A water removal device, a water removal method, a method of preparing activated carbon, activated carbon, and an electrode

Abstract

This invention provides a dehydration device, a dehydration method, a method for preparing activated carbon, activated carbon, and an electrode. The dehydration device includes a dehydration chamber, a feed pipe, a conveyor belt, a heater, a condenser plate, a condensate receiver, and a discharge pipe. The conveyor belt, heater, condenser plate, and condensate receiver are located within the dehydration chamber. The feed pipe extends into the dehydration chamber, with one end positioned above one end of the conveyor belt for feeding material. The discharge pipe is located at the other end of the conveyor belt and extends out of the dehydration chamber for discharging material. The conveyor belt includes an upper belt and a lower belt. The heater is located below the upper belt to heat petroleum coke to evaporate and remove water. The condenser plate is located above the conveyor belt to cool the evaporated water vapor into condensate. The condensate receiver is located below the condenser plate to collect the condensate. The activated carbon of this invention has a high specific capacitance, as well as a high specific surface area and pore volume. This activated carbon is used to prepare electrochemical capacitor electrodes and can effectively improve the specific capacitance of the capacitor.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of activated carbon preparation, and particularly relates to a water removal device, a water removal method, a method for preparing activated carbon, activated carbon and an electrode. BACKGROUND

[0002] Electrochemical capacitors are a new type of electrochemical energy storage device developed in recent years, which have high energy density and excellent rapid charge and discharge performance, and have potential application value in electric vehicles, electric tools and mobile communications. Carbon materials, as electrode materials of electrochemical capacitors, have good electrical conductivity and thermal conductivity, stable chemical properties, small thermal expansion coefficient, low price, and easy industrialization, etc. are the most promising electrode materials for electrochemical capacitors. At present, a large amount of low-value heavy oil is produced in the process of oil refining and coal coking. These heavy oils have high carbon content and low price, which can be used as ideal raw materials for activated carbon, but the activated carbon produced by general methods has poor performance, such as low specific capacitance, low specific surface area and pore volume, etc. SUMMARY

[0003] In order to solve at least one problem existing in the prior art, the present application provides a water removal device, a water removal method, a method for preparing activated carbon, activated carbon and an electrode. The activated carbon prepared by the method of the present application has a high specific surface area and pore volume. The activated carbon used for electrochemical capacitor electrodes has a high specific capacitance.

[0004] In a first aspect, the present application provides a petroleum coke water removal device, which comprises a water removal bin, a feed pipe, a conveying belt, a heater, a condensation plate, a condensate water receiver and a discharge pipe.

[0005] The conveying belt, the heater, the condensation plate and the condensate water receiver are arranged in the water removal bin.

[0006] The feed pipe extends into the water removal bin and one end thereof is located above one end of the conveying belt for feeding the water removal bin, and the discharge pipe is located at the other end of the conveying belt and extends out of the water removal bin for discharging.

[0007] The conveying belt comprises an upper belt and a lower belt, and the heater is arranged below the upper belt for heating the petroleum coke on the conveying belt to volatilize water.

[0008] The condensation plate is arranged above the conveying belt for cooling the water vapor formed by volatilization into condensate water.

[0009] The condensate water receiver is arranged below the condensation plate for collecting the condensate water.

[0010] Preferably, the condenser plate is inclined downward from one end near the feed pipe to the other end near the discharge pipe, and the inclination angle is preferably 25-70°.

[0011] Preferably, the water removal device further includes a telescopic scraper, the lower end of which is connected to the condensate receiver and the upper end which abuts against the lower surface of the condenser plate, for scraping condensate into the condensate receiver.

[0012] Preferably, the condensate receiver is configured to reciprocate along the conveying direction of the conveyor belt, and is used to carry the telescopic scraper to scrape water from the lower surface of the condensate plate.

[0013] Preferably, when the wiping action is performed, the telescopic squeegee extends and contacts the lower surface of the condenser plate; when the wiping action is stopped, the telescopic squeegee retracts and releases contact with the lower surface of the condenser plate.

[0014] Preferably, the dewatering device further includes a centrifugal fan, which is connected to the condensate receiver via a drain pipe to lower the pressure inside the dewatering chamber than the external pressure and to discharge the condensate from the condensate receiver into the dewatering chamber.

[0015] Preferably, the dewatering device further includes a vibrator disposed below the upper belt of the conveyor belt for vibrating the upper belt of the conveyor belt to loosen the petroleum coke on the conveyor belt.

[0016] Preferably, the petroleum coke on the conveyor belt is heated and dehydrated, then discharged through the discharge pipe and enters the carbonization furnace for carbonization treatment.

[0017] Secondly, the present invention provides a method for dewatering petroleum coke, wherein the dewatering method is implemented by the dewatering device described in claim 1 or 2, comprising: petroleum coke entering the dewatering chamber through a feed pipe and falling onto a conveyor belt; as the conveyor belt rotates, it is heated by a heater to volatilize water vapor to remove water; the volatilized water vapor contacts the condenser plate to form condensate and is collected by the condensate receiver; and the dewatered petroleum coke falls into the discharge pipe and is discharged from the dewatering chamber.

[0018] Preferably, the condensate receiver carries the telescopic scraper from one end of the condensing plate near the feed pipe to one end near the discharge pipe, scraping the condensate on the lower surface of the condensing plate into the condensate receiver.

[0019] Preferably, during the process of the condensate receiver carrying the telescopic scraper from one end of the condensate plate near the discharge pipe to one end near the inlet pipe, the telescopic scraper releases contact with the lower surface of the condensate plate.

[0020] Preferably, when the condensate receiver stops moving, the condensate receiver is fixed below the end of the condenser plate near the discharge pipe to receive dripping condensate.

[0021] Preferably, the petroleum coke is heated to 100-250°C by a heater as it passes through a conveyor belt.

[0022] Preferably, the pressure inside the dewatering chamber is 0.07-0.09 MPa.

[0023] Preferably, the petroleum coke is crushed before entering the dewatering device, and the particle size after crushing is 0.18-0.4 mm, preferably 0.2-0.3 mm.

[0024] Thirdly, the present invention provides a method for preparing activated carbon, the method comprising the following steps.

[0025] Step (1): Mix the metal-organic framework and the oil slurry in a mixing tank to obtain a mixture.

[0026] Step (2): The mixture obtained in step (1) is fed into the coking tower for coking treatment to obtain petroleum coke.

[0027] Step (3): The petroleum coke obtained in step (2) is dehydrated by the dehydration device described in the first aspect or the dehydration method described in the second aspect to obtain dehydrated petroleum coke.

[0028] Step (4): The dehydrated petroleum coke is sent to a carbonization furnace for carbonization treatment to obtain activated carbon precursor.

[0029] Step (5): The activated carbon precursor is fed into an activation device for activation treatment to obtain the activated carbon.

[0030] Preferably, the specific surface area of ​​the metal-organic framework is ≥500 m². 2 / g, preferably 500-1500m 2 / g.

[0031] Preferably, the pore volume of the metal-organic framework is ≥0.2 cm³. 3 / g, preferably 0.3-1.2cm 3 / g.

[0032] Preferably, the pore size of the metal-organic framework is ≥0.2 nm, and more preferably 0.2-5 nm.

[0033] Preferably, the metal-organic framework includes at least one of IRMOF, CPL, ZIFs, MIL, and UiO.

[0034] Preferably, the density of the oil slurry is ≥0.9 g / cm³.3 .

[0035] Preferably, the slurry comprises at least one of catalytic cracking slurry, high-end carbon heavy oil slurry, asphalt, and residual oil.

[0036] Preferably, the weight ratio of the metal-organic framework to the slurry is 1:6-150, more preferably 1:10-120.

[0037] Preferably, in step (1), the mixing conditions include: a mixing temperature of 50-160℃, preferably 100-140℃; and a mixing time of 1-3h, preferably 1.5-2.5h.

