concentration of 1 to 10% by weight. The drying process may be carried out at a temperature of 50 to 200°C, preferably 80 to 160°C. The drying process may be carried out in an air atmosphere, a nitrogen atmosphere, or a vacuum.

[0033] In the petroleum coke treatment method according to the present disclosure, in step (4), the precipitating agent may be calcium oxide and / or calcium hydroxide, preferably calcium hydroxide. The precipitating agent may be added in an amount of 70 to 100%, preferably 70 to 95%, more preferably 75 to 90% by mass of the carbonate ions in the first liquid phase material, based on calcium ions.

[0034] In the method for treating petroleum coke according to the present disclosure, in step (4), the first liquid phase material and the precipitant may be contacted and reacted at a temperature of 60 to 95°C, preferably 80 to 90°C.

[0035] In the petroleum coke processing method according to the present disclosure, in step (4), the fourth solid phase material may be dried and calcined, and then recycled as the precipitant. The drying process may be carried out at a temperature of 80 to 200°C, preferably 120 to 160°C, and the calcination process may be carried out at a temperature of 700 to 1200°C, preferably 800 to 1000°C.

[0036] In the petroleum coke processing method according to the present disclosure, in step (5), the third gaseous phase material obtained in the evaporation-crystallization may be condensed and recycled to step (3) to be mixed with the cooled second solid phase material.

[0037] In a second aspect of the present disclosure, there is provided an apparatus for processing petroleum coke, the apparatus comprising an activation unit, the activation unit being a tube furnace reactor, the tube furnace reactor comprising: (i) a housing forming an enclosed annular space divided into an inlet / outlet zone, a high temperature zone, and a cooling zone, the high temperature zone may include a heated section and a constant temperature section; (ii) a rotary table located within the housing and disposed along the annular space of the housing, the rotary table being rotatable relative to the housing to receive a mixed feed material of petroleum coke and activator at the inlet / outlet zone, convey the mixed feed material of petroleum coke and activator sequentially into the high temperature zone and the cooling zone, and then discharge the mixed feed material at the inlet / outlet zone; (iii) a plurality of baffles located within the housing, fixed on the housing, and spaced apart above the rotary table, the baffles including a plurality of guide holes; Equipped with.

[0038] In one variation, the petroleum coke processing apparatus according to the present disclosure is used to prepare porous carbon materials, such as activated carbon, from petroleum coke.

[0039] Furthermore, in some of the above embodiments, the heating section may be heated to a temperature of 700-1000°C in 30-300 minutes, and the constant temperature section may be operated using microwave heating at a constant temperature of 700-1000°C for 10-120 minutes.

[0040] Furthermore, in some of the above embodiments, the heating section may be heated to a temperature of 800-950°C in 60-180 minutes, and the constant temperature section may be operated using microwave heating at a constant temperature of 800-950°C for 20-60 minutes.

[0041] Furthermore, in the above embodiments, the mixed feed that has passed through the constant temperature section may be cooled to 300 to 500° C. in the cooling zone. For example, the cooling treatment in the cooling zone may be performed via a water-cooled coil.

[0042] Furthermore, in some of the above embodiments, the activation unit may further include one or more carrier gas inlets disposed in the inlet / outlet zone and a gas outlet disposed in the high temperature zone. There may be three carrier gas inlets, disposed at the beginning, middle, and end of the inlet / outlet zone, respectively.

[0043] Furthermore, in the above embodiments, the baffles may be perpendicular to the surface of the rotary table, the guide holes may be arranged in the upper one-third to the upper one-half of the baffles, and the guide holes may be formed with an opening ratio of 20% to 30%. The inlet side of the guide holes may have a larger hole diameter than the outlet side. The guide holes may be conical.

[0044] Furthermore, in some of the above embodiments, the gas outlet may be located in the constant temperature section of the high temperature zone.

[0045] Additionally, in some of the above embodiments, the inlet / outlet area may include a feeder, which may include one or more star valves to prevent gas within the housing from entering a line for the mixed feed material, and a distributor to evenly distribute the mixed feed material entering the housing onto the rotary table.

[0046] Furthermore, in some of the above embodiments, the inlet / outlet zone may include a discharge system fixed inside the housing, the discharge system including: (i) a spiral discharge device that outputs discharged material horizontally from a top of the spiral discharge device; (ii) a conveyor belt that is inclined with one end disposed on the top of the spiral discharge device and delivers the discharged material to the top of the spiral discharge device; and (iii) a lifting surface that is inclined to pick up the discharged material disposed on the rotating table and to the other end of the conveyor belt.

[0047] Further, in several of the above embodiments, the lifting surface may include a primary lifting surface that picks up particles of the material having a particle size distribution greater than D10 onto the conveyor belt, and a secondary lifting surface that picks up particles of the material having a particle size distribution smaller than D10 onto the conveyor belt.

[0048] Furthermore, in some of the above embodiments, the lowermost edge of the primary lifting surface may be out of contact with the surface of the rotary table, may be made of a rigid material, and may have a sawtooth shape, and the lowermost edge of the secondary lifting surface may be in contact with the surface of the rotary table and may be made of a flexible material.

[0049] Furthermore, in some of the above embodiments, the apparatus according to the present disclosure may further include an activator recovery unit, in which the discharged material is subjected to a washing and separation process, and the resulting liquid-phase product is subjected to a causticizing process to recover the activator.

