CN111232979A - Device for preparing super-capacitor activated carbon by alkali activation method and preparation method thereof - Google Patents
Device for preparing super-capacitor activated carbon by alkali activation method and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a device for preparing super-capacitor activated carbon by an alkali activation method and a preparation method thereof, belonging to the technical field of super-capacitor carbon preparation. The invention has the advantages that: firstly, the mixing of the carbonized material and the activating agent can be more uniform by the wedge-shaped blade stirring shaft in the furnace body, so that the batch stability of the product is ensured; and the relative movement of material particles in the furnace body and the wedge-shaped surface generates a washing effect, so that materials attached to the wedge-shaped surface can be washed away, the wedge-shaped blades have a self-cleaning function, the materials are prevented from being bonded on the stirring shaft of the wedge-shaped blades, the materials are prevented from being bonded on the furnace wall, the normal discharging in the activation process is ensured, and the continuous production of activation is realized.
Description
Technical Field
The invention belongs to the technical field of super-capacitor carbon preparation, and particularly relates to a device for preparing super-capacitor activated carbon by an alkali activation method and a preparation method thereof.
Background
The super-capacitor activated carbon has high specific surface area, abundant pore volume, stable physical and chemical properties and high heat resistance and acid-base resistance, and is widely applied to the fields of super capacitors, lead-carbon batteries, hydrogen storage, medical treatment, military industry, railway systems, power systems and the like.
The prior process for preparing the super-capacitor activated carbon mainly adopts an alkali activation method. In the industrial production process, during the heating reaction process of the mixed material of KOH and the raw material containing carbon, KOH melts along with the rise of temperature, and the mixed material can adhere to the wall of the reactor, which is not beneficial to the activation. For example, Wangdanzhi (patent publication No. CN 108163855A) and the like melt an activating agent in equipment outside an activation furnace, add a carbonized material after melting, mix, heat and boil the materials until the materials are solidified, and then transfer the materials into the activation furnace for activation to prepare the supercapacitor activated carbon, although the problem of wall adhesion is solved to a certain extent, due to the two-section structural design, the continuous operation is difficult to realize, and the activating agent seriously corrodes the equipment; for example, the method comprises the steps of mixing activated carbon raw materials with strong base, heating to 300-500 ℃ for 2-4 hours under the protection of inert gas to obtain pretreated activated carbon, continuously heating to 700-900 ℃, introducing mixed gas of water vapor and carbon dioxide, and heating for 1-2 hours to obtain activated carbon, wherein the method adopts segmented temperature rise, and has the disadvantages of complex process and long time consumption; steam and carbon dioxide are introduced in the activation process, the steam can react with potassium in the activation process and is easy to explode slightly, potential safety hazards exist, the carbon dioxide can react with an alkali metal activator to produce potassium carbonate, and the using amount of the activator is increased.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a device for preparing super-capacitor activated carbon by an alkali activation method and a preparation method thereof.
The design concept of the invention is as follows: the furnace body is fixed, and a wedge-shaped paddle stirring shaft is adopted as a stirring shaft in the furnace body, so that on one hand, materials in the furnace body can move forwards; on the other hand, the carbonized material and the activating agent can be mixed more uniformly, and the batch stability of the product is ensured; meanwhile, the relative movement of the material particles in the furnace body and the wedge-shaped surface generates a washing effect, materials attached to the wedge-shaped surface can be washed away, the self-cleaning function is achieved, the materials are prevented from being bonded on the wedge-shaped blade stirring shaft, the materials are prevented from being bonded on the furnace wall, normal discharging in the activation process is guaranteed, and continuous activation production is achieved.
The invention is realized by the following technical scheme.