[0038] Preferably, the mixture obtained in step (1) is cooled to room temperature before step (2).

[0039] Preferably, in step (2), the coking process includes: performing a first coking process on the mixture under a first coking condition, then performing a second coking process under a second coking condition, and obtaining the petroleum coke after cooling.

[0040] Preferably, the first coking conditions include: a first coking temperature of 200-300℃, more preferably 240-290℃; and a first coking time of 1-5h, more preferably 1.5-3h.

[0041] Preferably, step (2) further includes: before performing the first coking treatment, heating at 1-10°C for 1 minute. -1 The mixture from step (1) is heated to the first coking temperature at a rate of 2-8°C / min; preferably at 2-8°C / min. -1 The temperature is increased at a rate to the first coking temperature.

[0042] Preferably, the second coking conditions include: a second coking temperature of 450-550℃, more preferably 490-510℃; and a second coking time of 8-20 hours, more preferably 10-15 hours.

[0043] Preferably, step (2) further includes: before performing the second coking treatment, heating at 1-10°C for 1 minute. -1 The material after the first coking treatment is heated from the first coking temperature to the second coking temperature at a rate of 1.5-5℃ / min; preferably, this rate is 1.5-5℃ / min. -1 The temperature is increased at a rate to the second coking temperature.

[0044] Preferably, step (3) further includes: before removing water from the petroleum coke obtained in step (2), grinding the petroleum coke to a particle size of 0.18-0.4 mm, preferably 0.2-0.3 mm.

[0045] Preferably, in step (4), the carbonization process is carried out in an argon-hydrogen mixed atmosphere or an inert atmosphere; more preferably, it is carried out in an argon-hydrogen mixed atmosphere.

[0046] Preferably, the carbonization conditions include: a carbonization temperature of 400-1000℃, more preferably 500-900℃; and a carbonization time of 0.5-300 min, more preferably 50-200 min.

[0047] Preferably, step (4) further includes: before the carbonization treatment, heating the dehydrated petroleum coke from step (3) at 0.5-10℃ for 1 minute. -1 The temperature is increased to the carbonization temperature at a rate of 1-5°C / min, preferably 1-5°C / min. -1 The temperature is increased to the carbonization temperature at a rate that allows it to rise.

[0048] Preferably, the method further includes cooling the activated carbon precursor to room temperature before performing step (5).

[0049] Preferably, in step (5), the activation treatment method includes: immersing the activated carbon precursor in an activator solution, and then taking it out and activating it.

[0050] Preferably, the activation conditions include: an activation temperature of 400-1000℃, more preferably 600-950℃; and an activation time of 0.5-600 min, more preferably 60-500 min.

[0051] Preferably, step (5) further includes: before activation, immersing the activated carbon precursor taken from the activator solution at 0.5-10°C for min. -1 The temperature is increased to the activation temperature at a rate of 2-8°C / min; preferably at a rate of 2-8°C / min. -1 The temperature is increased at a rate to the activation temperature.

[0052] More preferably, the activation treatment method in step (5) further includes: drying the activated carbon precursor taken from the activator solution and then heating it.

[0053] Preferably, the activator includes at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate.

[0054] Preferably, the weight ratio of the activated carbon precursor to the activator is 1:0.2-50, more preferably 1:5-15.

[0055] Preferably, the concentration of the activator solution is 1-20g / 100ml, more preferably 2-15g / 100ml.

[0056] Preferably, the soaking time is 5-30 hours, more preferably 8-20 hours.

[0057] Preferably, step (5) further includes: cooling and washing the activated carbon obtained from the activation treatment.

[0058] Preferably, the washing method involves sequential acid washing and water washing.

[0059] Preferably, the number of pickling cycles is 3-5 times, and the number of water washing cycles is 3-5 times.

[0060] Fourthly, the present invention provides activated carbon prepared by the method described in the third aspect.

[0061] Preferably, the activated carbon has a nitrogen content of 0.1-15% by weight, more preferably 1-8%, and even more preferably 1.5-3%.

[0062] And / or, the pore volume of the activated carbon is 0.1-2.1 cm³. 3 / g, preferably 0.5-0.7cm 3 / g.

[0063] And / or, the specific surface area of ​​the activated carbon is 300-2000 m². 2 / g, preferably 1000-1500m 2 / g.

[0064] Fifthly, the present invention provides an electrode for an electrochemical capacitor, the electrode being made of activated carbon as described in the fourth aspect.

[0065] Preferably, the electrode further includes a conductive agent, a binder, and a conductive substrate.

[0066] More preferably, the weight ratio of the activated carbon, the conductive agent, and the binder is 4-12:0.5-3:1, and more preferably 6-10:0.5-2:1.

[0067] This invention provides a water removal device, a water removal method, a method for preparing activated carbon, activated carbon, and an electrode. Compared with the prior art, this invention has the following advantages:

[0068] The activated carbon prepared by this invention possesses structural advantages such as porosity, impurity atom (e.g., N) doping, and a large specific surface area, resulting in excellent electrochemical performance. Electrochemical capacitor electrodes prepared using the activated carbon of this invention exhibit excellent specific capacitance (at 1 A g). -1 The specific capacitance at current density can reach 158.7 F / g. This invention provides a new approach for developing electrochemical capacitor electrode materials with excellent comprehensive performance. Attached Figure Description

[0069] Figure 1 This is a schematic diagram of the water removal device of the present invention;

[0070] Figure 2 This is a side view of the conveyor belt 3 and vibrator 13 of the present invention;

[0071] Figure 3 This is the Raman spectrum of the activated carbon in Example 1 of the present invention. Detailed Implementation

[0072] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0073] In a first aspect, the present invention provides a petroleum coke dewatering device, such as... Figure 1 As shown, the dewatering device includes a dewatering chamber 1, a feed pipe 2, a conveyor belt 3, a heater 4, a condenser plate 5, a condensate receiver 6, and a discharge pipe 8;

[0074] The conveyor belt 3, the heater 4, the condenser plate 5, and the condensate receiver 6 are disposed inside the dewatering chamber 1.

[0075] The feed pipe 2 extends into the dewatering chamber 1 and one end of it is located above one end of the conveyor belt 3 for feeding material into the dewatering chamber 1. The discharge pipe 8 is located at the other end of the conveyor belt 3 and extends out of the dewatering chamber 1 for discharging material.

[0076] The conveyor belt 3 includes an upper belt and a lower belt, and the heater 4 is located below the upper belt for heating the petroleum coke on the conveyor belt 3 to evaporate and remove water.

[0077] The condenser plate 5 is disposed above the conveyor belt 3 and is used to cool the water vapor formed by evaporation into condensate.

[0078] The condensate receiver 6 is located below the condenser plate 5 and is used to collect the condensate.

[0079] The dehydration device of the present invention can effectively remove free water and crystal water from the petroleum coke, which is beneficial to subsequent carbonization and activation treatments. The dehydration device of the present invention can effectively prevent water vapor and dust from escaping into the air, thus avoiding resource waste and environmental pollution.

[0080] In a preferred embodiment of the present invention, the condenser plate 5 is inclined downward from one end near the feed pipe 2 to the other end near the discharge pipe 8, and the inclination angle is preferably 25-70°.

[0081] In a preferred embodiment of the present invention, the water removal device further includes a telescopic scraper 7, the lower end of which is connected to the condensate receiver 6 and the upper end which abuts against the lower surface of the condenser plate 5, for scraping condensate into the condensate receiver 6.

[0082] In a preferred embodiment of the present invention, the condensate receiver 6 is configured to reciprocate along the conveying direction of the conveyor belt 3, and is used to carry the telescopic scraper 7 to scrape water from the lower surface of the condensate plate 5.