[0050] Furthermore, in some of the above embodiments, the apparatus according to the present disclosure may further include a pre-treatment unit. In the pre-treatment unit, petroleum coke is mixed with an activator and pulverized. The mixture is heated to 400-500°C to pre-convert the mixture, and then sent to the activation unit. The activator and petroleum coke may be mixed in a weight ratio of 1:1 to 5:1. The pre-treatment unit may be a rotary kiln for pre-converting the mixture.

[0051] Furthermore, in some of the above embodiments, the apparatus according to the present disclosure may further include a gas processing unit, in which the gas-phase products discharged from the gas outlet of the activation unit are subjected to purification and separation processes to output hydrogen gas.

[0052] Furthermore, in some of the above embodiments, the apparatus according to the present disclosure may further include a washing and purification unit, in which the discharged material from the activation unit is subjected to a washing and separation process, and the solid product after the separation process is dried to obtain the activated carbon.

[0053] In a third aspect of the present disclosure, there is provided a system for processing petroleum coke, the system comprising: a first reactor for receiving and processing a feed of petroleum coke and an activator to obtain a first gas phase material and a first solid phase material; a second reactor for receiving and processing the first gas phase material and the first solid phase material to obtain a second gas phase material and a second solid phase material; a scrubbing and separation unit for receiving and treating the second gaseous material from the second reactor to obtain nitrogen, hydrogen and other gases; a cooling unit for receiving the second solid phase material from the second reactor and cooling it to obtain a cooled second solid phase material; a dissolving and separating unit for receiving the cooled second solid phase material and water from the cooling unit and subjecting them to a mixing treatment and liquid-solid separation to obtain a first liquid phase material and a third solid phase material; a washing and drying unit for receiving the third solid phase material and a washing solution from the dissolving and separating unit, wherein the third solid phase material is subjected to a washing treatment and a drying treatment so as to obtain activated carbon; Equipped with.

[0054] Preferably, said system for treating petroleum coke comprises: a regeneration unit for receiving the first liquid phase material and a precipitant from the dissolution and separation unit, wherein the first liquid phase material is subjected to treatment and liquid-solid separation so as to obtain a second liquid phase material and a fourth solid phase material; a drying and calcination unit for receiving and processing the fourth solid phase material from the regeneration unit, wherein the fourth solid phase material is subjected to a drying treatment and a calcination treatment so as to obtain the regenerated precipitant; may further comprise:

[0055] More preferably, said system for treating petroleum coke comprises: an evaporation-crystallization unit for receiving and processing the second liquid phase material from the regeneration unit, wherein the second liquid phase material is subjected to evaporation-crystallization to obtain a third gas phase material and a fifth solid phase material, and the fifth solid phase material is recycled as the activating agent; may further comprise:

[0056] In the petroleum coke processing system according to the present disclosure, the first reactor is provided with a feed inlet communicating with a feed line for petroleum coke and a feed line for activator; The second reactor comprises a gas inlet communicating with a gas phase outlet of the first reactor via a first gas phase line, and a solid phase inlet communicating with a solid phase outlet of the first reactor via a first solid phase line; the washing and separation unit comprises a feed inlet communicating with a vapor phase outlet of the second reactor via a second vapor phase line; the cooling unit includes a feed inlet communicating with a solid phase outlet of the second reactor via a second solid phase line; the dissolution and separation unit comprises a feed inlet communicating with an outlet of the cooling unit via a third solid phase line; the washing and drying unit comprises a feed inlet communicating with a solid phase outlet of the lysis unit via a fourth solid phase line; the regeneration unit comprises a feed inlet communicating with a liquid phase outlet of the dissolution and separation unit via a first liquid phase line; the drying and calcining unit having a feed inlet communicating with a solid phase outlet of the regeneration unit via a fifth solid phase line; A treatment system wherein the evaporation-crystallization unit comprises a feed inlet communicating with the liquid phase outlet of the regeneration unit via a second liquid phase line.

[0057] In the petroleum coke processing system according to the present disclosure, the feed line for petroleum coke may further communicate with a drying unit and a pulverizing unit. In the drying unit and the pulverizing unit, the petroleum coke feed is first subjected to a drying process and a pulverizing process. The drying process may be carried out according to methods well known in the art. Generally, the dried petroleum coke feed may have a moisture content of 2% by weight or less, preferably 1% by weight or less. The pulverizing process may be carried out according to methods well known in the art. The pulverized petroleum coke feed may have a particle size of 200 μm or less, preferably 150 μm or less.

[0058] In the petroleum coke processing system of the present disclosure, the first reactor may be a rotary kiln reactor. The rotary kiln reactor may have any structure commonly used in the art. Those skilled in the art may select an appropriate one according to their needs.

[0059] In the petroleum coke processing system according to the present disclosure, the washing and separation unit may include a washing unit and a separation unit connected in series. The washing unit may include one or more washing devices, preferably a venturi scrubber for washing the second gaseous material. The washed second gaseous material is sent to the separation unit for separation. After separation, nitrogen, hydrogen, carbon dioxide, hydrocarbon-containing gas, and carbon monoxide are obtained. The separation unit may include one or more devices, such as a device for cryogenic separation, a device for pressure swing adsorption, a device for membrane separation, etc. Those skilled in the art can select appropriate devices for the separation unit based on the gas composition and actual needs, which is a basic skill for those skilled in the art.

[0060] In the petroleum coke processing system according to the present disclosure, the second reactor may be a tube furnace reactor, such as the tube furnace reactor described above, the description of which will not be repeated here.