A device for alkali activation method preparation super capacitor activated carbon, it includes furnace body, feed unit and drive unit, wherein:
the feeding unit comprises a feeding bin and a spiral feeder, a first protective gas interface is arranged on the side wall of the feeding bin, a discharging port of the feeding bin is communicated with a feeding port of the spiral feeder, and a discharging port of the spiral feeder is communicated with the head end of the furnace body; the furnace body is arranged on the support frame, the furnace cover is covered outside the furnace body, a tail gas discharge pipe is arranged at the head end of the furnace body, a pressure gauge is arranged on one side, close to the furnace cover, of the tail gas discharge pipe, and the furnace cover is far away from the tail gas discharge pipeOne side is provided with CO2Air inlet, pressure gauge and CO2A valve is arranged on a tail gas discharge pipe between the gas inlets, a heating zone is arranged at the head end of the furnace body in the furnace hood, a heating element is arranged in the heating zone, a cooling water jacket is arranged at the tail part of the furnace body in the furnace hood, a water inlet is arranged above the cooling water jacket on the furnace hood, a water outlet is arranged below the cooling water jacket on the furnace hood, a second protective gas interface is arranged at the tail end of the furnace body, the tail end of the furnace body is communicated with a material receiving bin through a pipeline, and a third protective gas interface is arranged at the position of a material inlet of the material receiving bin;
a stirring shaft is arranged through the furnace body, wedge-shaped blades are arranged on the outer circular surface of the stirring shaft, a material guide plate is arranged in the middle of each blade, air seal packing is respectively arranged at the connection positions of the head end and the tail end of the stirring shaft and the furnace body, and a driven chain wheel is arranged at the head end of the stirring shaft;
the driving unit comprises a motor, a speed reducer and a driving chain wheel, a rotor of the motor is connected with a power input shaft of the speed reducer through a belt, the driving chain wheel is installed on a power output shaft of the speed reducer, and the driving chain wheel is connected with a driven chain wheel through a chain.
Further, the included angle between the material guide plate and the horizontal direction is 30 degrees.
Furthermore, the material of the contact part of the device and the material is one of nickel or 310S.
The preparation method of the device for preparing the super-capacitor activated carbon by the alkali activation method comprises the following steps:
s1, mixing the carbonized material and the activating agent according to the mass ratio of 1: 1-4, crushing the mixed raw materials in a crusher to 100-650 meshes, and then adding the mixed raw materials into a feeding bin after the mixed raw materials are uniform;
s2, introducing shielding gas through the shielding gas interface, adjusting the opening of the valve to make the pressure gauge be micro-positive pressure, and introducing CO2CO is introduced into the air inlet2The water inlet and the water outlet of the cooling water jacket are connected with circulating water;
s3, starting a motor, wherein the motor drives a stirring shaft to rotate through a speed reducer and a chain and sprocket transmission mechanism; turning on the heater and the screw feeder, and setting the temperature of the furnace body and the rotating speed of the stirring shaft to activate the mixed raw materials for 30-120 min at 780-900 ℃;
s4, the activated material enters a material collecting bin through a cooling water jacket under the action of a stirring shaft;
and S5, washing and drying the activated material to obtain the super-capacitor activated carbon.
Further, in the step S1, the carbonized material is one of starch carbonized material, coconut shell carbonized material, petroleum coke, coal and coal tar pitch.
Further, in step S1, the activating agent is one or a mixture of potassium hydroxide, sodium hydroxide and potassium carbonate.
Further, in step S2, the shielding gas is nitrogen or argon.
Further, in the step S5, the specific surface area of the prepared super-capacitor activated carbon is 1500-3000 m2A pore volume of 0.8 to 1.5 cm/g3/g。
Compared with the prior art, the invention has the beneficial effects that:
the wedge-shaped blade has a self-cleaning function, so that materials cannot be bonded on the stirring shaft of the wedge-shaped blade, the materials are prevented from being bonded on the furnace wall, and a pretreatment stage in a general preparation process can be omitted; in addition, the temperature rising speed is not limited; the purpose of realizing continuous production can be achieved.
Drawings
FIG. 1 is a schematic front view of the present invention;
FIG. 2 is a schematic side view of the present invention.