[0083] In a preferred embodiment of the present invention, during the wiping action, the telescopic scraper 7 extends and contacts the lower surface of the condenser plate 5. During the wiping action, as the vertical distance between the condensate receiver 6 and the lower surface of the condenser plate 5 changes, the telescopic scraper 7 automatically adjusts its extension length to ensure that the upper end of the telescopic scraper 7 remains in contact with the lower surface of the condenser plate 5. When the wiping action stops, the telescopic scraper 7 retracts and releases contact with the lower surface of the condenser plate 5.

[0084] In a preferred embodiment of the present invention, the dewatering device further includes a centrifugal fan 9, which is connected to the condensate receiver 6 via a drain pipe, for making the pressure inside the dewatering chamber 1 lower than the external pressure and for discharging the condensate from the condensate receiver 6 into the dewatering chamber 1.

[0085] A preferred embodiment of the present invention, such as Figure 2 As shown, the dewatering device also includes a vibrator 13 disposed below the upper belt of the conveyor belt 3, used to vibrate the upper belt of the conveyor belt 3 to loosen the petroleum coke on the conveyor belt 3. The number of vibrators 13 can be determined according to the length of the conveyor belt 3. Preferably, the interval between adjacent vibrators 13 is 0.5-1.5m according to the running direction of the conveyor belt 3.

[0086] In a preferred embodiment of the present invention, the petroleum coke on the conveyor belt 3 is heated and dehydrated, discharged through the discharge pipe 8, and enters the carbonization furnace for carbonization treatment.

[0087] like Figure 1 As shown, the side closer to the feed pipe 2 is designated as the left inner wall of the dewatering chamber 1, and the side closer to the discharge pipe 8 is designated as the right inner wall of the dewatering chamber 1.

[0088] In a preferred embodiment of the present invention, the distance between the end of the condenser plate 5 near the feed pipe 2 and the feed pipe 2 is 10-30cm.

[0089] In a preferred embodiment of the present invention, the distance between the end of the condenser plate 5 near the discharge pipe 8 and the inner wall of the right side of the dewatering chamber is 10-30cm.

[0090] In a preferred embodiment of the present invention, the distance between the condenser plate 5 and the inner walls of the front and rear sides of the dewatering chamber 1 is 10-30 cm.

[0091] Secondly, the present invention provides a method for dewatering petroleum coke, wherein the dewatering method is implemented by the dewatering device described in the first aspect, comprising: petroleum coke entering the dewatering chamber 1 through the feed pipe 2 and falling onto the conveyor belt 3; as the conveyor belt 3 rotates, it is heated by the heater 4 to volatilize water vapor to remove water; the volatilized water vapor comes into contact with the condenser plate 5 to form condensate and is collected by the condensate receiver 6; and the dewatered petroleum coke falls into the discharge pipe 8 and is discharged from the dewatering chamber 1.

[0092] In a preferred embodiment of the present invention, the condensate receiver 6 carries the telescopic scraper 7 from one end of the condenser plate 5 near the feed pipe 2 to one end near the discharge pipe 8, scraping the condensate on the lower surface of the condenser plate 5 into the condensate receiver 6.

[0093] In a preferred embodiment of the present invention, as the condensate receiver 6 carries the telescopic scraper 7 from one end of the condensate plate 5 near the discharge pipe 8 to one end near the feed pipe 2, the telescopic scraper 7 disengages from the lower surface of the condensate plate 5. This design prevents the condensate receiver 6 from scraping condensate onto the conveyor belt 3 as it moves from below the lower end of the condensate plate 5 to below the higher end.

[0094] In a preferred embodiment of the present invention, when the condensate receiver 6 stops moving, it is fixed below the end of the condenser plate 5 near the discharge pipe 8 to receive dripping condensate. Because the condenser plate 5 is inclined, some of the condensate will collect along its surface at the lower end and finally fall into the condensate receiver 6 below. The moving frequency of the condensate receiver 6 can be set according to the actual application to prevent condensate from falling onto the conveyor belt 3.

[0095] In a preferred embodiment of the present invention, the petroleum coke is heated to 100-250°C by a heater 4 while being conveyed by a conveyor belt 3. This preferred temperature effectively removes moisture from the petroleum coke and also prevents condensation from forming on the inner wall of the dewatering chamber.

[0096] In a preferred embodiment of the present invention, the pressure inside the dewatering chamber 1 is 0.07-0.09 MPa. Using this preferred pressure effectively prevents the escape of evaporated water vapor and dust from the inlet of the feed pipe 2.

[0097] In a preferred embodiment of the present invention, the petroleum coke is first crushed before entering the dewatering device, and the particle size after crushing is 0.18-0.4 mm, preferably 0.2-0.3 mm.

[0098] In this invention, the surface temperature of the condenser plate 5 is 2-10℃.

[0099] In this invention, a condenser tube 10 may be installed inside the condenser plate 5 to provide cooling energy.

[0100] The inventors of this invention have discovered that by compounding a metal-organic framework with an oil slurry, followed by coking, specific dehydration, carbonization, and activation treatments, the prepared activated carbon exhibits a larger specific surface area and pore volume. The activated carbon of this invention, when used as an electrode in an electrochemical capacitor, demonstrates excellent electrochemical performance (specific capacitance). Analysis suggests that the compounding of the metal-organic framework with the oil slurry can synergistically improve the specific surface area. Furthermore, it is believed that the metal atoms and impurity atoms (such as N, O, and S) introduced by the metal-organic framework can give the activated carbon a larger active surface area, resulting in higher specific capacitance when used as an electrode in an electrochemical capacitor.

[0101] Thirdly, the present invention provides a method for preparing activated carbon, the method comprising the following steps:

[0102] Step (1): Mix the metal-organic framework and the oil slurry in a mixing tank to obtain a mixture;

[0103] Step (2): The mixture obtained in step (1) is fed into a coking tower for coking treatment to obtain petroleum coke;

[0104] Step (3): The petroleum coke is dehydrated by the dehydration device described in the first aspect or the dehydration method described in the second aspect;

[0105] Step (4): The dehydrated petroleum coke is fed into a carbonization furnace for carbonization treatment to obtain activated carbon precursor.

[0106] Step (5): The activated carbon precursor is fed into an activation device for activation treatment to obtain the activated carbon.

[0107] In a preferred embodiment of the present invention, the metal-organic framework has a specific surface area ≥ 500 m². 2 / g, preferably 500-1500m 2 / g; and / or, the pore volume of the metal-organic framework is ≥0.2cm³.3 / g, preferably 0.3-1.2cm 3 / g; and / or, the pore size of the metal-organic framework is ≥0.2nm, preferably 0.2-5nm. Using this preferred metal-organic framework can not only effectively improve the electrochemical performance of activated carbon, but also allow for flexible control of the pore structure of activated carbon, thus expanding its application range.

[0108] In a preferred embodiment of the present invention, the metal-organic framework includes at least one of IRMOF, CPL, ZIFs, MIL, and UiO; preferably ZIFs and / or IRMOF; preferably, the ZIFs are selected from ZIF-8 or ZIF-67, more preferably ZIF-8.

[0109] The IRMOF is composed of separate secondary structural units [Zn4O]. 6+ Inorganic groups and a series of aromatic carboxylic acid ligands form a microporous crystalline material that is self-assembled in an octahedral bridge; the CPL is formed by coordination of a six-coordinate metal element with a neutral nitrogen-containing heterocyclic ligand; ZIFs are zeolite-like materials synthesized by reacting Zn(III) or Co(III) with imidazole ligands; the MIL is a material synthesized using different transition metal elements and dicarboxylic acid ligands; UiO is a material with a three-dimensional microporous structure formed by connecting a Zr (zirconium)-containing regular octahedron [Zr6O4(OH)4] with a terephthalic acid (BDC) organic ligand.

[0110] In this invention, the metal-organic framework can be purchased from commercially available products or prepared in-house, and the preparation method can be a conventional method in the art.

[0111] In this invention, the oil slurry refers to a heavy byproduct obtained during crude oil refining. Preferably, the density of the oil slurry is ≥0.9 g / cm³. 3 .

