Device and method for co-producing hydrogen-rich syngas and activated carbon, and activated carbon

Abstract

The present invention provides a device and method for co-producing hydrogen-rich syngas and activated carbon, and activated carbon. The device is an integrated furnace, which has an inner cavity. The inner cavity is divided into a carbonization cavity and an activation cavity from top to bottom. In the activation cavity, a plurality of hollow plates are arranged from top to bottom, and a plurality of through holes communicating with the hollow cavities thereof are distributed on the surfaces of the hollow plates; a steam supply unit is also arranged in the activation cavity, which is connected to a steam inlet, and the steam supply unit is respectively communicated with the hollow cavities of each hollow plate for supplying steam through the through holes of the hollow plates. Based on the above device, the present invention can effectively achieve seamless connection between carbonization and gasification activation to realize continuous gasification activation production, and no solid waste is generated in this process. Moreover, due to incomplete gasification, the CO2 generation amount is greatly reduced, thus significantly improving the atom economy of the coal gasification process. At the same time, the present invention can ensure the quality of activated carbon and generate hydrogen-rich syngas while greatly improving the activation efficiency.

Description

Technical Field

[0001] The present invention relates to the field of activated carbon preparation, and in particular, to an apparatus and method for co-producing hydrogen-rich syngas and activated carbon, and activated carbon. Background Art

[0002] Coal particle-based activated carbon is widely used in industries such as industrial wastewater or urban sewage treatment, flue gas treatment, etc. due to its advantages of well-developed pores, good adsorption performance, high strength, easy regeneration and recyclability. Under the domestic "dual carbon" background, the preparation of coal particle-based activated carbon is also one of the important ways for clean and low-carbon utilization of coal. At present, coal particle-based activated carbon is mainly prepared by mixing coal powder and binder and then extruding into shape, and then through processes such as drying, carbonization, and activation. The commonly used binder and activator are coal tar and water vapor respectively. For example, the document of CN113148983A discloses a method for co-producing carbon nanotubes / porous carbon materials and hydrogen-rich syngas by biomass pyrolysis, which can obtain carbon nanotubes / porous carbon materials and hydrogen-rich syngas at the same time. However, this method uses NiCl2 and CaCl2, resulting in problems of wastewater pollution and ineffective utilization of tar. The document of CN109678156B discloses a rotary activation furnace for preparing high-quality coal-based activated carbon. The interior of the activation furnace is divided into a feeding section, a lifting and preheating section, a carbonized material activation section, and a discharging section. The temperature of water vapor increases sequentially in the three sections. High-temperature water vapor contacts and activates the carbonized material efficiently and rapidly, improving the contact and activation reaction between water vapor and coal material, and increasing the specific surface area of activated carbon. However, this device uses refractory castables and silicon carbide materials, with high device investment cost and usage cost. The document of CN207435036U discloses a high-efficiency rotary steam activation furnace, in which a spiral steam pipeline is provided on the inner wall of the activation furnace body, and a number of steam nozzles are evenly arranged around the outer wall, increasing the contact area between water vapor and raw materials and strengthening the activation effect. However, it does not consider the energy consumption of water vapor preheating, the wear of coal material on the inner wall of the furnace, and the corrosion of the furnace body by high-temperature tar and water vapor.

[0003] In summary, the existing preparation and mature production methods of coal particle-based activated carbon can only produce intermittently, and there are problems such as low activation efficiency, difficult treatment of VOC in flue gas emissions, or high energy consumption. How to improve the activation reaction efficiency of activated carbon production while taking into account the strength and adsorption performance of columnar activated carbon products is a problem that needs to be solved at present. Summary of the Invention

[0004] The main object of the present invention is to provide an apparatus and method for co-producing hydrogen-rich syngas and activated carbon, and activated carbon, so as to solve the problems such as poor activation efficiency existing in the existing activated carbon preparation technology.

[0005] To achieve the above object, according to one aspect of the present invention, there is provided a device for co-producing hydrogen-rich syngas and activated carbon. The device is an integrated furnace, and the integrated furnace has an inner cavity, which is divided into a carbonization cavity and an activation cavity from top to bottom; wherein, the carbonization cavity has a coal particle feed inlet and a steam inlet; and the carbonization cavity has a bottom wall, on which a carbonized material outlet is provided; the bottom wall is further provided with a pressurizing device for providing a pressure environment to the carbonization cavity; the activation cavity is connected to the carbonization cavity through the carbonized material outlet, and the activation cavity also has a hydrogen-rich syngas outlet and an activated carbon discharge outlet; a plurality of hollow plates are arranged in the activation cavity from top to bottom, and a plurality of through holes communicating with the hollow cavities thereof are distributed on the surface of the hollow plates; a steam supply unit is also arranged in the activation cavity, which is connected to the steam inlet, and the steam supply unit is respectively communicated with the hollow cavities of each hollow plate for supplying steam through the through holes of the hollow plates; the hollow plate has a first end and a second end arranged oppositely, the first end is fixedly arranged on the inner wall of the activation cavity, there is a gap between the second end and the inner wall of the activation cavity, and the hollow plate is arranged obliquely downward from the first end to the second end; a zigzag channel for allowing the carbonized material to move downward is formed between the plurality of hollow plates.