[0061] In the petroleum coke processing system according to the present disclosure, the cooling unit may include one or more cooling devices. The cooling device is preferably a slag cooler. The slag cooler may be one or more slag coolers selected from the group consisting of a drum slag cooler, a vibration slag cooler, a water-cooled slag cooler, and a disk slag cooler. The slag cooler is preferably a drum slag cooler. The cooling unit is for further cooling the second solid phase material from the second reactor to 20-100°C, preferably 50-80°C. The slag cooler may be a commercially available product in the art. The type of slag cooler may be selected by a person skilled in the art based on his or her requirements; such selection is a basic skill for a person skilled in the art.

[0062] In the petroleum coke processing system according to the present disclosure, the dissolving and separation unit may be a vessel having an agitator for receiving the cooled second solid phase material from the cooling unit and the wash water from the feedwater line. The cooled second solid phase material and the wash water are subjected to mixing and liquid-solid separation to obtain the first liquid phase material and the third solid phase material. The amount of the wash water is generally 2 to 10 times, preferably 3 to 5 times, the weight of the second solid phase material. The petroleum coke processing system according to the present disclosure may include one or more dissolving and separation units, preferably two or more dissolving and separation units, and more preferably two dissolving and separation units. When there are two or more dissolving and separation units, they can be switched between. The number of units may be determined based on the amount of the second solid phase material. The dissolving and separation unit according to the present disclosure may be operated intermittently. The liquid phase material produced during evaporation and crystallization in the evaporation and crystallization unit may be used as the wash water.

[0063] In the petroleum coke processing system according to the present disclosure, the washing and drying unit may include a washing unit and a drying unit. The washing unit may include a water washing process and an acid pickling process. Preferably, the water washing process is carried out until the filtrate becomes neutral. The water washing process may be carried out one by one in a container or on a belt. The acid pickling process may be carried out using an acid, which may be hydrochloric acid, sulfuric acid, or a mixture thereof. Typically, the acid is used as an aqueous solution with a concentration of 1 to 10% by weight. The drying process may be carried out at a temperature of 50 to 200°C, preferably 80 to 160°C. The drying process may be carried out in an air atmosphere, a nitrogen atmosphere, or a vacuum.

[0064] In the petroleum coke processing system according to the present disclosure, the regeneration unit may be a heatable vessel made of alkali-resistant material with a stirring device, preferably an autoclave.

[0065] In the petroleum coke processing system according to the present disclosure, the evaporation-crystallization unit may be one or more of an autoclave evaporator, a tubular thin film evaporator, a scraper vacuum evaporator, a centrifugal thin film evaporator, etc. Preferably, the evaporation-crystallization unit is an autoclave evaporator.

[0066] Compared with the prior art, the petroleum coke processing method, the processing device, and the processing system according to the present disclosure have the following advantages:

[0067] 1. It is applicable to the continuous production of porous carbon materials from petroleum coke, which is advantageous for large-scale industrial production.

[0068] 2.(i) A tube furnace reactor is used in which a rotary table rotates relative to the housing. During use, the rotary table carries the feed material, which moves inside the tube furnace housing. During feeding and movement, the rotary table remains stationary relative to the moving parts, thereby preventing the feed material from being disturbed and ensuring uniformity of product properties. Furthermore, the tube furnace reactor avoids the problems of material sticking to the walls, which commonly occur in methods using rotary kilns, and the conveyor collapse, which commonly occurs in tunnel kilns due to their excessive length. (ii) Furthermore, in the high-temperature zone of the tube furnace reactor, the heating section is heated by fuel gas or electric radiant heating, and the constant-temperature section is heated using microwave heating. Heating by fuel gas or electric radiant heating has the advantage of being cost-effective, and heat is transferred from the surface of the material to the interior of the material. In microwave heating, heat is transferred from the interior of the material to the exterior of the material. Therefore, by combining the two, a better heating effect can be achieved in the high-temperature zone while making the heating more uniform, thereby avoiding the problem of non-uniform product properties associated with the high-temperature zone. In addition, the isothermal section can be configured to consist of a conventional isothermal section and a microwave isothermal section. In this case, the conventional isothermal section is still operated by fuel gas or electric radiation heating, and the microwave isothermal section is operated using microwave heating. This configuration can avoid the increased energy consumption and cost caused by using microwave heating throughout the isothermal section. (iii) Furthermore, the tube furnace reactor includes multiple baffles above the rotary table, and multiple guide holes are formed on the multiple baffles. This design not only moves the high-temperature gas distilled from the heated feed material out of the housing and reduces backmixing, but also accumulates ash generated during activation on the multiple baffles, thereby effectively preventing ash accumulation at the gas outlet, which may block the line.

[0069] 3. A step of regenerating the activator is included. By recycling the activator, the amount of activator used is reduced, thereby saving costs. At the same time, general industrial resources such as carrier gas and washing water are also recycled, thereby reducing emissions and meeting the requirements of a green economy.

[0070] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing the flow of a method for treating petroleum coke according to the present disclosure.

[0071] FIG. 2 is a three-dimensional schematic diagram of a tube furnace reactor according to the present disclosure (mainly showing the housing and the configuration for microwave heating).

[0072] FIG. 3 is a top schematic view of a tube furnace reactor according to the present disclosure.

[0073] FIG. 4 is a cross-sectional schematic view of a tube furnace reactor according to the present disclosure (mainly showing a partial cross-section of the rotary table).

[0074] FIG. 5 is a cross-sectional schematic diagram of a baffle according to the present disclosure (showing the guide hole configuration on the baffle).

[0075] FIG. 6 is a schematic diagram showing the structure of an exhaust system according to the present disclosure.

[0076] FIG. 7 is a schematic diagram illustrating the configuration of the lowermost portion of a primary lifting surface according to the present disclosure.

