CN210656168U - Equipment for producing thin graphene on large scale - Google Patents
Equipment for producing thin graphene on large scale Download PDFInfo
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- CN210656168U CN210656168U CN201921445428.1U CN201921445428U CN210656168U CN 210656168 U CN210656168 U CN 210656168U CN 201921445428 U CN201921445428 U CN 201921445428U CN 210656168 U CN210656168 U CN 210656168U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Carbon And Carbon Compounds (AREA)
Abstract
The utility model relates to a scale production thin layer graphite alkene equipment. The apparatus includes a gas stream milling system for milling graphite; the supercritical stripping system is used for stripping the ground graphite in a supercritical state to obtain coarse graphene; and the grading system is used for grading the coarse graphene to obtain the thin-layer graphene meeting the requirement of the layer number. The graphite can be crushed into micron-sized coarse products by utilizing the equipment in an air flow grinding mode, the advantages of short preparation time, no pollution, simple process and the like are utilized by utilizing a supercritical fluid stripping method, the functionalized coarse products are stripped, and the condition of incomplete graphite stripping can also exist by innovatively combining the air flow grinding stripping method with the supercritical fluid method, so that the graphene coarse products are graded by the grading device, the graphite and the graphene can be separated, the functionalized graphene with different layers and sizes can be obtained, the cost is lower, the production efficiency is high, and the commercialization degree is high.
Description
Technical Field
The utility model relates to a graphite alkene production facility technical field especially relates to scale production thin layer graphite alkene equipment.
Background
Graphene is a monolayer of carbon atoms employing sp2Two-dimensional (2D) atomic crystals obtained by hybridization, discovered in 2004 by geom and Novoselov et al, have thus won the prize on the physics of 2010 nobel. Then, the graphene becomes the materialThe fields of science and physics are new stars rising. Since then, graphene has become a new star in the fields of material science and physics. Since then, graphene has many properties that exceed those of other existing materials, such as an ultra-large specific surface area, extremely fast electron mobility, high ultra-modulus, high strength, ultra-high thermal conductivity, ultra-low visible light absorbance, capability of withstanding extremely high current, impermeability to any gas, and convenience in chemical modification. Due to the excellent performance of graphene, the graphene has been developed in the fields of physics, optics, materials science, new energy, electronic information, computers, aerospace and the like. But the implementation of these applications is dependent on low cost, large scale preparation of high quality graphene.
The low-cost and large-scale production of high-quality graphene is extremely important. Therefore, how to strip the graphene without reunion is quite critical, and how to keep the few-layer high-purity powder. Due to strong pi-pi bond attraction among graphene sheet layers, the produced graphene powder is easy to stack layer by layer, so that the originally separated sheet layers are reunited. Therefore, when graphene is compounded with a material or a matrix, not only dispersion is difficult, but also due to the inertia of graphene, the interaction between graphene and other materials is weak, and the unique advantages of graphene are difficult to exert.
Today, graphene is mainly prepared in two ways, "Bottom-Up" and "Top-Down". The mode of "from bottom to top" refers to the growth of graphene on a substrate by a process such as catalysis from a carbon-containing compound. At present, Chemical Vapor Deposition (CVD), epitaxial growth, and the like are mainly used. The bottom-up method can prepare high-quality and large-sheet graphene, and is difficult to realize industrialization and large-scale production due to harsh production conditions and high cost. The preparation of the graphene from top to bottom refers to that graphite is used as a raw material, and Van der Waals acting force between graphite layers is destroyed through a physical means (mechanical force, ultrasonic wave, thermal stress, microwave and the like) or a chemical method (intercalation of molecules, ions, atomic groups and the like) to separate the graphite layers, so that the graphene is obtained. Therefore, such methods can be further subdivided into chemical intercalation methods (redox methods, etc.) and mechanical exfoliation methods (ultrasonic exfoliation, abrasive exfoliation, supercritical fluid exfoliation, gas flow exfoliation, etc.). The redox method is simple to operate and can be used for mass production, but the prepared graphene contains a large amount of oxygen-containing functional groups, the conductivity and other properties are poor, and even after reduction, the graphene also contains a large amount of defects; furthermore, a large amount of foreign species such as intercalation agents, oxidizing agents, reducing agents and the like are added in the production process of the redox method and are difficult to remove, so that the industrialization process is limited. Thus, mechanical exfoliation methods have received much attention, particularly grinding exfoliation and supercritical fluid exfoliation, which allow large-scale production of thin-layer graphene.