In the figure: 1 is the feeding storehouse, 2 is the screw feeder, 3, 22 are the atmoseal packing, 4 are the motor, 5 are the belt, 6 are the reduction gear, 7 are the chain, 8 are drive sprocket, 9 are first protection gas interface, 10 are the valve, 11 are the tail gas delivery pipe, 12 are CO2The device comprises an air inlet, a pressure gauge 13, a heating element 14, a furnace cover 15, a furnace body 16, a water inlet 17, a cooling water jacket 18, a second protective gas interface 19, a material guide plate 20, wedge-shaped blades 21, a stirring shaft 23, a third protective gas interface 24, a material receiving bin 25 and a water outlet 26The mouth, 27, is a support.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements can be made to the material components and amounts in these embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
Example one
The device for preparing the supercapacitor activated carbon by the alkali activation method as shown in fig. 1 and 2 comprises a furnace body, a feeding unit and a driving unit, wherein:
the feeding unit comprises a feeding bin 1 and a spiral feeder 2, a first protective gas interface 9 is arranged on the side wall of the feeding bin 1, a discharging port of the feeding bin 1 is communicated with a feeding port of the spiral feeder 2, and a discharging port of the spiral feeder 2 is communicated with the head end of a furnace body 16; the furnace body 16 is arranged on the support frame 27, the furnace cover 15 covers the outside of the furnace body 16, the tail gas discharge pipe 11 is arranged at the head end of the furnace body 16, the pressure gauge 13 is arranged on one side, close to the furnace cover 15, of the tail gas discharge pipe 11, and CO is arranged on one side, far away from the furnace cover 15, of the tail gas discharge pipe 112An air inlet 12, a pressure gauge 13 and CO2A valve 10 is arranged on a tail gas discharge pipe 11 between gas inlets 12, a heating zone is arranged at the head end of a furnace body 16 in a furnace cover 15, a heating element 14 is arranged in the heating zone, a cooling water jacket 18 is arranged at the tail part of the furnace body 16 in the furnace cover 15, a water inlet 17 is arranged above the cooling water jacket 18 on the furnace cover 15, a water outlet 26 is arranged below the cooling water jacket 18 on the furnace cover 15, a second protective gas interface 19 is arranged at the tail end of the furnace body 16, the tail end of the furnace body 16 is communicated with a material receiving bin 25 through a pipeline, and a third protective gas interface 24 is arranged at the position of a material inlet of the material receiving bin 25;
a stirring shaft 23 is arranged through the furnace body 16, wedge-shaped blades 21 are arranged on the outer circular surface of the stirring shaft 23, a material guide plate 20 is arranged in the middle of each blade 21, air seal packing sets 3 and 22 are respectively arranged at the joints of the head end and the tail end of the stirring shaft 23 and the furnace body 16, and a driven sprocket is arranged at the head end of the stirring shaft 23;
the driving unit comprises a motor 4, a speed reducer 6 and a driving chain wheel 8, wherein a rotor of the motor 4 is connected with a power input shaft of the speed reducer 6 through a belt 5, the driving chain wheel 8 is installed on a power output shaft of the speed reducer 6, and the driving chain wheel 8 is connected with a driven chain wheel through a chain 7.
Further, the included angle between the material guide plate 20 and the horizontal direction is 30 °.
Furthermore, the material of the contact part of the device and the material is 310S.
The preparation method of the device for preparing the super-capacitor activated carbon by the alkali activation method comprises the following steps:
s1, mixing the starch carbonization material with potassium hydroxide according to the mass ratio of 1: 1, mixing, namely crushing the mixed raw materials in a crusher to 100 meshes, and then adding the mixed raw materials into a feeding bin 1 after the mixed raw materials are uniform;
s2, introducing nitrogen through the protective gas interfaces 9, 19 and 24, adjusting the opening of the valve 10 to ensure that the pressure gauge 13 is in micro-positive pressure and CO is used2The gas inlet 12 is filled with CO2The water inlet 26 and the water outlet 17 of the cooling water jacket 18 are connected with circulating water;
s3, starting the motor 11, wherein the motor 11 drives the stirring shaft 23 to rotate through the speed reducer 6 and the chain and sprocket transmission mechanism; turning on the heater 14 and the screw feeder 2, setting the temperature of the furnace body 16 and the rotating speed of the stirring shaft 23, and activating the mixed raw materials for 60min at 850 ℃;
s4, the activated material enters a material collecting bin 25 through a cooling water jacket 18 under the action of a stirring shaft 23;
and S5, washing and drying the activated material to obtain the super-capacitor activated carbon.
Example two
The device for preparing super-capacitor activated carbon by an alkali activation method provided in the second embodiment is the same as the content described in the first embodiment, and details are not repeated herein.