[0006] Further, steam nozzles are arranged at the through holes; preferably, 9 to 10 hollow plates are arranged in the activation cavity from top to bottom; preferably, 10 to 15 through holes communicating with the hollow cavities are distributed on the surface of the hollow plate; preferably, a heating device is arranged in the hollow cavity of the hollow plate.

[0007] Further, the width of the gap between the second end and the inner wall of the activation cavity is 0.4 to 1.2 m, and the minimum vertical distance between two adjacent hollow plates is 0.2 to 0.3 m.

[0008] Further, the angle of the hollow plate inclined downward from the first end to the second end is 15 to 45°; preferably, the zigzag channel is a "zigzag" channel.

[0009] Further, the steam supply unit is a steam supply pipe, one end of which extends to the outside of the integrated furnace to serve as the steam inlet, and the other end extends along the inner wall of the activation cavity and is communicated with the hollow cavities of each hollow plate; or, the steam supply unit is an inner jacket arranged inside the activation cavity.

[0010] Further, the bottom wall has two ends, the end far from the carbonized material outlet is denoted as the first end, and the end close to the carbonized material outlet is denoted as the second end; in the order of traveling from the first end to the second end, the bottom wall gradually inclines downward; preferably, the inclination angle of the bottom wall is 25 to 35°; preferably, the length distance from the first end to the carbonized material outlet is 6.5 to 7.0 m.

[0011] Further, the carbonization chamber is also provided with a first heating device for supplying heat energy to the carbonization chamber; preferably, the activation chamber is also provided with a second heating device for supplying heat energy to the activation chamber.

[0012] Further, the aspect ratio of the length to the diameter of the carbonization chamber is (5.5 - 6):1, and the aspect ratio of the height to the diameter of the activation chamber is (4.5 - 5):1.

[0013] Further, the carbonization chamber also has a circulating gas inlet, and the circulating gas inlet is connected to the hydrogen-rich syngas outlet.

[0014] To achieve the above object, according to one aspect of the present invention, there is provided a method for co-producing hydrogen-rich syngas and activated carbon, using the aforementioned device to co-produce hydrogen-rich syngas and activated carbon. The method includes the following steps: allowing coal particles to enter the carbonization chamber through the coal particle feed port for carbonization reaction to obtain carbonized materials; the carbonized materials enter the activation chamber through the carbonized material outlet and undergo an activation reaction in a steam atmosphere to obtain hydrogen-rich syngas and activated carbon.

[0015] Further, the treatment temperature of the activation reaction is 910 - 1050 °C; preferably, the treatment time of the activation reaction is 15 - 60 min.

[0016] Further, the coal particles are formed from bituminous coal, anthracite, binder, and potassium salt; preferably, the coal particles are spherical particles with an average diameter of 1.5 mm - 9 mm or columnar formed coal particles with an aspect ratio of (1 - 7):1; preferably, the dosage of bituminous coal is 15 - 25% of the total weight of bituminous coal and anthracite; preferably, the dosage of potassium salt is 0.5 - 5% of the total weight of bituminous coal and anthracite; more preferably, the potassium salt is K2CO3; preferably, the dosage of the binder is 30 - 36% of the total weight of bituminous coal and anthracite.

[0017] Further, the treatment temperature of the carbonization reaction is 685 - 715 °C; preferably, the treatment time of the carbonization reaction is 0.6 - 1 h.

[0018] Further, based on each gram of coal particles, the gas flow rate of steam is 1.5 - 2.5 mL / min.

[0019] According to another aspect of the present invention, there is provided an activated carbon, which is prepared by the aforementioned method for co-producing hydrogen-rich syngas and activated carbon.