[0112] In a preferred embodiment of the present invention, the slurry includes at least one of catalytic cracking slurry, high-end carbon heavy oil slurry, asphalt, and residual oil, preferably at least one of high-end carbon heavy oil slurry, residual oil, and catalytic cracking slurry.

[0113] The catalytic cracking slurry refers to the heavy oil component obtained during petroleum refining through catalytic cracking followed by solidification treatment, with a density of 0.96-1.05 g / cm³. 3 .

[0114] The high-end carbon heavy oil slurry refers to the heavy oil component obtained from the bottom of the catalytic cracking slurry after processing by a vacuum unit, with a density of 1-1.14 g / cm³. 3 .

[0115] The asphalt is a heavy oil slurry obtained from the bottom of the catalytic cracking slurry tower after treatment by the vacuum distillation unit, with a density of 1.19-1.22 g / cm³. 3 .

[0116] The residue oil is the bottom heavy oil slurry of the catalytic cracking slurry after slurry-bed hydrotreating, with a density of 1.17-1.19 g / cm³. 3 .

[0117] In a preferred embodiment of the present invention, the weight ratio of the metal-organic framework to the oil slurry is 1:6-150, preferably 1:10-120, and more preferably 1:15-50. Using this preferred ratio not only effectively improves the electrochemical performance of activated carbon but also allows for flexible control of the specific surface area and pore structure of the activated carbon.

[0118] In step (1), the mixing conditions include: a mixing temperature of 50-160℃, preferably 100-140℃; and a mixing time of 1-3h, preferably 1.5-2.5h.

[0119] In a preferred embodiment of the present invention, the mixture obtained in step (1) is cooled to room temperature before step (2).

[0120] In a preferred embodiment of the present invention, step (2) of the coking process includes: performing a first coking process on the mixture under a first coking condition, then performing a second coking process under a second coking condition, and obtaining the petroleum coke after cooling.

[0121] In a preferred embodiment of the present invention, the first coking conditions include: a first coking temperature of 200-300℃, preferably 240-290℃; and a first coking time of 1-5h, preferably 1.5-3h.

[0122] In a preferred embodiment of the present invention, step (2) further includes: before performing the first coking treatment, at 1-10℃ min -1 The mixture from step (1) is heated to the first coking temperature at a rate of 2-8°C / min; preferably at 2-8°C / min. -1 The temperature is increased at a rate to the first coking temperature.

[0123] In a preferred embodiment of the present invention, the second coking conditions include: a second coking temperature of 450-550℃, preferably 490-510℃; and a second coking time of 8-20h, preferably 10-15h.

[0124] In a preferred embodiment of the present invention, step (2) further includes: before performing the second coking treatment, at 1-10℃ min -1The material after the first coking treatment is heated from the first coking temperature to the second coking temperature at a rate of 1.5-5℃ / min; preferably, this rate is 1.5-5℃ / min. -1 The temperature is increased at a rate to the second coking temperature.

[0125] In a preferred embodiment of the present invention, step (3) further includes: before dehydrating the petroleum coke obtained in step (2), grinding the petroleum coke, wherein the particle size after grinding is 0.18-0.4 mm, preferably 0.2-0.3 mm.

[0126] In a preferred embodiment of the present invention, in step (4), the carbonization treatment is carried out in an argon-hydrogen mixed atmosphere or an inert atmosphere; preferably, it is carried out in an argon-hydrogen mixed atmosphere. The volume ratio of argon to hydrogen in the argon-hydrogen mixed atmosphere is 15-20:1.

[0127] In a preferred embodiment of the present invention, the carbonization treatment conditions include: a carbonization temperature of 400-1000℃, preferably 500-900℃; and a carbonization time of 0.5-300 min, preferably 50-200 min.

[0128] In a preferred embodiment of the present invention, step (4) further includes: before the carbonization treatment, the petroleum coke after dehydration in step (3) is heated at 0.5-10℃ for a period of time. -1 The temperature is increased to the carbonization temperature at a rate of 1-5°C / min, preferably 1-5°C / min. -1 The temperature is increased to the carbonization temperature at a rate that allows it to rise.

[0129] In a preferred embodiment of the present invention, the method further includes cooling the activated carbon precursor to room temperature before performing step (5).

[0130] In a preferred embodiment of the present invention, step (5) includes immersing the activated carbon precursor obtained in step (4) in an activator solution, and then taking it out and activating it.

[0131] In a preferred embodiment of the present invention, the activation conditions include: an activation temperature of 400-1000℃, preferably 600-950℃; and an activation time of 0.5-600 min, preferably 60-500 min.

[0132] In a preferred embodiment of the present invention, step (5) further includes: before activation, activating the activated carbon precursor taken from the activator solution at 0.5-10°C for min. -1 The temperature is increased to the activation temperature at a rate of 2-8°C / min. -1 The temperature is increased at a rate to the activation temperature.

[0133] In a preferred embodiment of the present invention, the activation treatment method in step (5) further includes: drying the activated carbon precursor taken from the activator solution and then heating it.

[0134] In a preferred embodiment of the present invention, the activator includes at least one selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate; preferably sodium hydroxide and / or potassium hydroxide.

[0135] In a preferred embodiment of the present invention, the weight ratio of the activated carbon precursor to the activator is 1:0.2-50, preferably 1:5-15.

[0136] In a preferred embodiment of the present invention, the concentration of the activator solution is 1-20g / 100ml, preferably 2-15g / 100ml.

[0137] In a preferred embodiment of the present invention, the soaking time is 5-30 hours, preferably 8-20 hours.

[0138] In a preferred embodiment of the present invention, step (5) further includes: cooling and washing the activated carbon obtained from the activation treatment. The acid used for acid washing is selected from hydrochloric acid or nitric acid, preferably hydrochloric acid; and / or, the concentration of the acid used for acid washing is 5-15 wt%.

[0139] In a preferred embodiment of the present invention, the washing method is to perform acid washing and water washing in sequence.

[0140] In a preferred embodiment of the present invention, the number of acid washings is 3-5 times, and the number of water washings is 3-5 times.

[0141] In a fourth aspect, the present invention provides activated carbon prepared by the method described in the third aspect.

[0142] In a preferred embodiment of the present invention, the N content in the activated carbon is 0.1-15 wt%, preferably 1-8 wt%, and more preferably 1.5-3 wt%.

[0143] In a preferred embodiment of the present invention, the activated carbon has a pore volume of 0.1-2.1 cm³. 3 / g, preferably 0.5-0.7cm 3 / g.

[0144] In a preferred embodiment of the present invention, the specific surface area of ​​the activated carbon is 300-2000 m². 2 / g, preferably 1000-1500m 2 / g.

[0145] In a preferred embodiment of the present invention, the activated carbon has a pore size of 0.1-50 nm, preferably 1-15 nm, and more preferably 2-5 nm.

[0146] In this invention, the pore size is measured using methods commonly used in the art, such as using the BET method to obtain a pore size distribution map with a single peak, and the horizontal axis corresponding to the peak value in the pore size distribution map is identified as the pore size of the activated carbon.

[0147] Fifthly, the present invention provides an electrode for an electrochemical capacitor, the electrode being made of activated carbon as described in the fourth aspect.

[0148] In a preferred embodiment of the present invention, the electrode further includes a conductive agent, a binder, and a conductive substrate.

[0149] In a preferred embodiment of the present invention, the weight ratio of the activated carbon, the conductive agent and the binder is 4-12:0.5-3:1, preferably 6-10:0.5-2:1.

[0150] In this invention, the conductive agent can be a commonly used conductive agent in the art, such as acetylene black or graphene.

[0151] In this invention, the adhesive can be a commonly used adhesive in the art, such as polytetrafluoroethylene.

[0152] In this invention, the conductive substrate can be a commonly used conductive substrate in the art, such as nickel foam, nickel sheet, stainless steel felt, or stainless steel mesh.