The preparation method of the device for preparing the super-capacitor activated carbon by the alkali activation method comprises the following steps:
s1, mixing the coconut shell carbonized material and potassium hydroxide according to the mass ratio of 1: 2, mixing, crushing the mixed raw materials in a crusher to 650 meshes, and then adding the mixed raw materials into a feeding bin 1 after the mixed raw materials are uniform;
s2, introducing argon gas through the protective gas interfaces 9, 19 and 24, adjusting the opening of the valve 10 to ensure that the pressure gauge 13 is in micro-positive pressure and CO is used2The gas inlet 12 is filled with CO2The water inlet 26 and the water outlet 17 of the cooling water jacket 18 are connected with circulating water;
s3, starting the motor 11, wherein the motor 11 drives the stirring shaft 23 to rotate through the speed reducer 6 and the chain and sprocket transmission mechanism; turning on the heater 14 and the screw feeder 2, setting the temperature of the furnace body 16 and the rotating speed of the stirring shaft 23, and activating the mixed raw material at 780 ℃ for 120 min;
s4, the activated material enters a material collecting bin 25 through a cooling water jacket 18 under the action of a stirring shaft 23;
and S5, washing and drying the activated material to obtain the super-capacitor activated carbon.
EXAMPLE III
The content of the device for preparing the supercapacitor activated carbon by the alkali activation method provided in the third embodiment is the same as that described in the first embodiment, and details are not described herein.
The preparation method of the device for preparing the super-capacitor activated carbon by the alkali activation method comprises the following steps:
s1, mixing petroleum coke, potassium hydroxide, sodium hydroxide and potassium carbonate according to the mass ratio of 1: 1: 1: 1, mixing, namely crushing the mixed raw materials in a crusher to 325 meshes, and then adding the mixed raw materials into a feeding bin 1 after the mixed raw materials are uniform;
s2, introducing nitrogen through the protective gas interfaces 9, 19 and 24, adjusting the opening of the valve 10 to ensure that the pressure gauge 13 is in micro-positive pressure and CO is used2The gas inlet 12 is filled with CO2The water inlet 26 and the water outlet 17 of the cooling water jacket 18 are connected with circulating water;
s3, starting the motor 11, wherein the motor 11 drives the stirring shaft 23 to rotate through the speed reducer 6 and the chain and sprocket transmission mechanism; turning on the heater 14 and the screw feeder 2, setting the temperature of the furnace body 16 and the rotating speed of the stirring shaft 23, and activating the mixed raw materials at 900 ℃ for 30 min;
s4, the activated material enters a material collecting bin 25 through a cooling water jacket 18 under the action of a stirring shaft 23;
and S5, washing and drying the activated material to obtain the super-capacitor activated carbon.
Further, in the step S1, the carbonized material is one of starch carbonized material, coconut shell carbonized material, petroleum coke, coal and coal tar pitch.
Further, in step S1, the activating agent is one or a mixture of potassium hydroxide, sodium hydroxide and potassium carbonate.
Further, in step S2, the shielding gas is nitrogen or argon.
Further, in the step S5, the prepared super capacitor activated carbon.
Example four
The content of the device for preparing the supercapacitor activated carbon by the alkali activation method provided in the fourth embodiment is the same as that described in the first embodiment, and details are not described herein.
The preparation method of the device for preparing the super-capacitor activated carbon by the alkali activation method comprises the following steps:
s1, mixing coal and sodium hydroxide according to a mass ratio of 1: 3, mixing, namely crushing the mixed raw materials in a crusher to 400 meshes, and then adding the mixed raw materials into the feeding bin 1 after the mixed raw materials are uniform;
s2, introducing argon gas through the protective gas interfaces 9, 19 and 24, adjusting the opening of the valve 10 to ensure that the pressure gauge 13 is in micro-positive pressure and CO is used2The gas inlet 12 is filled with CO2The water inlet 26 and the water outlet 17 of the cooling water jacket 18 are connected with circulating water;
s3, starting the motor 11, wherein the motor 11 drives the stirring shaft 23 to rotate through the speed reducer 6 and the chain and sprocket transmission mechanism; turning on the heater 14 and the screw feeder 2, setting the temperature of the furnace body 16 and the rotating speed of the stirring shaft 23, and activating the mixed raw materials at 800 ℃ for 90 min;
s4, the activated material enters a material collecting bin 25 through a cooling water jacket 18 under the action of a stirring shaft 23;
and S5, washing and drying the activated material to obtain the super-capacitor activated carbon.