[0020] Based on the above device, first, the present invention can effectively achieve seamless connection between carbonization and gasification activation to realize continuous gasification activation production. During this process, no solid waste is generated. Moreover, due to incomplete gasification, the CO2 production is significantly reduced, thus significantly improving the atomic economy of the coal gasification process. Second, it can improve the contact mode between steam and raw coal particles on the basis of low corrosion and low cost, and improve the steam activation efficiency of raw coal. Third, it can reduce the generation of tar and generate hydrogen-rich syngas while ensuring the quality of activated carbon. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The accompanying drawings forming a part of this application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0022] Figure 1 The schematic diagram of the device for co-producing hydrogen-rich syngas and activated carbon in one embodiment of the present invention is shown;

[0023] Figure 2 The schematic diagram of the volume fraction curve of the gas composition in the system after the activation reaction in Example 6 of the present invention is shown;

[0024] Figure 3 The schematic diagram of the volume fraction curve of the gas composition in the system after the activation reaction in Example 1 of the present invention is shown;

[0025] Figure 4 The schematic diagram of the volume fraction curve of the gas composition in the system after the activation reaction in Example 8 of the present invention is shown;

[0026] Figure 5 The schematic diagram of the volume fraction curve of the gas composition in the system after the activation reaction in Example 9 of the present invention is shown.

[0027] Among them, the above-mentioned drawings include the following reference numerals:

[0028] 10, carbonization chamber; 20, activation chamber; 21, hollow plate; 22, steam supply unit. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0029] It should be noted that, without conflict, the embodiments in this application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the drawings and in combination with the embodiments.

[0030] As described in the background art part of the present invention, there are problems such as poor activation efficiency in the existing activated carbon preparation technology. To solve this problem, the present invention provides a device for co-producing hydrogen-rich syngas and activated carbon, as Figure 1As shown, the device is an integrated furnace, which has an inner cavity. The inner cavity is divided into a carbonization chamber 10 and an activation chamber 20 from top to bottom. Among them, the carbonization chamber 10 has a coal particle feed port and a steam inlet. And the carbonization chamber 10 has a bottom wall, on which a carbonized material outlet is provided. The bottom wall is also provided with a pressurizing device for providing a pressure environment in the carbonization chamber 10. The activation chamber 20 is connected to the carbonization chamber 10 through the carbonized material outlet, and the activation chamber 20 also has a hydrogen-rich syngas outlet and an activated carbon discharge port. In the activation chamber 20, a plurality of hollow plates 21 are arranged from top to bottom. A plurality of through holes communicating with their hollow cavities are distributed on the surface of the hollow plates 21. A steam supply unit 22 is also arranged in the activation chamber 20. It is connected to the steam inlet, and the steam supply unit 22 is respectively communicated with the hollow cavities of each hollow plate 21 for supplying steam through the through holes of the hollow plates 21. The hollow plate 21 has a first end and a second end arranged oppositely. The first end is fixedly arranged on the inner wall of the activation chamber 20, and there is a gap between the second end and the inner wall of the activation chamber 20. And the hollow plate 21 is arranged obliquely downward from the first end to the second end. A bent channel for allowing the carbonized material to move downward is formed between the plurality of hollow plates.

[0031] In the above device of the present application, the carbonization chamber 10 can pyrolyze and carbonize the coal particles entering the chamber through the coal particle feed port to generate carbonized materials, which include coal char, tar and pyrolysis gases (such as CH4, CO and H2, etc.). The carbonization chamber 10 and the activation chamber 20 are connected, so that these carbonized materials can enter the activation chamber 20 at the same time. During this process, the coal char enters the activation chamber 20 by its own gravity, while the tar and pyrolysis gases enter the activation chamber 20 at the same time as the above coal char under the pressurized state, with a small amount of air entering the chamber through the coal particle feed port as the carrier gas. After the carbonized materials (at a temperature of 690 - 710 °C) enter the activation chamber 20, a reforming reaction and a gasification activation reaction will occur in the steam atmosphere, thereby generating hydrogen-rich syngas (mainly composed of H2, followed by CO, and the volume fraction ratio of H2 / CO is between 2 and 7) and activated carbon. In the activation chamber 20, the above carbonized materials move downward along the bent channel from the upper hollow plate 21 to the lower hollow plate 21. During this movement process, the through holes distributed on the surface of the hollow plate 21 increase the contact between the steam and the materials, thereby greatly improving the activation efficiency and obtaining activated carbon with excellent adsorption performance. After the reaction, the hydrogen-rich syngas is discharged from the furnace through the hydrogen-rich syngas outlet and can directly enter the downstream application section of the syngas subsequently, while the activated carbon is discharged from the furnace through the activated carbon discharge port.

[0032] In summary, based on the above device, first, the present invention can effectively achieve seamless connection between carbonization and gasification activation to realize continuous gasification activation production. There is no solid waste generated during this process, and due to incomplete gasification, the CO2 generation amount is significantly reduced, thus significantly improving the atomic economy of the coal gasification process. Second, it can improve the contact mode between water vapor and raw coal particles on the basis of low corrosion and low cost, and improve the water vapor activation efficiency of raw coal. Third, it can reduce the generation of tar and generate hydrogen-rich syngas while ensuring the quality of activated carbon.