[0153] In this invention, the specific capacitance of the electrode is determined using conventional electrochemical testing methods in the art, such as cyclic voltammetry, including the following steps:

[0154] a. Electrode preparation: The activated carbon, acetylene black and polytetrafluoroethylene are mixed in a mass ratio of 8:1:1 and spread evenly on nickel foam, and then pressed into a circular electrode.

[0155] b. Electrode Testing: Under room temperature conditions, a three-electrode system was used. The reference electrode was a saturated calomel electrode, the auxiliary electrode was a platinum electrode, and the electrolyte solution was a 30% KOH solution. The original sheet electrode was immersed in the electrolyte solution for 1 hour before testing began.

[0156] c. Cyclic voltammetry tests were performed using an Ivium-n-Stat electrochemical workstation.

[0157] The following detailed description of preferred embodiments of the present invention illustrates the principles of the invention and is not intended to limit the scope of the invention.

[0158] The nitrogen content in activated carbon was obtained using XPS elemental analysis.

[0159] The pore volume and pore size of activated carbon were obtained by BET method; in the pore size test, a peak appeared in the pore size distribution diagram, and the horizontal axis corresponding to the peak value was identified as the pore size of activated carbon.

[0160] Specific capacitance was determined using a DH7000 electrochemical workstation via cyclic voltammetry.

[0161] High-end carbon heavy oil slurry: The heavy oil component obtained from the bottom of the catalytic cracking slurry after processing by a vacuum unit, with a density of 1.12 g / cm³. 3 ;

[0162] Residue oil: Heavy oil slurry from the bottom of the tower after crude oil has undergone slurry bed hydrotreating, with a density of 1.18 g / cm³. 3 ;

[0163] Vacuum residue: The residual oil obtained from crude oil through vacuum distillation, with a density of 0.98 g / cm³. 3 ;

[0164] ZIF-8 (CAS: 59061-53-9) was purchased from Xi'an Qiyue Biotechnology.

[0165] ZIF-67 (CAS:46201-07-4), purchased from Xi'an Qiyue Biotechnology;

[0166] Needle coke: specific surface area 8.3 m² 2 / g, pore size 0.4-4nm, pore volume 0.11cm³ 3 / g;

[0167] In the following examples and comparative examples, the parts by weight are (g) and the parts by volume are (ml).

[0168] Example 1

[0169] The preparation process and steps in this embodiment are as follows:

[0170] Step (1): The high-end carbon heavy oil slurry is transported to the mixing tank and heated to 120°C. ZIF-8 (CAS:59061-53-9) is transported to the high-end carbon heavy oil slurry at 120°C and stirred for 2 hours. Then it is cooled to room temperature to obtain a mixture (the weight ratio of ZIF-8 (CAS:59061-53-9) to high-end carbon heavy oil slurry is 1:22).

[0171] Step (2): The obtained mixture is fed into a coke oven, where it is heated at 5°C / min. -1 The temperature is increased to 280℃ at a rate of [missing information] and held for 2 hours to complete the first coking treatment, and then [missing information] is increased at 3℃ / min. -1The temperature is increased to 500℃ and held for 12 hours to complete the second raw coke treatment. The coke is then cooled to room temperature to obtain petroleum coke. The obtained petroleum coke is crushed to a particle size of 0.2-0.3 mm in a crushing device.

[0172] Step (3): As Figure 1 As shown, the centrifugal fan 9 is turned on, so that the pressure in the dewatering chamber 1 is 0.07-0.09MPa. The crushed petroleum coke enters the dewatering chamber 1 through the feed pipe 2 and falls onto the conveyor belt 3. As the conveyor belt 3 rotates, it is loosened by the vibration of the vibrator 13 (the interval between two adjacent vibrators 13 is 1m). At the same time, it is heated to 200℃ by the heater 4 to release water vapor to remove water. The evaporated water vapor comes into contact with the condenser plate 5 (the angle with the horizontal plane is 35°, and the distance between the condenser plate 5 and the feed pipe 2, the rear inner wall, the front inner wall and the rear inner wall of the dewatering chamber 1 is 15cm) to form condensate.

[0173] The condensate receiver 6 and the telescopic scraper 7 move horizontally from below the higher end of the condensate plate 5 to below the lower end of the condensate plate 5. The telescopic scraper 7 scrapes the condensate on the lower surface of the condensate plate 5 into the condensate receiver 6. After scraping, the condensate receiver 6 and the telescopic scraper 7 stop below the lower end of the condensate plate 5. The scraping is repeated once every 10 minutes.

[0174] After the dewatering process, the petroleum coke falls into the discharge pipe 8 and is discharged from the dewatering chamber 1. The discharged petroleum coke then enters the carbonization process.

[0175] Step (4): The petroleum coke discharged in step (3) enters a tubular furnace (carbonization furnace) filled with argon-hydrogen gas (the volume ratio of argon to hydrogen is 18:1), and is heated at 2℃ / min. -1 The temperature was increased to 600℃ at a rate of 120 min and held for 120 min to complete carbonization. After cooling, activated carbon precursor was obtained.

[0176] Step (5): The activated carbon precursor from step (4) is immersed in an activation solvent tank containing potassium hydroxide solution for 12 hours (the weight ratio of activated carbon precursor to potassium hydroxide in the activation solvent tank is 1:10, and the concentration of potassium hydroxide solution is 10g / 100ml). Then, it is taken out, dried, and sent to a tube furnace (activation equipment) filled with argon-hydrogen gas (the volume ratio of argon to hydrogen is 18:1), and activated at 5℃ for 1 minute. -1 The temperature was increased to 800℃ and held for 200 min to complete the activation. After cooling to room temperature, the activated carbon M1 was prepared by washing it 4 times with dilute hydrochloric acid (7% by mass) and then washing it 4 times with distilled water.

[0177] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M1 are shown in Table 1.

[0178] Example 2

[0179] Activated carbon was prepared according to the method of Example 1, except that in step (1), ZIF-8 (CAS:59061-53-9) was replaced with an equal amount of ZIF-67 (CAS:46201-07-4).

[0180] Activated carbon M2 was prepared.

[0181] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M2 are shown in Table 1.

[0182] Example 3

[0183] Activated carbon was prepared according to the method of Example 1, except that in step (1), the weight ratio of ZIF-8 (CAS:59061-53-9) to high-end carbon heavy oil slurry was 1:37.

[0184] Activated carbon M3 was prepared.

[0185] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M3 are shown in Table 1.

[0186] Example 4

[0187] Step (1): The high-end carbon heavy oil slurry is transported to the mixing tank and heated to 100°C. ZIF-8 (CAS:59061-53-9) is transported to the high-end carbon heavy oil slurry at 100°C and stirred for 1.5 hours. Then it is cooled to room temperature to obtain a mixture (the weight ratio of ZIF-8 (CAS:59061-53-9) to high-end carbon heavy oil slurry is 1:10).

[0188] Step (2): The obtained mixture is conveyed to a coke oven, where it is heated at 2°C / min. -1 The temperature is increased to 240℃ at a rate of [missing information] and held for 3 hours to complete the first coking treatment, and then [missing information] is increased at 5℃ / min [missing information]. -1 The temperature is increased to 510℃ and held for 10 hours to complete the second raw coke treatment. The coke is then cooled to room temperature to obtain petroleum coke. The obtained petroleum coke is crushed in a crushing device to a particle size of 0.2-0.3 mm.

[0189] Step (3): As Figure 1As shown, the centrifugal fan 9 is turned on, so that the pressure in the dewatering chamber 1 is 0.07-0.09MPa. The crushed petroleum coke enters the dewatering chamber 1 through the feed pipe 2 and falls onto the conveyor belt 3. As the conveyor belt 3 rotates, it is loosened by the vibration of the vibrator 13 (the interval between two adjacent vibrators 13 is 0.5m). At the same time, it is heated to 250℃ by the heater 4 to release water vapor to remove water. The evaporated water vapor comes into contact with the condenser plate 5 (the angle with the horizontal plane is 25°, and the distance between the condenser plate 5 and the feed pipe 2, the rear inner wall, the front inner wall and the rear inner wall of the dewatering chamber 1 is 10cm) to form condensate.