[0077] Detailed Description The techniques and advantages of the present invention will now be described with reference to exemplary embodiments, without limiting the invention thereto.

[0078] Unless otherwise stated, as used throughout the specification and claims, the word "comprises" or equivalent words such as "including" or "having" should be understood to include stated elements or components, but not to exclude other elements or components.

[0079] Spatially or temporally relative terms, such as "below," "belower," "lower side," "up," "above," "upper," and the like, may be used herein to facilitate a description of the relationship of an element or feature shown in a figure to another element(s) or feature(s). It should be understood that spatially relative terms may be intended to encompass various orientations of an object during use or operation in addition to the orientation shown in the figure. For example, if an object in a figure were turned over, an element described as being "below" or "below" another element(s) or feature(s) would be oriented as being "above" the element(s) or feature(s). Thus, the exemplary term "below" can encompass both an orientation of below and above. An object may have other orientations (rotated 90 degrees or other orientations), and the corresponding description should be left to the spatially relative terms used herein.

[0080] As used herein, the terms "first," "second," etc. are used to distinguish between two different elements or locations. In other words, in some embodiments, the terms "first," "second," etc. may be interchangeable.

[0081] All numerical values ​​of parameters (e.g., amounts or conditions) herein should be understood to be modified in all instances by the word "about," regardless of whether "about" actually appears before the numerical value.

[0082] 1 illustrates one embodiment of a method for processing petroleum coke according to the present disclosure. The method includes the following steps: subjecting a petroleum coke feed 101 to drying and pulverization in a drying unit A and a pulverization unit B. The petroleum coke feed after drying and pulverization is mixed with an activator 102 in a mixing unit C. The resulting mixture 103 is sent to a first reactor D and subjected to a first treatment in the presence of an inert atmosphere 121 to obtain a first gas phase material 104 and a first solid phase material 105. The resulting first solid phase material 105 and first gas phase material 104 are sent to a second reactor E and subjected to a second heat treatment to obtain a second gas phase material 106 and a second solid phase material 107. The obtained second gaseous material 106 is subjected to processing in a washing and separation unit G (e.g., washing in a gas scrubber and separation in a separation unit) to obtain nitrogen 120, hydrogen 118, and other gases 119 (the other gases mainly include carbon monoxide, carbon dioxide, hydrocarbon gases such as methane, etc.). The separation unit may use one or more devices such as a cryogenic separation device, a pressure swing adsorption device, and a membrane separation device. The hydrocarbon-containing gas and carbon monoxide obtained after the separation process may be used as fuel for heating in the second reactor. The nitrogen obtained after the separation process may be recycled to the first reactor as a non-reactive atmosphere. The hydrogen obtained after the separation process may be stored as a product. The obtained second solid-phase material 107 is subjected to cooling in a cooling unit H (e.g., a slag cooler). The cooled second solid phase material is sent to a dissolving and separating unit I for mixing with water and liquid-solid separation to obtain a first liquid phase material 109 and a third solid phase material 108. The third solid phase material 108 is sent to a washing and drying unit J for washing with water and pickling, and then dried in a drying unit K to obtain a porous carbon material product (e.g., activated carbon) 122. The obtained first liquid phase material 109 is sent to a regeneration unit L for contact and reaction with a precipitant 110. The effluent of the reaction is subjected to liquid-solid separation to obtain a second liquid phase material 111 and a fourth solid phase material 112.The fourth solid phase material 112 is then dried and calcined in the drying and calcining unit to obtain a regenerated precipitant 113 and carbon dioxide 114. The regenerated precipitant 113 may be recycled and reused in the regeneration unit L. The second liquid phase material 111 is sent to the evaporation-crystallization unit and subjected to evaporation-crystallization to obtain a third gas phase material 115 and a fifth solid phase material 116. The fifth solid phase material 116 is recycled and reused in the mixing unit C as a regenerated activator. The third gas phase material 115 is condensed and then recycled and reused in the dissolution and separation unit I.

[0083] As shown in FIGS. 2 to 4, the second reactor E is a tubular furnace reactor according to the present disclosure. The tubular furnace reactor includes an annular housing 2. The annular housing 2 forms a sealed annular space divided into an inlet / outlet zone (upper left of the ring in FIG. 3), a high-temperature zone (right half of the ring in FIG. 3), and a cooling zone (lower left of the ring in FIG. 3). In the tubular furnace reactor, the pressure may be set to 10 to 100 Pa (gauge pressure), preferably 20 to 50 Pa (gauge pressure). The tubular furnace reactor further includes a rotary table 25. The rotary table 25 is located inside the annular housing 2 and is arranged along the annular space of the annular housing 2. The rotary table 25 may be driven by a transmission mechanism 250 at its bottom. The transmission mechanism 250 rotates the rotary table 25 relative to the housing 2. A feeder 21 in the inlet / outlet zone distributes the first solid phase material onto the rotary table 25. During rotation, the turntable 25 receives the first solid phase material and sequentially transports it through a high temperature zone (where the first solid phase material is activated by high temperature) and a cooling zone (where the material is cooled), and then transports it into an entrance / exit zone (where the cooled first solid phase material is discharged through a discharge system). The material of the turntable is not particularly limited. However, a hard material is preferred. The turntable may have a greater thickness, and its bottom may be reinforced with ribs, so that the problem of structural collapse of a flexible conveyor may be further avoided.