EXAMPLE five
The content of the device for preparing the supercapacitor activated carbon by the alkali activation method provided in the fifth embodiment is the same as that described in the first embodiment, and details are not described herein.
The preparation method of the device for preparing the super-capacitor activated carbon by the alkali activation method comprises the following steps:
s1, mixing coal tar pitch and potassium hydroxide according to the mass ratio of 1: 4, mixing, namely crushing the mixed raw materials in a crusher to 400 meshes, and then adding the mixed raw materials into the feeding bin 1 after the mixed raw materials are uniform;
s2, introducing nitrogen through the protective gas interfaces 9, 19 and 24, adjusting the opening of the valve 10 to ensure that the pressure gauge 13 is in micro-positive pressure and CO is used2The gas inlet 12 is filled with CO2The water inlet 26 and the water outlet 17 of the cooling water jacket 18 are connected with circulating water;
s3, starting the motor 11, wherein the motor 11 drives the stirring shaft 23 to rotate through the speed reducer 6 and the chain and sprocket transmission mechanism; turning on the heater 14 and the screw feeder 2, setting the temperature of the furnace body 16 and the rotating speed of the stirring shaft 23, and activating the mixed raw materials at 900 ℃ for 60 min;
s4, the activated material enters a material collecting bin 25 through a cooling water jacket 18 under the action of a stirring shaft 23;
and S5, washing and drying the activated material to obtain the super-capacitor activated carbon.
EXAMPLE six
The device for preparing supercapacitor activated carbon by an alkali activation method provided in the sixth embodiment is the same as the content recorded in the first embodiment, and details are not described herein.
The preparation method of the device for preparing the super-capacitor activated carbon by the alkali activation method comprises the following steps:
s1, mixing the starch carbonization material with potassium carbonate according to the mass ratio of 1: 4, mixing, namely crushing the mixed raw materials in a crusher to 140 meshes, and then adding the mixed raw materials into the feeding bin 1 after the mixed raw materials are uniform;
s2, introducing nitrogen through the protective gas interfaces 9, 19 and 24, adjusting the opening of the valve 10 to ensure that the pressure gauge 13 is in micro-positive pressure and CO is used2The gas inlet 12 is filled with CO2The water inlet 26 and the water outlet 17 of the cooling water jacket 18 are connected into a circulationWater circulation;
s3, starting the motor 11, wherein the motor 11 drives the stirring shaft 23 to rotate through the speed reducer 6 and the chain and sprocket transmission mechanism; turning on the heater 14 and the screw feeder 2, setting the temperature of the furnace body 16 and the rotating speed of the stirring shaft 23, and activating the mixed raw materials for 30min at 880 ℃;
s4, the activated material enters a material collecting bin 25 through a cooling water jacket 18 under the action of a stirring shaft 23;
and S5, washing and drying the activated material to obtain the super-capacitor activated carbon.