[0190] The condensate receiver 6 and the telescopic scraper 7 move horizontally from below the higher end of the condensate plate 5 to below the lower end of the condensate plate 5. The telescopic scraper 7 scrapes the condensate on the lower surface of the condensate plate 5 into the condensate receiver 6. After scraping, the condensate receiver 6 and the telescopic scraper 7 stop below the lower end of the condensate plate 5. The scraping is repeated once every 5 minutes.

[0191] After the dewatering process, the petroleum coke falls into the discharge pipe 8 and is discharged from the dewatering chamber 1. The discharged petroleum coke then enters the carbonization process.

[0192] Step (4): The petroleum coke discharged in step (3) enters a tubular furnace (carbonization furnace) filled with argon-hydrogen gas (the volume ratio of argon to hydrogen is 18:1), and is heated at 5°C / min. -1 The temperature was increased to 500℃ at a certain rate and held for 200 min to complete carbonization. After cooling, activated carbon precursor was obtained.

[0193] Step (5): The activated carbon precursor from step (4) is immersed in an activation solvent tank containing potassium hydroxide solution for 8 hours (the weight ratio of activated carbon precursor to potassium hydroxide in the activation solvent tank is 1:15, and the concentration of potassium hydroxide solution is 15g / 100ml). Then, it is taken out, dried, and sent to a tube furnace (activation equipment) filled with argon-hydrogen gas (the volume ratio of argon to hydrogen is 18:1), and activated at 2℃ for 1 minute. -1 The temperature was increased to 600℃ and held for 500 min to complete the activation. After cooling to room temperature, the activated carbon M4 was prepared by washing it four times with dilute hydrochloric acid (7% by mass) and then washing it four times with distilled water.

[0194] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M4 are shown in Table 1.

[0195] Example 5

[0196] Step (1): The high-end carbon heavy oil slurry is transported to the mixing tank and heated to 140°C. ZIF-8 (CAS:59061-53-9) is transported to the high-end carbon heavy oil slurry at 140°C and stirred for 2.5 hours. Then it is cooled to room temperature to obtain a mixture (the weight ratio of ZIF-8 (CAS:59061-53-9) to high-end carbon heavy oil slurry is 1:30).

[0197] Step (2): The obtained mixture is fed into a coke oven, where it is heated at 8°C / min. -1 The temperature is increased to 290℃ at a rate of [missing information] and held for 1.5 hours to complete the first coking treatment, and then [missing information] is increased at 1.5℃ per minute. -1 The temperature is increased to 490℃ and held for 15 hours to complete the second raw coke treatment. The coke is then cooled to room temperature to obtain petroleum coke. The obtained petroleum coke is crushed in a crushing device to a particle size of 0.2-0.3 mm.

[0198] Step (3): As Figure 1 As shown, the centrifugal fan 9 is turned on, so that the pressure in the dewatering chamber 1 is 0.07-0.09MPa. The crushed petroleum coke enters the dewatering chamber 1 through the feed pipe 2 and falls onto the conveyor belt 3. As the conveyor belt 3 rotates, it is loosened by the vibration of the vibrator 13 (the interval between two adjacent vibrators 13 is 1.5m). At the same time, it is heated to 100℃ by the heater 4 to release water vapor to remove water. The evaporated water vapor comes into contact with the condenser plate 5 (the angle with the horizontal plane is 70°, and the distance between the condenser plate 5 and the feed pipe 2, the rear inner wall, the front inner wall and the rear inner wall of the dewatering chamber 1 is 30cm) to form condensate.

[0199] The condensate receiver 6 and the telescopic scraper 7 move horizontally from below the higher end of the condensate plate 5 to below the lower end of the condensate plate 5. The telescopic scraper 7 scrapes the condensate on the lower surface of the condensate plate 5 into the condensate receiver 6. After scraping, the condensate receiver 6 and the telescopic scraper 7 stop below the lower end of the condensate plate 5. The scraping is repeated once every 15 minutes.

[0200] After the dewatering process, the petroleum coke falls into the discharge pipe 8 and is discharged from the dewatering chamber 1. The discharged petroleum coke then enters the carbonization process.

[0201] Step (4): The petroleum coke discharged in step (3) enters a tubular furnace (carbonization furnace) filled with argon-hydrogen gas (the volume ratio of argon to hydrogen is 18:1), and is heated at 1℃ / min. -1 The temperature was increased to 900℃ at a rate of 100℃ and held for 50 min to complete carbonization. After cooling, activated carbon precursor was obtained.

[0202] Step (5): The activated carbon precursor from step (4) is immersed in an activation solvent tank containing potassium hydroxide solution for 20 hours (the weight ratio of activated carbon precursor to potassium hydroxide in the activation solvent tank is 1:5, and the concentration of potassium hydroxide solution is 5g / 100ml). Then, it is taken out, dried, and sent to a tube furnace (activation equipment) filled with argon-hydrogen gas (the volume ratio of argon to hydrogen is 18:1), and activated at 8℃ for 1 minute. -1 The temperature was increased to 950℃ and held for 50 minutes to complete the activation. After cooling to room temperature, the activated carbon M5 was prepared by washing it four times with dilute hydrochloric acid (7% by mass) and then washing it four times with distilled water.

[0203] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M5 are shown in Table 1.

[0204] Example 6

[0205] Activated carbon was prepared according to the method of Example 1, except that in step (1), the weight ratio of ZIF-8 (CAS:59061-53-9) to high-end carbon heavy oil slurry was 1:5.

[0206] Activated carbon M6 was prepared.

[0207] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M6 are shown in Table 1.

[0208] Example 7

[0209] Activated carbon was prepared according to the method of Example 1, except that in step (1), heavy oil slurry (high-end carbon heavy oil slurry) was replaced with an equal amount of vacuum residue.

[0210] Activated carbon M7 was prepared.

[0211] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M7 are shown in Table 1.

[0212] Example 8

[0213] Activated carbon was prepared according to the method of Example 1, except that in step (2), the mixture was heated at 15°C for 1 minute. -1 The temperature was increased to 450℃ and held for 6 hours to complete the first coking process.

[0214] Activated carbon M8 was prepared.

[0215] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M8 are shown in Table 1.

[0216] Example 9

[0217] Activated carbon was prepared according to the method of Example 1, except that in step (2), the temperature was increased to 15°C for 1 minute. -1 The temperature is increased to 600℃ and held for 5 hours to complete the second coking process.

[0218] Activated carbon M9 was prepared.

[0219] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M9 are shown in Table 1.

[0220] Example 10

[0221] Activated carbon was prepared according to the method of Example 1, except that in step (4), the temperature was increased to 15°C for 1 minute. -1 The temperature was increased to 1100℃ at a certain rate and held for 350 minutes to complete carbonization.

[0222] Activated carbon M10 was prepared.

[0223] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M10 are shown in Table 1.

[0224] Example 11

[0225] Activated carbon was prepared according to the method of Example 1, except that in step (5), the temperature was increased to 15°C for 1 minute. -1 The temperature was increased to 1100℃ and held for 700 minutes to complete the activation.

[0226] Activated carbon M11 was prepared.

[0227] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M11 are shown in Table 1.

[0228] Example 12

[0229] Activated carbon was prepared according to the method of Example 1, except that in step (2), the first coking treatment was not performed, and the mixture was directly heated at 2°C / min in the coking oven. -1 The temperature is increased to 500℃ and held for 12 hours to complete the second coking process.

[0230] Activated carbon M12 was prepared.

[0231] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M12 are shown in Table 1.

[0232] Example 13

[0233] Activated carbon was prepared according to the method of Example 1, except that in step (3), the vibrator 13 was not installed.

[0234] Activated carbon M13 was prepared.

[0235] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon M13 are shown in Table 1.