[0084] In the tube furnace reactor of the present disclosure, the turntable rotates relative to the housing. During use, the turntable carries the feed material and moves inside the tube furnace housing. During feeding and movement, the turntable remains stationary relative to the moving parts, which prevents disturbance of the feed material and ensures uniformity of product properties. Furthermore, the tube furnace reactor avoids the problems of material sticking to the walls that commonly occur in methods using rotary kilns and the structural collapse of conveyors that commonly occur due to the excessive length of tunnel kilns.

[0085] Furthermore, as shown in FIG. 3, the high-temperature zone is divided into a heating section and a constant-temperature section. The heating section may be heated by fuel gas or electric radiation heating, and the time in the heating section is 30 to 300 minutes, preferably 60 to 180 minutes, to heat the first solid phase material to 700 to 1000°C, preferably 800 to 950°C. The constant-temperature section may be heated entirely using microwave heating. Alternatively, as shown in FIG. 3, the constant-temperature section may consist of a conventional constant-temperature section and a microwave constant-temperature section. In this case, the conventional constant-temperature section is operated by fuel gas or electric radiation heating, and the microwave constant-temperature section is operated by microwave heating. Heating by fuel gas or electric radiation heating may be performed by a heat radiation tube 202. In this case, the heat radiation tube 202 extends through the housing 200 (see FIG. 4). The isothermal section maintains the material at a temperature of 700-1000°C, preferably 800-950°C, for a time period of 10-120 minutes, preferably 20-60 minutes. The time in the heating section and the time in the isothermal section may be controlled by factors such as the structural dimensions of the annular housing 2, the area of ​​each zone and section, and the rotation speed of the rotary table 25. In the high-temperature zone of the annular furnace reactor, the heating section is heated by fuel gas or electric radiant heating, and the isothermal section is heated using microwave heating. Heating by fuel gas or electric radiant heating has the advantage of being cost-effective, and heat is transferred from the surface of the material to the interior of the material. In microwave heating, heat is transferred from the interior of the material to the exterior of the material. Therefore, by combining the two, more effective and uniform heating is achieved in the high-temperature zone, thereby avoiding the problem of non-uniform product properties associated with high-temperature zones. In addition, the isothermal section can be configured to consist of a conventional isothermal section and a microwave isothermal section. In this case, the conventional isothermal section is operated by fuel gas or electric radiant heating, and the microwave isothermal section is operated using microwave heating.Such a configuration may avoid the increased energy consumption and costs that would result from using microwave heating throughout the isothermal section.

[0086] After high temperature activation, the material may be sent into a cooling zone and subjected to a cooling treatment such that the material that has passed through the constant temperature section may be cooled to 300-500° C. In one variation, the material that has passed through the constant temperature section may be cooled to 300-500° C. in the cooling zone via water-cooled coils.

[0087] 2, microwaves for heating are supplied via microwave source 11. Cooling water is transported through cooling water inlet / outlet main 120 into cooling coil 12 and then into the cooling zone to cool the high temperature activated material. Microwave heating is powered and controlled through weak current cable tray 13 and strong current cable tray 14.

[0088] Nitrogen is typically used as a carrier gas during the activation of petroleum coke. Therefore, the tube furnace reactor further includes one or more carrier gas inlets and gas outlets. To ensure carrier gas flux and uniformity, one or more carrier gas inlets may be located in the inlet / outlet zone. Preferably, but not exclusively, there are three carrier gas inlets, located at the beginning, middle, and end of the inlet / outlet zone. The gas outlet may be located in the constant temperature section of the high temperature zone.

[0089] Furthermore, as shown in FIGS. 4 and 5 , the baffles 24 are arranged at intervals (preferably at equal intervals) above the rotary table 25 (without contacting the rotary table 25). To ensure that the carrier gas A and the high-temperature gas distilled during activation can pass through the baffles 24, these are considered to be the second gas-phase material (gas B in FIG. 3 ) that is ultimately discharged outside the housing through the gas outlet. Preferably, but not exclusively, the baffles 24 may be arranged perpendicular to the surface of the rotary table 25, and the guide holes 240 may be arranged in the upper one-third to one-half of the baffles, with an opening ratio of 20% to 30%. When the feed material on the rotary table 25 is heated, the high-temperature gas is distilled off and concentrated toward the upper part of the annular housing. To effectively remove these hot gases from the housing and reduce backmixing and the resulting adverse effects on conversion, multiple guide holes are opened in the upper portion of the baffle 24. As a result, a circulating environment is created in which cool carrier gas flows under the baffle 24 and the generated hot gas exits through the upper portion of the baffle 24. During the high-temperature activation of the first solid phase material, fine ash is generated. The fine ash is carried and transported by the hot gas. To avoid accumulation of this fine ash at the gas outlet, which could block the line, a change in the gas flow rate in the guide holes 240 is used to settle this fine ash inside the baffle 24 and transport the fine ash out of the tube furnace reactor containing the solid material. Furthermore, the diameter of the inlet side of the guide holes 240 may be larger than the diameter of the outlet side. In one variant, the diameter of the outlet side may be set to 40 to 60% of the diameter of the inlet side. In one variant, the guide holes may be conical or have other shapes similar to a cone shape.

[0090] Furthermore, as shown in Fig. 4, a sealing layer 201 is provided at the bottom of the housing 200 of the annular furnace reactor, isolating the housing 200 from a base (not shown) and forming a sealed space. A rotary table 25 is located in this sealed space and rotates relative to the housing 200 by driving a transmission mechanism 250. As shown in Fig. 3, a first solid phase material is fed to the rotary table 25 through a feeder 21 and distributed onto the rotary table 25. The first solid phase material is transported by the rotary table 25 and moves sequentially through a heating section, a conventional constant temperature section, a microwave constant temperature section, and a cooling section, and finally exits the annular housing 2 through an exhaust system 22.