[0033] It is further supplemented here that, in an alternative embodiment, the activation chamber 20 of the present application is connected to the carbonization chamber 10 through a carbonized material outlet, and the carbonized material outlet has a first open state and a second closed state to further effectively balance the carbonization degree and activation degree of the material. In a preferred embodiment, when the carbonization reaction is carried out in the carbonization chamber, the carbonized material outlet has a second closed state. After the carbonization reaction is completed and the temperature of the carbonized material reaches 690 - 710 °C, the carbonized material outlet has a first open state, and the carbonized material enters the activation chamber 20.

[0034] It is further explained here that, in a preferred embodiment, the above raw materials of coal particles include bituminous coal, anthracite, binder and potassium salt. After the raw materials are formed, they form coal particle materials. In some alternative embodiments, the coal particles are amorphous coal particles with the longest diagonal length of 6 - 10 mm, spherical coal particles with an average diameter of 1.5 mm - 9 mm, or columnar coal particles with an aspect ratio of (1 - 7):1. The main chemical reactions involved in the above device of the present application are as follows:

[0035] C + H2O → CO + H2

[0036]

[0037]

[0038] In order to further improve the efficiency of the activation reaction, it is preferred that a water vapor spray head is provided at the through hole; preferably, 9 - 10 hollow plates 21 are arranged from top to bottom in the activation chamber 20; preferably, 10 - 15 through holes communicating with the hollow cavity are distributed on the surface of the hollow plate 21. In a preferred embodiment, a heating device is arranged in the hollow cavity of the above hollow plate 21, which can further assist in regulating the internal temperature of the activation chamber to be 910 - 1050 °C. Under this temperature condition, the activation efficiency is higher and the adsorption performance of the obtained activated carbon product is better.

[0039] In a preferred embodiment, the gap width between the second end and the inner wall of the activation chamber 20 is 0.4 - 1.2 m, and the minimum vertical distance between two adjacent hollow plates 21 is 0.2 - 0.3 m. Based on this, the reaction of the material in the activation chamber is more sufficient, and the yield of the product is higher. More preferably, the angle at which the hollow plate 21 inclines downward from the first end to the second end (the included angle between the extending direction and the horizontal direction) is 15 - 45°. Adjusting this angle can make the activation reaction time of the material in the activation chamber adjustable within 30 - 60 min, so as to better balance the moving speed and activation degree of the material. Moreover, by adjusting the inclination angle of the folding plate, the residence time of the carbonized material in the activation section can be adjusted to obtain activated carbon products with different indexes. Under this time condition, the activation efficiency is higher and the adsorption performance of the obtained activated carbon product is better. Further preferably, the bent channel is a zigzag channel.

[0040] In a preferred embodiment, the steam supply unit 22 is a steam supply pipe, one end of which extends to the outside of the integrated furnace to serve as the steam inlet, and the other end extends along the inner wall of the activation chamber 20 and communicates with the hollow cavities of each hollow plate 21; alternatively, the steam supply unit 22 is an internal jacket provided in the activation chamber 20. Based on this, the present application can provide a sufficient steam atmosphere in the activation chamber 20 to further make the reaction of the material more sufficient and the product yield higher.

[0041] In a preferred embodiment, the bottom wall has two ends. The end far from the carbonized material outlet is denoted as the first end, and the end close to the carbonized material outlet is denoted as the second end; in the order of traveling from the first end to the second end, the bottom wall gradually inclines downward. Based on this, the material enters the carbonization chamber 10, undergoes a carbonization reaction in the chamber while sliding downward to the carbonized material outlet to enter the activation chamber 20. During this process, the carbonization of the material is more sufficient. To further balance the moving speed and carbonization degree of the material, preferably, the inclination angle of the bottom wall is 25 - 35°; preferably, the length distance from the first end to the carbonized material outlet is 6.5 - 7 m.

[0042] In a preferred embodiment, the carbonization chamber 10 is further equipped with a first heating device for providing heat energy to the carbonization chamber 10. Based on this, the internal temperature of the carbonization chamber can be further assisted to be 700°C ± 15°C. Under this temperature condition, the carbonization efficiency is higher, and the carbonized material obtained therefrom has a better activation effect and lower energy consumption after entering the activation chamber.

[0043] In a preferred embodiment, the activation chamber 20 is further equipped with a second heating device for providing heat energy to the activation chamber 20. It can further assist the internal temperature of the activation chamber to be 910 - 1050°C. Under this temperature condition, the activation efficiency is higher and the adsorption performance of the obtained activated carbon product is better.

[0044] In order to further balance the carbonization degree and activation degree, so as to efficiently obtain activated carbon and hydrogen-rich syngas with better performance, it is preferred that the aspect ratio of the carbonization chamber 10 is (5.5 - 6):1, and the aspect ratio of the activation chamber 20 is (4.5 - 5):1.