[0236] Comparative Example 1

[0237] Activated carbon was prepared according to the method of Example 1, except that ZIF-8 (CAS: 59061-53-9) was not added in step (1).

[0238] Activated carbon D1 was prepared.

[0239] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon D1 are shown in Table 1.

[0240] Comparative Example 2

[0241] Activated carbon was prepared according to the method of Example 1, except that in step (1), ZIF-8 (CAS:59061-53-9) was replaced with an equal amount of needle coke.

[0242] Activated carbon D2 was prepared.

[0243] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon D2 are shown in Table 1.

[0244] Comparative Example 3

[0245] Activated carbon was prepared according to the method of Example 1, except that no oil slurry was added in step (1).

[0246] Activated carbon D3 was prepared.

[0247] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon D3 are shown in Table 1.

[0248] Comparative Example 4

[0249] Activated carbon was prepared according to the method of Example 1, except that step (3) was not performed.

[0250] Activated carbon D4 was prepared.

[0251] The results of the detection of N content, pore volume, specific surface area and pore size of activated carbon D4 are shown in Table 1.

[0252] Test Example 1

[0253] Raman spectroscopy analysis was performed on the activated carbon from the above examples and comparative examples.

[0254] The Raman spectrum of activated carbon M1 is as follows: Figure 2 As shown, from Figure 2 It can be seen that the two characteristic peaks of activated carbon M1 are located at 1345.6 cm⁻¹. -1(D-band) and 1587.6cm -1 (G band). The intensity ratio of these two characteristic peaks is approximately 0.99, indicating that MP-C still contains a large number of defects after calcination, which is beneficial for increasing the active sites for electrochemical reactions.

[0255] Test Example 2

[0256] Electrochemical tests were performed on the activated carbon from the above examples and comparative examples.

[0257] a. Electrode preparation: First, the activated carbon, acetylene black and polytetrafluoroethylene are mixed in a mass ratio of 8:1:1 and then spread evenly on the nickel foam, and then pressed into a circular electrode.

[0258] b. Electrode testing: Under room temperature conditions, a three-electrode system was used, with a saturated calomel electrode as the reference electrode, a platinum electrode as the auxiliary electrode, and a 30% KOH solution as the electrolyte solution. The disc electrode was first immersed in the electrolyte solution for 1 hour, and then the electrochemical performance was tested.

[0259] c. Cyclic voltammetry was performed using an Ivium-n-Stat electrochemical workstation to determine 1 A g. -1 Total specific capacitance at current density.

[0260] The test results are shown in Table 1.

[0261] Table 1

[0262] Example N content wt% Pore volume, cm3 / g 3 / g]]> Specific surface area m 2 / g]] Pore size nm Total specific capacitance (F / g) Example 1 2.3 0.66 1389.1 2.1 158.7 Example 2 2.2 0.61 1243.1 3.1 135.3 Example 3 2 0.57 1176.3 2.1 127.9 Example 4 2.9 0.63 1322.4 2 154.4 Example 5 1.8 0.61 1298.9 2 152.8 Example 6 7.9 0.83 1670.4 1.9 90.8 Example 7 2.1 0.45 1187.5 2.6 88.1 Example 8 2.2 0.5 927.3 2.9 119.7 Example 9 2.2 0.45 915.8 3.1 112.1 Example 10 2 0.48 833.3 3.2 108.8 Example 11 2 0.47 911.1 5.2 117.3 Example 12 2.3 0.29 1074.6 2.9 109.9 Example 13 2.1 0.4 841.3 2.6 86.5 Comparative Example 1 0.5 0.28 437.9 1.8 44.1 Comparative Example 2 0.41 0.46 866.1 1.7 98.3 Comparative Example 3 0.45 0.45 1602.8 1.8 96 Comparative Example 4 2.3 0.65 1341.5 2.1 151.1

[0263] As shown in Table 1, the activated carbon prepared in this invention exhibits a high specific capacitance for electrochemical capacitor electrodes, with a capacitance of 1 Ag. -1 The specific capacitance at current density can reach 158.7 F / g.

[0264] Compared to Example 2, which uses ZIF-67 and high-end carbon heavy oil slurry to prepare activated carbon, Example 7, which uses ZIF-8 and vacuum residue to prepare activated carbon, and Comparative Example 2, which uses needle coke and high-end carbon heavy oil slurry to prepare activated carbon, Example 1 uses ZIF-8 and high-end carbon heavy oil slurry to prepare activated carbon, which has a larger specific surface area and pore volume, and a pore size of 2.1 nm. The electrode used to prepare it has a higher specific capacitance.

[0265] Compared to Example 13, which does not have a vibrator installed under the conveyor belt, Example 1, which has a vibrator installed, is more conducive to improving the dehydration effect on petroleum coke, and the prepared activated carbon used in the electrode has a higher specific capacitance.

[0266] Compared to Comparative Example 3, which used ZIF-8 alone to prepare activated carbon, the activated carbon prepared in Example 1 using a blend of ZIF-8 and oil slurry exhibited a higher specific capacitance for use as an electrode in an electrochemical capacitor. Analysis suggests that while the activated carbon prepared using a standalone metal-organic framework possessed a higher specific surface area (reaching 1602.8 m²), the latter was less effective. 2 However, an excessively high specific surface area results in too many internal voids, making it difficult for the electrolyte to fully wet the surface, thus reducing the effective area and consequently lowering the specific capacitance.

[0267] Compared to Comparative Example 4, which did not use a dehydration device (i.e., the petroleum coke was not dehydrated), the activated carbon prepared by the dehydration device of the present invention in Example 1 has a more suitable pore volume and specific surface area, and the electrode used to prepare it has a higher specific capacitance.

[0268] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A petroleum coke dewatering device, characterized in that, The dewatering device includes a dewatering chamber (1), a feed pipe (2), a conveyor belt (3), a heater (4), a condenser plate (5), a condensate receiver (6), and a discharge pipe (8); The conveyor belt (3), the heater (4), the condenser plate (5) and the condensate receiver (6) are disposed inside the dewatering chamber (1); The feed pipe (2) extends into the dewatering chamber (1) and one end of it is located above one end of the conveyor belt (3) for feeding material into the dewatering chamber (1). The discharge pipe (8) is located at the other end of the conveyor belt (3) and extends out of the dewatering chamber (1) for discharging material. The conveyor belt (3) includes an upper belt and a lower belt, and the heater (4) is located below the upper belt for heating the petroleum coke on the conveyor belt (3) to evaporate and remove water. The condenser plate (5) is disposed above the conveyor belt (3) and is used to cool the water vapor formed by evaporation into condensate. The condensate receiver (6) is located below the condenser plate (5) and is used to collect the condensate.

2. The water removal device according to claim 1, characterized in that, The condenser plate (5) is inclined downward from one end near the feed pipe (2) to the other end near the discharge pipe (8), and the inclination angle is preferably 25-70°. Alternatively, the water removal device may also include a telescopic scraper (7), the lower end of which is connected to the condensate receiver (6) and the upper end of which abuts against the lower surface of the condensate plate (5), for scraping condensate into the condensate receiver (6); Preferably, the condensate receiver (6) is configured to reciprocate along the conveying direction of the conveyor belt (3) to carry the telescopic scraper (7) to scrape water from the lower surface of the condensate plate (5); Preferably, when the wiping action is performed, the telescopic squeegee (7) extends and contacts the lower surface of the condenser plate (5); when the wiping action is stopped, the telescopic squeegee (7) retracts and releases contact with the lower surface of the condenser plate (5); And / or, the dewatering device further includes a centrifugal fan (9), which is connected to the condensate receiver (6) via a drain line, for making the pressure inside the dewatering chamber (1) lower than the external pressure and for discharging the condensate inside the condensate receiver (6) from the dewatering chamber (1). And / or, the dewatering device further includes a vibrator (13) disposed below the upper belt of the conveyor belt (3) for vibrating the upper belt of the conveyor belt (3) to loosen the petroleum coke on the conveyor belt (3); And / or, the petroleum coke on the conveyor belt (3) is heated and dehydrated, discharged through the discharge pipe (8), and enters the carbonization furnace for carbonization treatment.