[0091] Also shown in Figure 3, a feeder 21 is disposed in the inlet / outlet zone. The feeder 21 may include a star valve and a distributor (not shown). One or more star valves may be used. The star valve may prevent gas in the housing 2 from entering the line for the first solid phase material. The distributor is used to distribute the first solid phase material entering the housing onto the rotary table 25.

[0092] Furthermore, as shown in FIG. 3 , a discharge system 22 is also disposed in the inlet / outlet zone. The discharge system 22 is fixed inside the housing 2. As shown in FIGS. 6 and 7 , the discharge system 22 may include a spiral discharge device 221, a conveyor belt 222, and a lifting surface. The lifting surface may include a primary lifting surface 223 and a secondary lifting surface 224. The two lifting surfaces are slightly inclined with respect to the surface of the rotary table. The primary lifting surface 223 may pick up particles of material having a particle size distribution larger than D10 onto the conveyor belt 222, and the secondary lifting surface 224 may pick up particles of material having a particle size distribution smaller than D10 onto the conveyor belt 222. The material (second solid-phase material) after being activated at high temperature and cooled may have a certain viscosity and may adhere to the surface of the rotary table 25. Therefore, the bottom end of the primary lifting surface 223 may be made of a hard material and may have a sawtooth shape (e.g., like the sawtooth structure 2230 shown in FIG. 7 ) so that material particles are effectively separated from the surface of the turntable 25 and picked up. To prevent damage to the surface of the turntable 25, the bottom end of the primary lifting surface 223 does not contact the surface of the turntable 25, and the distance between it and the surface of the turntable 25 is the particle size distribution of D10. This protects the turntable and allows material particles with a particle size distribution larger than D10 to be picked up. The bottom end of the secondary lifting surface 224 contacts the surface of the turntable 25. To protect the surface of the turntable, the bottom end of the secondary lifting surface 224 may be made of a flexible material. Material particles that leak from the bottom end of the primary lifting surface 223 (i.e., material particles with a particle size distribution smaller than D10) can be picked up by the secondary lifting surface 224. The conveyor belt 222 is also inclined. As the rotary table 25 moves, the two lifting surfaces continuously pick up particles of material. The particles of material are gradually piled up and transferred to the lower end of the conveyor belt 222, then transferred to the upper end of the conveyor belt, and dropped into the spiral discharge device 221. The spiral discharge device 221 outputs the discharged material horizontally from its top.As a result, the particles of material are moved out of the annular housing 2 through the material conveyor 23 .

[0093] The petroleum coke processing apparatus according to the present disclosure may further include a washing and refining unit, in which the discharge material from the activation unit is subjected to a washing and separation process, and the solid product after separation is dried to obtain a porous carbon material (e.g., activated carbon).

[0094] Due to the fact that a large amount of activator is used in the activation of petroleum coke, the apparatus according to the present disclosure may further include an activator recovery unit for realizing the regeneration and recovery of the activator, thereby effectively reducing the consumption of the activator and saving costs. In particular, in the activator recovery unit, the liquid phase product obtained after washing and separating the discharge material in the washing and refining unit is subjected to a causticizing reaction with calcium hydroxide, and the activator (e.g., potassium hydroxide) is recovered for reuse. In one variant, the purified water produced in the causticizing reaction may be recycled to the washing and refining unit.

[0095] Furthermore, the apparatus according to the present disclosure may further include a gas processing unit, in which the gas-phase products discharged from the gas outlet of the activation unit are subjected to purification and separation to output hydrogen gas, and the remaining gas is discharged through torch combustion.

[0096] By introducing an activator recovery unit and a gas treatment unit to recover the activator and carrier gas, the apparatus according to the present disclosure reduces the consumption of activator, saves costs, reduces emissions, and meets the requirements of a green economy.

[0097] [Example] In the examples and comparative examples according to the present disclosure, the petroleum coke feed had the properties shown in Table 1. The second reactor in the examples according to the present disclosure was a tube furnace reactor as described above.

[0098] [Table 1]