The air flow grinding and stripping method has attracted much attention in recent years, and graphene obtained by stripping is widely applied to energy fields such as catalysts, lithium batteries and solar batteries. The grinding and stripping method is to strip graphite by using collision and shearing action to prepare graphene. In the grinding process, the graphite can be subjected to two actions of shearing and vertical impact, and the shearing action force can be graphite stripping, so that the graphite stripping is an ideal mechanical force for preparing large-size graphene. The vertical impact action can then be broken into small particles with graphite, which can promote graphite stripping, but is not favorable for producing large-area graphene, and amorphous carbon can be formed to influence the overall performance of graphene products.
The supercritical fluid exfoliation method is to adopt a dispersing agent (such as dinitrophenol, sodium dodecyl sulfate, N-dimethylformamide, N-methylpyrrolidone and the like), a supercritical fluid (such as carbon dioxide, water, nitrogen and the like) and a cleaning agent (such as ethanol, methanol and the like), adjust the properties of viscosity, density, diffusion coefficient and the like of a solvent in a critical state through temperature, pressure and the like in the critical state, intercalate graphite by utilizing high dispersibility and strong permeability of the solvent, rapidly release pressure after a period of time, rapidly expand a graphite interlayer solvent, enlarge interlayer distance and achieve graphite exfoliation to obtain graphene. The supercritical fluid stripping method has high efficiency and can be used for large-scale production, and the obtained graphene also has high conductivity. In addition, the flexibility is strong, different additives can be added to obtain different products, but the graphene layers obtained by the supercritical fluid stripping method are different in number and cannot be completely stripped, and the number of thin-layer graphene is small. The problems that graphene products are easy to stack and agglomerate and are difficult to disperse in the using process exist.
Therefore, new methods and apparatuses are needed for the mass production of thin-layer functionalized graphene, particularly for cost reduction and efficiency improvement, and commercialization.
SUMMERY OF THE UTILITY MODEL
The technical problem to be solved
The to-be-solved technical problem of the utility model is: provides a device for producing thin-layer graphene in a large scale.
Two technical schemes
In order to solve the technical problem, the utility model provides a following technical scheme:
the equipment for producing the thin-layer graphene in large scale comprises:
the airflow grinding system is used for grinding the graphite;
the supercritical stripping system is used for stripping the ground graphite in a supercritical state to obtain coarse graphene; and
and the grading system is used for grading the coarse graphene to obtain the thin-layer graphene meeting the requirement of the layer number.
Preferably, the gas flow grinding system comprises a gas flow grinder and a compressed gas source device for pumping compressed gas into the gas flow grinder; wherein the compressed air source apparatus comprises:
a gas storage device (12);
the gas compression device (13) is used for compressing the gas in the gas storage device (12) and conveying the gas to the jet mill; and
and an air flow control device (14) for controlling the flow of air delivered into the jet mill.
Preferably, the gas stream mill is a fluidized bed gas stream mill;
the gas storage device (12) is a compressed gas tank;
the gas compression device (13) is a centrifugal compression pump;
the gas flow control device (14) is a flow control valve.
Preferably, the supercritical stripping system comprises a high-pressure resistant reaction device with a stirring device, a pressure reduction container, a gas medium conveying device, a liquid medium conveying device, a temperature detection device and a pressure detection device;
the gas medium conveying device is used for compressing and heating gas and pumping the compressed and heated gas into the high-pressure resistant reaction device;
the liquid medium conveying device is used for compressing liquid and pumping the compressed liquid into the high-pressure resistant reaction device;
the high-pressure resistant reaction device is used for stirring the graphite ground by the airflow grinding system in a supercritical state of a gas medium and a liquid medium;
the pressure reduction container is used for relieving the pressure of the high-pressure resistant reaction device after the stirring is finished;
the temperature detection device is used for detecting the temperature inside the high-pressure resistant reaction device;
the pressure detection device is used for detecting the pressure inside the high-pressure resistant reaction device.