3. A method for removing water from petroleum coke, characterized in that, The dewatering method is implemented by the dewatering device described in claim 1 or 2, comprising: petroleum coke enters the dewatering chamber (1) through the feed pipe (2) and falls onto the conveyor belt (3), and as the conveyor belt (3) rotates, it is heated by the heater (4) to volatilize water vapor to remove water. The volatilized water vapor comes into contact with the condenser plate (5) to form condensate and is collected by the condensate receiver (6). The dewatered petroleum coke falls into the discharge pipe (8) and is discharged from the dewatering chamber (1). Preferably, the condensate receiver (6) carries a telescopic scraper (7) which moves from one end of the condensate plate (5) near the feed pipe (2) to one end near the discharge pipe (8) to scrape the condensate on the lower surface of the condensate plate (5) into the condensate receiver (6); Preferably, during the process of the condensate receiver (6) carrying the telescopic scraper (7) from one end of the condensate plate (5) near the discharge pipe (8) to one end near the feed pipe (2), the telescopic scraper (7) releases contact with the lower surface of the condensate plate (5); Preferably, when the condensate receiver (6) stops moving, the condensate receiver (6) is fixed below one end of the condenser plate (5) near the discharge pipe (8) to receive dripping condensate; And / or, the petroleum coke is heated to 100-250°C by the heater (4) as it passes through the conveyor belt (3); And / or, the pressure inside the dewatering chamber (1) is 0.07-0.09 MPa; And / or, the petroleum coke is crushed before entering the dewatering device, and the particle size after crushing is 0.18-0.4 mm, preferably 0.2-0.3 mm.

4. A method for preparing activated carbon, characterized in that, The method includes the following steps: Step (1): Mix the metal-organic framework and the oil slurry in a mixing tank to obtain a mixture; Step (2): The mixture obtained in step (1) is fed into a coking tower for coking treatment to obtain petroleum coke; Step (3): The petroleum coke obtained in step (2) is dehydrated by the dehydration device described in claim 1 or 2 or the dehydration method described in claim 3 to obtain dehydrated petroleum coke; Step (4): The dehydrated petroleum coke is fed into a carbonization furnace for carbonization treatment to obtain activated carbon precursor. Step (5): The activated carbon precursor is fed into an activation device for activation treatment to obtain the activated carbon.

5. The method according to claim 4, characterized in that, The specific surface area of ​​the metal-organic framework is ≥500 m². 2 / g, preferably 500-1500m 2 / g; And / or, the pore volume of the metal-organic framework is ≥0.2 cm³. 3 / g, preferably 0.3-1.2cm 3 / g; And / or, the pore size of the metal-organic framework is ≥0.2 nm, preferably 0.2-5 nm; And / or, the metal-organic framework includes at least one of IRMOF, CPL, ZIFs, MIL and UiO; And / or, the density of the oil slurry is ≥0.9 g / cm³. 3 ; And / or, the slurry includes at least one of catalytic cracking slurry, high-end carbon heavy oil slurry, bitumen, and residual oil; And / or, the weight ratio of the metal-organic framework to the slurry is 1:6-150, preferably 1:10-120; And / or, in step (1), the mixing conditions include: a mixing temperature of 50-160°C, preferably 100-140°C; and a mixing time of 1-3 hours, preferably 1.5-2.5 hours. And / or, before performing step (2), the mixture obtained in step (1) is cooled to room temperature.

6. The method according to claim 4 or 5, characterized in that, In step (2), the coking treatment method includes: performing a first coking treatment on the mixture under a first coking condition, then performing a second coking treatment under a second coking condition, and obtaining the petroleum coke after cooling; Preferably, the first coking conditions include: a first coking temperature of 200-300℃, more preferably 240-290℃; and a first coking time of 1-5 hours, more preferably 1.5-3 hours. Preferably, step (2) further includes: before performing the first coking treatment, heating at 1-10°C for 1 minute. -1 The mixture from step (1) is heated to the first coking temperature at a rate of 2-8°C / min; preferably at 2-8°C / min. -1 The temperature is increased at a rate to the first coking temperature; And / or, the second coking conditions include: a second coking temperature of 450-550℃, preferably 490-510℃; and a second coking time of 8-20h, preferably 10-15h. Preferably, step (2) further includes: before performing the second coking treatment, heating at 1-10°C for 1 minute. -1 The material after the first coking treatment is heated from the first coking temperature to the second coking temperature at a rate of 1.5-5℃ / min; preferably, this rate is 1.5-5℃ / min. -1 The temperature is increased at a rate to the second coking temperature; And / or, step (3) further includes: grinding the petroleum coke obtained in step (2) before dehydrating it, wherein the particle size after grinding is 0.18-0.4 mm, preferably 0.2-0.3 mm.

7. The method according to any one of claims 4-6, characterized in that, In step (4), the carbonization process is carried out in an argon-hydrogen mixed atmosphere or an inert atmosphere; preferably, it is carried out in an argon-hydrogen mixed atmosphere. Preferably, the carbonization conditions include: a carbonization temperature of 400-1000℃, more preferably 500-900℃; and a carbonization time of 0.5-300 min, more preferably 50-200 min. Preferably, step (4) further includes: before the carbonization treatment, heating the petroleum coke after dehydration in step (3) at 0.5-10℃ for 1 minute. -1 The temperature is increased to the carbonization temperature at a rate of 1-5°C / min, preferably 1-5°C / min. -1 The temperature is increased to the carbonization temperature at a rate that allows it to rise. And / or, the method further includes cooling the activated carbon precursor to room temperature before performing step (5).

8. The method according to any one of claims 4-7, characterized in that, In step (5), the activation treatment method includes: immersing the activated carbon precursor in an activating agent solution, then taking it out and activating it; Preferably, the activation conditions include: an activation temperature of 400-1000℃, more preferably 600-950℃; and an activation time of 0.5-600 min, more preferably 60-500 min. Preferably, step (5) further includes: before activation, immersing the activated carbon precursor taken from the activator solution at 0.5-10°C for min. -1 The temperature is increased to the activation temperature at a rate of 2-8°C / min; preferably at a rate of 2-8°C / min. -1 The temperature is increased to the activation temperature at a rate that allows it to rise. More preferably, the activation treatment method in step (5) further includes: drying the activated carbon precursor taken from the activator solution and then heating it; And / or, the activator includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate; And / or, the weight ratio of the activated carbon precursor to the activator is 1:0.2-50, preferably 1:5-15; And / or, the concentration of the activator solution is 1-20 g / 100 ml, preferably 2-15 g / 100 ml; And / or, the impregnation time is 5-30 hours, preferably 8-20 hours; And / or, step (5) further includes: cooling and washing the activated carbon obtained from the activation treatment; Preferably, the washing method is to perform acid washing and water washing in sequence; Preferably, the number of pickling cycles is 3-5 times, and the number of water washing cycles is 3-5 times.

9. Activated carbon prepared by the method of any one of claims 4-8; Preferably, the N content in the activated carbon is 0.1-15% by weight, more preferably 1-8%, and even more preferably 1.5-3%. And / or, the pore volume of the activated carbon is 0.1-2.1 cm³. 3 / g, preferably 0.5-0.7cm 3 / g; And / or, the specific surface area of ​​the activated carbon is 300-2000 m². 2 / g, preferably 1000-1500m 2 / g.

10. An electrode for an electrochemical capacitor, characterized in that, The electrode is made from the activated carbon as described in claim 9; Preferably, the electrode further includes a conductive agent, a binder, and a conductive substrate; More preferably, the weight ratio of the activated carbon, the conductive agent, and the binder is 4-12: 0.5-3:1, preferably 6-10:0.5-2:1.

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