[0099] Example 1 This example followed the flow shown in Figure 1. A petroleum coke feed was dried in a drying unit (hot air circulation drying chamber) to reduce the moisture content to 0.77% by weight. In the pulverizing unit, the dried petroleum coke feed was pulverized as follows: first, it was pulverized to a particle size of less than 2 mm by a jaw crusher, and then it was pulverized to a particle size of less than 100 μm by an ultra-fine mill. The pulverized petroleum coke feed and an activator (a mixture of potassium hydroxide and potassium carbonate, the amount of potassium carbonate was 10% by weight) were added to a mixing unit (spiral belt mixer) and mixed. The mixture was sent to a storage bin with nitrogen protection and then sent to the first reactor (rotary kiln reactor). At the same time, fresh nitrogen gas was introduced into the first reactor at a rate of 500 L / kg based on the added petroleum coke feed. The rotary kiln reactor was operated at a temperature of 450°C, a rotation speed of 1 rpm, and a residence time of the material in the rotary kiln reactor of 1 hour. The effluent from the rotary kiln reactor was sent to a second reactor (a tube furnace reactor). The tube furnace reactor was operated under the following conditions: the constant temperature section was fully heated using microwave heating, the temperature in the constant temperature section was 900°C, the ratio of the length of the heating section to the length of the constant temperature section was 4:1, the residence time in the heating section was 120 minutes, the residence time in the constant temperature section was 30 minutes, and the pressure in the heating zone was 30 Pa (gauge pressure). After passing through the constant temperature section, the material was sent to a cooling section and finally discharged from the tube furnace reactor. The solid phase material from the tube furnace reactor was sent to a cooling unit (a slag cooler) for cooling. The solid material from the cooling unit and fresh water were sent to a dissolving and separating unit in a mass ratio of 1:4, mixed and stirred for 1 hour, and then subjected to solid-liquid separation. The solid material obtained from the dissolving and separating unit was sent to a washing and drying unit, where it was washed with water until neutral, washed with a 3% by weight hydrochloric acid solution, and further washed with water until neutral, and then subjected to solid-liquid separation. The obtained solid material was sent to a drying device and dried at 120°C for 8 hours to obtain an activated carbon product.The gaseous material discharged from the second reactor was sent to a scrubbing and separation unit. In the scrubbing and separation unit, the gaseous material was washed with water and further separated into hydrogen gas, combustible gas, and nitrogen gas via a pressure swing adsorption device. The combustible gas was used as fuel gas for radiant heating or torch combustion, and the nitrogen gas was recycled to the first reactor. The effluent from the dissolution and separation unit was sent to a regeneration unit. Simultaneously, calcium hydroxide was added as a precipitant in an amount of 80% of the mass of carbonate ions in the effluent. They were stirred and mixed at 80°C for 2 hours, cooled, and then subjected to solid-liquid separation. The solid material discharged from the regeneration unit was sent to a drying and calcination unit. The solid material obtained after calcining at 850°C for 4 hours was recycled to the regeneration unit and reused as a precipitant. The treatment conditions and product properties are shown in Table 2.

[0100] Example 2 Example 1 was repeated, except that the first reactor was operated at a temperature of 350°C, a rotation speed of 0.5 rpm, and a residence time of the material in the first reactor of 2 hours. The second reactor (tube furnace reactor) was operated under the following conditions: the ratio of the length of the heating section to the length of the constant temperature section was 9:1, the residence time in the heating section was 180 minutes, the residence time in the constant temperature section was 20 minutes, and the pressure in the heating zone was 20 Pa (gauge pressure). The process conditions and product properties are shown in Table 2.

[0101] Example 3 Example 1 was repeated, except that the petroleum coke feed and the activator (a mixture of potassium hydroxide and potassium carbonate, with 20% by weight of potassium carbonate) were added in a ratio of 1:5. The precipitant was added to the regeneration unit in an amount of 75% of the mass of carbonate ions in the effluent from the dissolution and separation unit. The first reactor was operated at a temperature of 400°C, a rotation speed of 1 rpm, and a residence time of the material in the first reactor of 1 hour. The second reactor (a tube furnace reactor) was operated under the following conditions: a temperature in the constant temperature section of 800°C, a ratio of the length of the heating section to the length of the constant temperature section of 2:1, a residence time in the heating section of 120 minutes, a residence time in the constant temperature section of 60 minutes, and a pressure in the heating zone of 50 Pa (gauge pressure). The process conditions and product properties are shown in Table 2.

[0102] Example 4 Example 1 was repeated, except that the petroleum coke feed and the activator (a mixture of potassium hydroxide and potassium carbonate, with the amount of potassium carbonate being 5% by weight) were added in a 1:1 ratio. The precipitant was added to the regeneration unit in an amount of 90% of the mass of carbonate ions in the effluent from the dissolution and separation unit. The first reactor was operated at a temperature of 450°C, a rotation speed of 1 rpm, and a residence time of the material in the first reactor of 1 hour. The second reactor (a tube furnace reactor) was operated under the following conditions: a temperature in the constant temperature section of 950°C, a ratio of the length of the heating section to the length of the constant temperature section of 3:1, a residence time in the heating section of 60 minutes, a residence time in the constant temperature section of 20 minutes, and a pressure in the heating zone of 40 Pa (gauge pressure). The process conditions and product properties are shown in Table 2.

[0103] (Comparative Example 1) Example 1 was repeated, except that the second reactor (tube furnace reactor) was operated under the following conditions: the constant temperature section was heated by a heat radiant tube instead of microwave heating, the temperature in the constant temperature section was 900°C, the ratio of the length of the heating section to the length of the constant temperature section was 4:1, the residence time in the heating section was 120 minutes, the residence time in the constant temperature section was 30 minutes, and the pressure in the heating zone was 30 Pa (gauge pressure). The process conditions and product properties are shown in Table 2.

[0104] [Table 2]

[0105] Example 5 Example 1 and Comparative Example 1 were each repeated 10 times. The properties of the products obtained in each repeat are shown in Table 3.

[0106] [Table 3]

[0107] As the data in the table above show, the product obtained from ten replicates of Example 1 according to the present disclosure had a standard deviation of specific surface area of ​​37 m 2 / g, with a standard deviation of pore volume of 0.03 cm 3 / g, indicating no significant change in properties. In contrast, the product obtained by repeating Comparative Example 1 ten times had a standard deviation of specific surface area of ​​162 m 2 / g, with a standard deviation of pore volume of 0.06 cm 3 / g, which indicates a significant change in properties. [Brief explanation of the drawings]

[0108] [Figure 1] FIG. 1 is a schematic diagram showing the flow of a petroleum coke processing method according to the present disclosure. [Figure 2]1 is a three-dimensional schematic diagram of a tube furnace reactor according to the present disclosure (mainly showing the housing and the configuration for microwave heating). [Figure 3] FIG. 1 is a top schematic view of a tube furnace reactor according to the present disclosure. [Figure 4] 1 is a cross-sectional schematic view of a tube furnace reactor according to the present disclosure (mainly showing a partial cross-section of the rotary table). FIG. [Figure 5] 1 is a cross-sectional schematic diagram of a baffle according to the present disclosure (showing the guide hole configuration on the baffle). [Figure 6] 1 is a schematic diagram illustrating the structure of an exhaust system according to the present disclosure. [Figure 7] 1 is a schematic diagram illustrating the configuration of the lowermost portion of a primary lifting surface according to the present disclosure. FIG.