Preferably, the high-pressure resistant reaction device is a high-pressure resistant reaction kettle;
the pressure reduction container is a pressure reduction kettle;
the liquid medium conveying device comprises a liquid storage tank for storing the liquid medium, a centrifugal compression pump for pressurizing the liquid medium and providing conveying power, and a flow control valve for controlling the flow of the liquid conveyed into the pressure-resistant reaction device;
the gas medium conveying device comprises a gas storage tank for storing a gas medium, a centrifugal compression pump for compressing the gas medium and providing conveying power, a heat exchanger for heating the gas medium, and a flow control valve for controlling the flow of the gas conveyed into the high-pressure resistant reaction device.
Preferably, the classification system comprises a plurality of cyclones, which are in series communication.
Preferably, the number of cyclones is from 3 to 5.
Preferably, the high-layer thick graphite or graphene collected by the first-stage cyclone separator is introduced into the grinding system again for grinding; and
the high-layer thick graphite or graphene collected by the second-stage cyclone separator is introduced into the supercritical system again for stripping.
Preferably, the outer layer of the cyclone separator is provided with a heating nest.
Preferably, the apparatus further comprises a drying system for drying the graphite.
Three beneficial effects
The above technical scheme of the utility model has following advantage:
utilize the utility model provides an equipment can smash into the thick result of micron order with graphite with the mode that the air current ground, it is short to utilize supercritical fluid to peel off the legal system preparation time, pollution-free, advantages such as simple process, peel off the thick product of functionalization, grind the organic combination of peeling off method and supercritical fluid method through innovatively with the air current, also can exist and peel off the incomplete condition to graphite, consequently, classify the thick product of graphite alkene through grading plant, not only can separate graphite and graphite alkene, still can obtain the functional graphite alkene of different numbers of piles and equidimension, be applied to different fields.
The utility model provides an equipment combines production method but large-scale production thin layer functionalized graphene, and the cost is lower, and production efficiency is high, and the commercialization degree is high.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for mass production of thin-layer graphene according to the present invention.
In the figure:
11: an air current grinder; 12: a gas storage device; 13: a gas compression device; 14: an airflow control device;
21: a high pressure resistant reaction device; 22: a pressure reducing vessel; 23: a liquid storage tank; 24: a first centrifugal compression pump; 25: a liquid flow control valve; 26: a gas storage tank; 27: a second centrifugal compression pump; 28: a heat exchanger; 29: a flow control valve;
31: a cyclone separator; 32: a product collection tank;
41: a centrifugal pump; 42: a condenser; 43: and a solvent collection tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "lateral", "longitudinal", "up", "down", "front", "back", "left", "right", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The utility model provides a scale production thin layer graphite alkene equipment. The structure of the apparatus is explained in detail below with reference to fig. 1.
The utility model provides a this equipment includes air current grinding system, supercritical stripping system and grading system. The air flow grinding system is used for grinding graphite. The supercritical stripping system is used for stripping the ground graphite in a supercritical state to obtain the coarse graphene. The grading system is used for grading coarse graphene to obtain thin-layer graphene meeting the requirement of the layer number.
Specifically, the airflow grinding system comprises an airflow grinder 11 and a compressed air source device for injecting compressed air into the airflow grinder 11, wherein a classifier is arranged in the airflow grinder 11, the grade of the classifier is set according to standards, and the airflow grinder cannot enter the next process when the grade is not reached in the grinding process and then continues grinding. Wherein the compressed air source apparatus comprises: a gas storage device 12; the gas compression device 13 is used for compressing the gas in the gas storage device 12 and conveying the gas to the jet mill 11; and a gas flow control device 14 for controlling the flow of gas delivered into the jet mill 11.