[0045] In a preferred embodiment, the carbonization chamber 10 further has a circulating gas inlet, and the circulating gas inlet is communicated with the hydrogen-rich syngas outlet. After the activation reaction, the unreacted water vapor and hydrogen-rich syngas are discharged through the hydrogen-rich syngas outlet. Most of the gas then directly enters the downstream application section of the syngas, and a small part of the gas can be transported to the circulating gas inlet of the carbonization chamber 10 through the communication channel to enter the carbonization chamber 10 for preheating and carbonizing the raw material. At the same time, this part of the gas can also cooperate with a small amount of air to bring the tar and pyrolysis gas generated during carbonization into the activation chamber to continue participating in the reaction, so as to improve the conversion rate of tar, reduce the generation of tar in the product gas, and the energy consumption of the device is lower.

[0046] The present invention also provides a method for co-producing hydrogen-rich syngas and activated carbon. The device described above is used to co-produce hydrogen-rich syngas and activated carbon. The method includes the following steps: making coal particles enter the carbonization chamber 10 through the coal particle feed port for carbonization reaction to obtain carbonized materials; the carbonized materials enter the activation chamber 20 through the carbonized material outlet and carry out an activation reaction in a water vapor atmosphere to obtain hydrogen-rich syngas and activated carbon.

[0047] For the reasons described above, firstly, the present invention can effectively achieve seamless connection between carbonization and gasification activation to realize continuous gasification activation production, and no solid waste is generated during this process. Moreover, due to incomplete gasification, the CO2 generation amount is significantly reduced, thus significantly improving the atomic economy of the coal gasification process. Secondly, it is possible to improve the contact mode between water vapor and raw coal particles on the basis of low corrosion and low cost, and improve the water vapor activation efficiency of raw coal. Thirdly, it is possible to reduce the generation of tar and generate hydrogen-rich syngas while ensuring the quality of activated carbon.

[0048] In order to further improve the activation efficiency, it is preferred that the treatment temperature of the activation reaction is 910 - 1050 °C; it is preferred that the treatment time of the activation reaction is 15 - 60 min.

[0049] In a preferred embodiment, the raw materials of the coal particles include bituminous coal, anthracite, binder and potassium salt; after the bituminous coal, anthracite, binder and potassium salt are formed into coal particle materials, and after the activation reaction, most of the potassium element remains in the activated carbon product, making the activated carbon exhibit obvious alkalinity and having excellent adsorption characteristics for CO2 gas, and can be directly used as a commercial activated carbon product for CO2 capture. In a preferred embodiment, the above-mentioned bituminous coal includes bituminous coal particles and / or bituminous coal powder, and the anthracite includes anthracite powder and / or anthracite particles. The above-mentioned bituminous coal, anthracite, binder and potassium salt are kneaded and extruded into amorphous, spherical or columnar coal particles. In some alternative embodiments, the coal particles are amorphous coal particles with a maximum diagonal length of 6-10 mm, spherical coal particles with an average diameter of 1.5 mm-9 mm or columnar coal particles with an aspect ratio of (1-7):1, and more preferably spherical coal particles with an average diameter of 1.5 mm-9 mm or columnar coal particles with an aspect ratio of (1-7):1. In addition, there are no special requirements for the selection of the above-mentioned binder in this application, and those skilled in the art can select conventional binders, which will not be elaborated here.

[0050] In order to further improve the adsorption performance of the activated carbon, in a preferred embodiment, the dosage of bituminous coal is 15-25% of the total weight of bituminous coal and anthracite. Preferably, the dosage of potassium salt is 0.5-5% of the total weight of bituminous coal and anthracite, and further preferably the potassium salt is K2CO3. Preferably, the dosage of binder is 30-36% of the total weight of bituminous coal and anthracite. Based on this, the performance stability of the product can be effectively improved.

[0051] In order to further improve the carbonization efficiency, preferably, the treatment temperature of the carbonization reaction is 685-715 °C; preferably, the treatment time of the carbonization reaction is 0.6-1 h.

[0052] In order to further balance the activation degree and the product adsorption capacity, based on each gram of coal particles, preferably, the gas flow rate of water vapor is 1.5-2.5 mL / min.

[0053] The present invention also provides an activated carbon, which is prepared by the method for co-producing hydrogen-rich syngas and activated carbon described above.

[0054] For the reasons described above, the activated carbon obtained in this application has a significant promoting effect on the adsorption of CO2 gas, with a large adsorption amount and excellent adsorption stability.

[0055] The following further describes the present application in detail with specific examples, and these examples should not be construed as limiting the scope claimed in the present application.

[0056] Example 1

[0057] Use Figure 1 the device to co-produce hydrogen-rich syngas and activated carbon.