Claims

1. 1. A tube furnace reactor comprising: a housing forming an enclosed annular space divided into an inlet / outlet zone, a high temperature zone, and a cooling zone, the high temperature zone including a heated section and a constant temperature section; a rotary table located within the housing and arranged along the annular space of the housing, the rotary table rotating relative to the housing to receive a feed material, which is a mixture of petroleum coke and an activator, at the inlet / outlet zone, convey the mixed feed material of petroleum coke and the activator into the high temperature zone and the cooling zone in sequence, and then discharge the feed material at the inlet / outlet zone; a plurality of baffles located within the housing, fixed on the housing, and spaced apart above the rotary table, the baffles including a plurality of guide holes; Equipped with the heating section is powered by fuel gas or electric radiant heating; Tube furnace reactor, wherein the constant temperature section is operated using microwave heating.

2. The heating section is heated for 30 to 300 minutes, 10. The tube furnace reactor of claim 1, wherein the constant temperature section is operated at a constant temperature of 700-1000°C for 10-120 minutes.

3. The heating section is heated for 60 to 180 minutes, 3. The tube furnace reactor of claim 2, wherein the constant temperature section is operated at a constant temperature of 800-950°C for 20-60 minutes.

4. one or more carrier gas inlets disposed in the inlet / outlet zone; a gas outlet disposed in the high temperature zone; 10. The tube furnace reactor of claim 1 further comprising:

5. Three carrier gas inlets, respectively positioned at a beginning, a middle, and an end of the inlet / outlet zone; a gas outlet disposed in the constant temperature section of the high temperature zone; 10. The tube furnace reactor of claim 1 further comprising:

6. The plurality of baffles are arranged perpendicular to the surface of the rotary table; the plurality of guide holes are disposed in the upper one-third to the upper one-half of the plurality of baffles; The plurality of guide holes are formed with an opening ratio of 20% to 30%; 2. The tubular furnace reactor according to claim 1, wherein the inlet side of the plurality of guide holes has a larger hole diameter than the outlet side of the plurality of guide holes.

7. A ring furnace reactor as described in claim 6, wherein the plurality of guide holes are conical in shape.

8. the inlet / outlet zone comprises an exhaust system fixed to the interior of the housing; The discharge system comprises: a spiral discharger for outputting discharged material horizontally from a top of the spiral discharger; a conveyor belt that is inclined with one end positioned at the top of the spiral discharge device and delivers the discharged material to the top of the spiral discharge device; a lifting surface inclined to pick up the discharged material on the rotating table to the other end of the conveyor belt; 10. The tube furnace reactor of claim 1, comprising:

9. The lifting surface is a primary lifting surface for picking up a plurality of particles of the material having a particle size distribution greater than D10 onto the conveyor belt; a secondary lifting surface for picking up a plurality of particles of the material having a particle size distribution smaller than D10 onto the conveyor belt; 9. The tube furnace reactor of claim 8, comprising:

10. 10. An apparatus for treating petroleum coke, comprising the tube furnace reactor of claim 1 as an activation unit.

11. 1. A method for treating petroleum coke, comprising: (1) adding a feed of petroleum coke and an activator into a first reactor and subjecting the feed to a first treatment under a non-reactive atmosphere to obtain a first gas phase material and a first solid phase material; (2) adding the first solid-phase material and the first gas-phase material obtained in step (1) into a second reactor and subjecting them to a second heat treatment to obtain a second gas-phase material and a second solid-phase material; (3) subjecting the second solid phase material obtained in step (2) to a cooling treatment, a mixing treatment with water, and a liquid-solid separation treatment to obtain a first liquid phase material and a third solid phase material, wherein the third solid phase material is further subjected to a washing treatment and a drying treatment to obtain a porous carbon material; Optionally, (4) contacting and reacting the first liquid phase material obtained in step (3) with a precipitating agent, wherein the effluent of the reaction is subjected to liquid-solid separation to obtain a second liquid phase material and a fourth solid phase material, and the fourth solid phase material is dried, calcined, and then recycled as the precipitating agent; and Optionally, (5) subjecting the second liquid phase material obtained in step (4) to evaporation-crystallization to obtain a third gas phase material and a fifth solid phase material, wherein the fifth solid phase material is reused as the activating agent. Including, 10. The method for processing petroleum coke, wherein the second reactor is a tube furnace reactor as defined in claim 1.

12. further comprising the step of previously subjecting said feed of petroleum coke to a drying and pulverization treatment; said feed of dried petroleum coke having a moisture content of 2 wt.% or less; 12. The method of claim 11, wherein said feed of finely divided petroleum coke has a particle size of 200 μm or less.

13. The first treatment in step (1) is carried out at a temperature of 200 to 500°C, 12. The method for treating petroleum coke according to claim 11, wherein the activator and the feed of petroleum coke in step (1) are in a mass ratio of 0.5:1 to 8:

1.

14. 12. The method for treating petroleum coke according to claim 11, wherein the activator in step (1) is one or more alkali metal compounds selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate.

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