During production, raw material graphite is added into the airflow grinder 11, compressed gas is pumped at high speed by using compressed gas source equipment, so that the graphite in the airflow grinder 11 is fluidized and collides with each other, and a functionalized coarse product is obtained after grinding for a period of time. The graphite includes but is not limited to natural graphite, artificial graphite, expanded graphite, thermal cracking graphite, etc., and natural graphite is preferred, so that the production cost can be reduced. The compressed gas to be injected includes, but is not limited to, inert gases such as air, carbon dioxide, nitrogen, etc. The inventor finds that the optimal process conditions for the air flow grinding of graphite are as follows: the crushing pressure is between 0.5 and 1MPa, and the gas flow input into the jet mill 11 is 500-3The grinding time is 10min-24h, and the rotation speed of the classifier is 1000-. And (3) grinding the raw material by air flow under the conditions of the crushing pressure, the air flow, the rotating speed of the classifier and the grinding time, wherein the granularity of the coarse product obtained by grinding is close to 2 microns, but the agglomeration phenomenon of graphite cannot occur. The jet mill 11 is operated in a manner including, but not limited to, a fluidized bed, a screw type, and preferably a fluidized bed type jet mill, and its operation parameters such as pulverizing pressure, grinding time, and classifier rotation speed are set under appropriate conditions. The utility model discloses can with the help of gas compression device 13 with the gas compression in the gas storage device 12 to required pressure then squeeze into the air current and grind the machine 11 in, can squeeze into the air current with the help of the control of air flow control device 14 and grind the gas flow in the machine 11 in the suitable range. More specifically, theThe gas storage device 12 may be a compressed gas tank, the gas compression device 13 may be a centrifugal compression pump, and the gas flow control device 14 may be a flow control valve.
Specifically, the supercritical stripping system includes a high-pressure-resistant reaction apparatus 21 equipped with a stirring apparatus, a pressure-reducing container 22, a gas medium transport apparatus, a liquid medium transport apparatus, a temperature detection apparatus, and a pressure detection apparatus. The gas medium conveying device is used for compressing and heating gas and driving the compressed and heated gas medium into the high-pressure resistant reaction device 21. The liquid medium conveying device is used for compressing liquid and driving the compressed liquid medium into the high pressure resistant reaction device 21. The high pressure resistant reaction device 21 is used for stirring the graphite ground by the gas flow grinding system in a supercritical state of a gas medium and a liquid medium. The decompression vessel 22 is used for decompressing the high pressure resistant reaction apparatus 21 after completion of the stirring. The temperature detection device is used for detecting the temperature inside the high pressure resistant reaction device 21. The pressure detection device is used for detecting the pressure inside the high pressure resistant reaction device 21. The high pressure resistant reaction device 21 may be a high pressure resistant reaction kettle. The depressurization vessel 22 can be a depressurization kettle. The liquid medium delivery device comprises a liquid storage tank 23 for storing the liquid medium, a first centrifugal compression pump 24 for pressurizing the liquid medium and providing delivery power, and a liquid flow control valve 25 for controlling the flow of the liquid delivered into the pressure-resistant reaction device. The gas medium delivery device comprises a gas storage tank 26 for storing the gas medium, a second centrifugal compressor 27 for compressing the gas medium and providing delivery power, a heat exchanger 28 for heating the gas medium, and a flow control valve 29 for controlling the flow of the gas delivered into the high pressure resistant reaction device 21.
In the production, the crude product obtained by gas stream milling is introduced into a high pressure resistant reaction apparatus 21 (e.g. a high pressure resistant reaction vessel), one or more kinds of previously heated mixed media (including a gas medium and a liquid medium) are introduced, and when a predetermined pressure value is reached, the media are brought into a supercritical state. Stirring for a period of time, beatingThe pressure reduction valve is opened to let the material enter the pressure reduction container 22, so that the pressure is reduced to normal pressure or even lower pressure in a short time. And (3) expanding the supercritical medium, releasing energy to overcome the van der Waals acting force between graphite layers, and obtaining the coarse graphene. The medium comprises a gaseous medium and a liquid medium. The gaseous medium comprises any one or more of carbon dioxide, ammonia, butane and butene mixtures, nitrogen, sulphur hexafluoride. The liquid medium comprises any one or more of water, methanol, ethanol, isopropanol, dinitrophenol, sodium dodecylsulphonate, sodium dodecylsulphate, N-dimethylformamide, N-methylpyrrolidone. Mass percentage content x of liquid medium in gas mediumLiquid for treating urinary tract infectionThe values of (A) are as follows: x is more than 0Liquid for treating urinary tract infectionLess than or equal to 10 percent. When carbon dioxide is used as a gas medium, because the critical parameters (304.5K, 7.3MPa) of the carbon dioxide are low, the energy consumption can be reduced, the service life of the high-pressure resistant reaction kettle is prolonged, and the cost is reduced, and any one or more media of 0 (not 0-10% (mass ratio) of water, a butane and butylene mixture, methanol, ethanol, isopropanol, ammonia gas, nitrogen gas, N-dimethylformamide, N-methylpyrrolidone and sulfur hexafluoride can be added into the carbon dioxide. The temperature or pressure of the high pressure resistant reaction device 21 (such as a high pressure resistant reaction kettle) or the addition of other media can be adjusted to change the physical and chemical properties of the supercritical fluid, match the type, critical pressure and critical temperature of the crude product, and be more beneficial to the dispersion of the crude product and the intercalation of the supercritical fluid to graphite. The pressure in the pressure reducing vessel 22 may be such that a certain amount of gas is pumped out to a pressure of 0.01-0.1MPa before the pressure reducing valve is opened. After the pressure reduction of the material is completed, the pressure is converted to normal pressure, and the temperature is preferably maintained above the boiling point of other media.