[0058] Among them, the length-diameter ratio of the carbonization chamber 10 is 6.5:1, and the height-diameter ratio of the activation chamber 20 is 5:1.

[0059] In the carbonization chamber 10, the inclination angle of the bottom wall is 30°; the length distance from the first end of the bottom wall to the carbonized material outlet is 6.8 m; a heating device is arranged on the outer wall of the bottom wall of the carbonization chamber 10 to provide heat energy to the carbonization chamber 10; a pressurizing device is also arranged on the inner wall of the bottom wall to provide a pressurized environment to the inside of the carbonization chamber 10.

[0060] In the activation chamber 20, nine hollow plates 21 are arranged from top to bottom; the gap width between the second end of the hollow plate and the inner wall of the activation chamber 20 is 0.8 m; the minimum vertical distance between two adjacent hollow plates 21 is 0.2 m; 15 through holes communicating with the hollow cavity are distributed on the surface of the hollow plate 21; a heat supply device is arranged in the hollow cavity of the hollow plate 21; the inclination angle of the hollow plate 21 from the first end to the second end is 15°; a heating device is arranged on the outer wall of the side wall of the activation chamber 20 to provide heat energy to the activation chamber 20.

[0061] After bituminous coal, anthracite, potassium carbonate and binder are formed into cylinders (cylindrical coal particles with a length-diameter ratio of 3-5:1), they enter the carbonization chamber 10 through the coal particle feed port and carry out a carbonization reaction with the air entering the carbonization chamber 10 through the circulating gas inlet to obtain carbonized materials.

[0062] The carbonized materials enter the activation chamber 20 through the carbonized material outlet and carry out an activation reaction in a water vapor and air atmosphere to obtain hydrogen-rich syngas and activated carbon.

[0063] Among them, the treatment temperature of the activation reaction is 950 °C; the treatment time of the activation reaction is 20 min; the dosage of bituminous coal is 20% of the total weight of bituminous coal and anthracite; the dosage of potassium salt is 5% of the total weight of bituminous coal and anthracite; the dosage of binder is 36% of the total weight of bituminous coal and anthracite; the treatment temperature of the carbonization reaction is 700 °C; the treatment time of the carbonization reaction is 1 h; the gas flow rate of water vapor is 2 mL / min.

[0064] Example 2

[0065] The difference from Example 1 is only that: the dosage of bituminous coal is 15% of the total weight of bituminous coal and anthracite.

[0066] Example 3

[0067] The difference from Example 1 is only that: the dosage of bituminous coal is 25% of the total weight of bituminous coal and anthracite.

[0068] Example 4

[0069] The difference from Example 1 is only that the amount of bituminous coal is 40% of the total weight of bituminous coal and anthracite.

[0070] Example 5

[0071] The difference from Example 1 is only that the amount of bituminous coal is 10% of the total weight of bituminous coal and anthracite.

[0072] The performance characterizations of Examples 1 to 5 are shown in Table 1.

[0073] Table 1

[0074]

[0075] It can be found from Table 1 that when the amount of bituminous coal is 15 - 25% of the total weight of bituminous coal and anthracite (such as in Examples 1 to 3), the adsorption performance and abrasion resistance of the product are better. When the amount of bituminous coal is not within this range, such as in Example 4 where the amount of bituminous coal is higher than this range, the CO2 adsorption amount and abrasion resistance of the product are poor; such as in Example 5 where the amount of bituminous coal is lower than this range, the CO2 adsorption amount of the product is low and poor.

[0076] Example 6

[0077] The difference from Example 1 is only that the treatment temperature of the activation reaction is 910 °C.

[0078] Example 7

[0079] The difference from Example 1 is only that the treatment temperature of the activation reaction is 980 °C.

[0080] Example 8

[0081] The difference from Example 1 is only that the treatment temperature of the activation reaction is 1000 °C.

[0082] Example 9

[0083] The difference from Example 1 is only that the treatment temperature of the activation reaction is 1050 °C.

[0084] Example 10

[0085] The difference from Example 1 is only that the treatment temperature of the activation reaction is 850 °C.

[0086] Example 11

[0087] The difference from Example 1 is only that the treatment temperature of the activation reaction is 1100 °C.

[0088] The performance characterizations of Examples 1, 6 to 11 are shown in Table 2.

[0089] Table 2

[0090]

[0091] As can be seen from Table 2, when the treatment temperature of the activation reaction is 910 - 1050 °C (such as in Examples 1, 6 to 9), on the basis of relatively good activation efficiency, the obtained product has better adsorption performance and wear resistance. When the treatment temperature of the activation reaction is not within this range, such as in Example 10 where the treatment temperature is lower than this range, the CO2 adsorption performance of the product is poor; such as in Example 11 where the treatment temperature is higher than this range, the wear resistance and CO2 adsorption performance of the product are also poor.