The characterization results of the supercapacitor activated carbon prepared in the first to sixth examples are shown in the following table:
the above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (8)
1. A device for alkali activation method preparation super capacitor activated carbon, it includes furnace body (16), feed unit and drive unit, its characterized in that:
the feeding unit comprises a feeding bin (1) and a spiral feeder (2), a first protective gas interface (9) is arranged on the side wall of the feeding bin (1), a discharging port of the feeding bin (1) is communicated with a feeding port of the spiral feeder (2), and a discharging port of the spiral feeder (2) is communicated with the head end of a furnace body (16); the furnace body (16) is arranged on the support frame (27), the furnace cover (15) covers the outside of the furnace body (16), the tail gas discharge pipe (11) is arranged at the head end of the furnace body (16), a pressure gauge (13) is arranged on one side, close to the furnace cover (15), of the tail gas discharge pipe (11), and CO is arranged on one side, far away from the furnace cover (15), of the tail gas discharge pipe (11)2An air inlet (12), a pressure gauge (13) and CO2A valve (10) is mounted on a tail gas discharge pipe (11) between the gas inlets (12), a heating zone is arranged at the head end of the furnace body (16) in the furnace cover (15), a heating element (14) is arranged in the heating zone, a cooling water jacket (18) is arranged at the tail part of the furnace body (16) in the furnace cover (15), a water inlet (17) is arranged above the cooling water jacket (18) on the furnace cover (15), a water outlet (26) is arranged below the cooling water jacket (18) on the furnace cover (15), a second protective gas interface (19) is arranged at the tail end of the furnace body (16), the tail end of the furnace body (16) is communicated with a material receiving bin (25) through a pipeline, and a third protective gas interface (24) is arranged at the position of a material inlet of the material receiving bin (25);
a stirring shaft (23) is arranged through the furnace body (16), wedge-shaped blades (21) are arranged on the outer circumferential surface of the stirring shaft (23), a material guide plate (20) is arranged in the middle of each blade (21), air seal packing (3) and air seal packing (22) are respectively arranged at the joints of the head end and the tail end of the stirring shaft (23) and the furnace body (16), and a driven chain wheel is arranged at the head end of the stirring shaft (23);
the driving unit comprises a motor (4), a speed reducer (6) and a driving chain wheel (8), a rotor of the motor (4) is connected with a power input shaft of the speed reducer (6) through a belt (5), the driving chain wheel (8) is installed on a power output shaft of the speed reducer (6), and the driving chain wheel (8) is connected with a driven chain wheel through a chain (7).
2. The device for preparing the supercapacitor activated carbon by the alkali activation method according to claim 1, wherein: the included angle between the material guide plate (20) and the horizontal direction is 30 degrees.
3. The device for preparing the supercapacitor activated carbon by the alkali activation method according to claim 1, wherein: the material of the contact part of the device and the material is one of nickel or 310S.
4. The preparation method of the device for preparing the supercapacitor activated carbon by the alkali activation method according to claim 1 is characterized by comprising the following steps of:
s1, mixing the carbonized material and the activating agent according to the mass ratio of 1: 1-4, crushing the mixed raw materials in a crusher to 100-650 meshes, and then adding the mixed raw materials into a feeding bin (1) after the mixed raw materials are uniform;
s2, introducing shielding gas through shielding gas connectors (9, 19 and 24), adjusting the opening degree of a valve (10) to enable a pressure gauge (13) to be micro-positive pressure, and introducing CO2CO is introduced into the gas inlet (12)2Circulating water is connected to a water inlet (26) and a water outlet (17) of the cooling water jacket (18);
s3, starting a motor (11), wherein the motor (11) drives a stirring shaft (23) to rotate through a speed reducer (6) and a chain and sprocket transmission mechanism; turning on the heater (14) and the screw feeder (2), setting the temperature of the furnace body (16) and the rotating speed of the stirring shaft (23), and activating the mixed raw materials for 30-120 min at 780-900 ℃;
s4, the activated material enters a material receiving bin (25) through a cooling water jacket (18) under the action of a stirring shaft (23);
and S5, washing and drying the activated material to obtain the super-capacitor activated carbon.
5. The preparation method of the device for preparing the supercapacitor activated carbon by the alkali activation method according to claim 4, wherein the device comprises: in the step S1, the carbonized material is one of starch carbonized material, coconut shell carbonized material, petroleum coke, coal and coal tar pitch.
6. The preparation method of the device for preparing the supercapacitor activated carbon by the alkali activation method according to claim 4, wherein the device comprises: in step S1, the activating agent is one or a mixture of potassium hydroxide, sodium hydroxide and potassium carbonate.
7. The preparation method of the device for preparing the supercapacitor activated carbon by the alkali activation method according to claim 4, wherein the device comprises: in step S2, the shielding gas is nitrogen or argon.
8. The preparation method of the device for preparing the supercapacitor activated carbon by the alkali activation method according to claim 4, wherein the device comprises: in the step S5, the specific surface area of the prepared super-capacitor activated carbon is 1500-3000 m2A pore volume of 0.8 to 1.5 cm/g3/g。
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CN111689499A (en) * | 2020-06-29 | 2020-09-22 | 舒克孝 | Uniform internal heat stirring type activation kiln |
CN114134038A (en) * | 2022-01-11 | 2022-03-04 | 南京农业大学 | Novel aerobic fermentation device for experiments |
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