[0092] Figure 2 Schematic diagram of the volume fraction curve of the gas composition after the activation reaction in Example 6 of the present invention; Figure 3 Schematic diagram of the volume fraction curve of the system gas composition after the activation reaction in Example 1 of the present invention; Figure 4 Schematic diagram of the volume fraction curve of the system gas composition after the activation reaction in Example 8 of the present invention; Figure 5 Schematic diagram of the volume fraction curve of the system gas composition after the activation reaction in Example 9 of the present invention. The test method is as follows: The gasification activation gas product is detected by an on-line infrared gas analyzer (Gasboard - 3100, Hubei Rayi Automatic Control System), with accuracy: (CO / CO2 / CH4 / CnHm) 1% FS (H2 / O2) 2% FS. The gas product is collected in a gas bag for a period of time, and the gas product composition measured by the on-line gas analyzer is verified by a gas chromatograph (GC - 2014, Shimadzu, Japan) equipped with a thermal conductivity detector (TCD) and a flame ionization detector (FID).

[0093] Example 12

[0094] The difference from Example 1 is only that the dosage of the potassium salt is 0.5% of the total weight of bituminous coal and anthracite.

[0095] Example 13

[0096] The difference from Example 1 is only that the dosage of the potassium salt is 1% of the total weight of bituminous coal and anthracite.

[0097] Example 14

[0098] The difference from Example 1 is only that the dosage of the potassium salt is 2.5% of the total weight of bituminous coal and anthracite.

[0099] Example 15

[0100] The difference from Example 1 is only that no potassium salt is added.

[0101] The performance characterizations of Examples 1, 12 to 15 are shown in Table 3.

[0102] Table 3

[0103]

[0104] As can be seen from Table 3, when the dosage of the potassium salt is 0.5-5% of the total weight of bituminous coal and anthracite (such as in Examples 1, 12 to 15), on the basis of having a relatively good activation efficiency, the obtained product has better adsorption performance and better abrasion resistance. When the treatment temperature of the activation reaction is not within this range, such as in Example 15 where no potassium salt is added, the CO2 adsorption capacity of the product is poor.

[0105] Example 16

[0106] The difference from Example 1 is only that: the treatment temperature of the carbonization temperature reaction is 685°C.

[0107] Example 17

[0108] The difference from Example 1 is only that: the treatment temperature of the carbonization temperature reaction is 715°C.

[0109] Example 18

[0110] The difference from Example 1 is only that: the treatment temperature of the carbonization temperature reaction is 650°C.

[0111] The performance characterizations of Examples 1, 16 to 18 are shown in Table 4.

[0112] Table 4

[0113]

[0114] As can be seen from Table 4, when the treatment temperature of the carbonization temperature reaction is 685-715°C (such as in Examples 1, 16 to 18), on the basis of having a relatively good activation efficiency, the obtained product has better adsorption performance and better abrasion resistance. When the carbonization temperature reaction is not within this range (such as in Example 18), both the abrasion resistance and the CO2 adsorption performance of the product are poor.

[0115] Example 19

[0116] The difference from Example 1 is only that: the angle of the hollow plate 21 inclined downward from the first end to the second end is 45°.

[0117] Example 20

[0118] The difference from Example 1 is only that: the angle of the hollow plate 21 inclined downward from the first end to the second end is 10°.

[0119] Example 21

[0120] The difference from Example 1 is only that: the angle of the hollow plate 21 inclined downward from the first end to the second end is 50°.

[0121] The performance characterizations of Examples 1, 19 to 21 are shown in Table 5.

[0122] Table 5

[0123]

[0124] It can be found from Table 5 that when the angle of the hollow plate 21 inclined downward from the first end to the second end is 15 - 45° (such as in Examples 1, 19 to 21), on the basis of relatively good activation efficiency, the obtained product has better adsorption performance and wear resistance. When the carbonization temperature reaction is not within this range, for example, the angle in Example 20 is lower than this range, the CO2 adsorption performance is poor; for example, the angle in Example 21 is higher than this range, both the CO2 adsorption performance and wear resistance of the product are poor.

[0125] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, various changes and modifications can be made to the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for co-producing hydrogen-rich syngas and activated carbon, characterized in that, The method includes the following steps: Coal particles enter the carbonization chamber (10) through the coal particle feed inlet for carbonization reaction to obtain carbonized materials. The carbonized materials enter the activation chamber (20) through the carbonized material outlet and undergo an activation reaction in a steam atmosphere to obtain hydrogen-rich syngas and activated carbon. The coal particles are formed from bituminous coal, anthracite, binder, and potassium salt; wherein, the dosage of the bituminous coal is 15-25% of the total weight of the bituminous coal and the anthracite; the dosage of the potassium salt is 0.5-5% of the total weight of the bituminous coal and the anthracite. The treatment temperature of the activation reaction is 910-1050 °C; the treatment temperature of the carbonization reaction is 685-715 °C. The method is carried out in a device for co-producing hydrogen-rich syngas and activated carbon. The device is an integrated furnace, and the integrated furnace has an inner cavity, which is divided into a carbonization chamber (10) and an activation chamber (20) from top to bottom; wherein, The carbonization chamber (10) has a coal particle feed inlet and a steam inlet; and the carbonization chamber (10) has a bottom wall, and a carbonized material outlet is provided on the bottom wall; a pressurizing device is further provided on the bottom wall for providing a pressure environment into the carbonization chamber (10). The activation chamber (20) is connected to the carbonization chamber (10) through the carbonized material outlet, and the activation chamber (20) also has a hydrogen-rich syngas outlet and an activated carbon discharge outlet; a plurality of hollow plates (21) are arranged in the activation chamber (20) from top to bottom, and a plurality of through holes communicating with their hollow cavities are distributed on the surface of the hollow plates (21); a steam supply unit (22) is further provided in the activation chamber (20), which is connected to the steam inlet, and the steam supply unit (22) is respectively communicated with the hollow cavities of each of the hollow plates (21) for supplying steam through the through holes; the hollow plates (21) have a first end and a second end arranged opposite to each other, the first end is fixedly arranged on the inner wall of the activation chamber (20), and there is a gap between the second end and the inner wall of the activation chamber (20), and the hollow plates (21) are arranged obliquely downward from the first end to the second end; a zigzag channel for the carbonized materials to move downward is formed between the plurality of hollow plates. Wherein, the angle of the hollow plate (21) inclined downward from the first end to the second end is 15-45°.

2. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein Steam nozzles are provided at the through holes.

3. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein 9-10 of the hollow plates (21) are arranged in the activation chamber (20) from top to bottom.

4. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein, 10-15 through holes communicating with their hollow cavities are distributed on the surface of the hollow plate (21).

5. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, characterized in that, A heating device is arranged in the hollow cavity of the hollow plate (21).

6. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, characterized in that, The width of the gap between the second end and the inner wall of the activation chamber (20) is 0.4-1.2 m, and the minimum vertical distance between adjacent two of the hollow plates (21) is 0.2-0.3 m.

7. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, characterized in that, The zigzag channel is a "zigzag" channel.

8. The method for co-producing hydrogen-rich syngas and activated carbon according to any one of claims 1 to 7, characterized in that, The water vapor supply unit (22) is a water vapor supply pipe, one end of which extends to the outside of the integrated furnace to serve as the water vapor inlet, and the other end extends along the inner wall of the activation chamber (20) and communicates with the hollow cavities of the hollow plates (21); alternatively, the water vapor supply unit (22) is an inner jacket provided inside the activation chamber (20).

9. The method for co-producing hydrogen-rich syngas and activated carbon according to any one of claims 1 to 7, characterized in that, The bottom wall has two ends. The end far from the carbonized material outlet is denoted as the first end, and the end close to the carbonized material outlet is denoted as the second end; in the order of traveling from the first end to the second end, the bottom wall gradually slopes downward.

10. The method for co-producing hydrogen-rich syngas and activated carbon according to any one of claims 1 to 7, characterized in that, The inclination angle of the bottom wall is 25 to 35°.

11. The method for co-producing hydrogen-rich syngas and activated carbon according to any one of claims 1 to 7, characterized in that, The carbonization chamber (10) is further provided with a first heating device for providing heat energy to the carbonization chamber (10); the activation chamber (20) is further provided with a second heating device for providing heat energy to the activation chamber (20).

12. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, characterized in that, The aspect ratio of the carbonization chamber (10) is (5.5 to 6):1, and the height-diameter ratio of the activation chamber (20) is (4.5 to 5):

1.

13. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein, The carbonization chamber (10) further has a circulating gas inlet, and the circulating gas inlet is communicated with the hydrogen-rich syngas outlet.

14. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein, The treatment time of the activation reaction is 15 to 60 min.

15. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein, The coal particles are spherical particles with an average diameter of 1.5 to 9 mm or columnar coal particles with an aspect ratio of (1 to 7):

1.

16. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein The potassium salt is K2CO3.

17. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein, The dosage of the binder is 30 to 36% of the total weight of the bituminous coal and the anthracite coal.

18. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein The treatment time of the carbonization reaction is 0.6 to 1 h.

19. The method for co-producing hydrogen-rich syngas and activated carbon according to claim 1, wherein Based on each gram of the coal particles, the gas flow rate of the water vapor is 1.5 to 2.5 mL / min.

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