Specifically, the grading system comprises a plurality of cyclones 31, the plurality of cyclones 31 are sequentially communicated, and the thin graphene obtained through grading can be collected in a product collection tank 32 for later use. In order to separate graphene with different layers and sizes, a cyclone separator is adopted to grade the coarse graphene. The utility model provides an it adopts multistage cyclone to carry out a lot of grades to thick graphite alkene to this is established to obtain the functional graphite alkene of the different number of piles and equidimension not, can be applied to different fields, can obtain the most excellent thin layer functional graphite alkene in suitable hierarchical position. Preferably, the present invention provides such apparatus with a heating nest in the outer cyclone layer to maintain the temperature above the boiling point of the other media.
The number of the cyclone separators is preferably 3 to 5, that is, multi-stage separation is performed using 3 to 5 stages of cyclone separators. In order to improve the production efficiency, a circulating production line can be added: introducing the thick graphite or graphene collected in the cyclone separator of the 1 st stage into the airflow grinding system (specifically, an airflow grinding device in the airflow grinding system, such as an airflow grinder) for airflow grinding; and introducing the thick graphite or graphene collected in the 2 nd-stage cyclone separator into a supercritical stripping system (specifically a high-pressure-resistant reaction device such as a high-pressure-resistant reaction kettle) for supercritical stripping.
In addition, the medium separated by the last stage cyclone separator can be recovered, namely, the equipment provided by the utility model also comprises a medium recovery system; the medium recovery system comprises a centrifugal pump 41 and a condenser 42, wherein the centrifugal pump 41 is a power device, the medium passing through the condenser 2 realizes gas-liquid separation, the gas medium can be conveyed to the gas storage tank 26, and the liquid medium can be conveyed to the solvent collection tank 43 for storage and standby.
Most comprehensively, the utility model provides a this equipment includes:
the airflow grinding system is used for grinding the graphite; the supercritical stripping system is used for stripping the ground graphite in a supercritical state to obtain coarse graphene; the grading system is used for grading the coarse graphene to obtain thin-layer graphene meeting the requirement of the layer number;
the gas flow grinding system comprises a gas flow grinder 11 and a compressed gas source device for injecting compressed gas into the gas flow grinder 11; the compressed air source device comprises: a gas storage device 12; the gas compression device 13 is used for compressing the gas in the gas storage device 12 and conveying the gas to the jet mill 11; an air flow control device 14 for controlling the flow of air delivered into the jet mill 11; the gas flow grinder 11 is a fluidized bed type gas flow grinder; the gas storage device 12 is a compressed gas tank; the gas compression device 13 is a centrifugal compression pump; the airflow control device 14 is a flow control valve;
the supercritical stripping system comprises a high-pressure resistant reaction device 21 with a stirring device, a pressure reduction container 22, a gas medium conveying device, a liquid medium conveying device, a temperature detection device and a pressure detection device; the gas medium conveying device is used for compressing and heating gas and pumping the compressed and heated gas into the high-pressure resistant reaction device 21; the liquid medium conveying device is used for compressing liquid and driving the compressed liquid into the high pressure resistant reaction device 21; the high-pressure resistant reaction device 21 is used for stirring the graphite ground by the gas flow grinding system in a supercritical state of a gas medium and a liquid medium; the decompression container 22 is used for decompressing the high-pressure-resistant reaction device 21 after stirring is finished; the temperature detection device is used for detecting the temperature inside the high-pressure resistant reaction device 21; the pressure detection device is used for detecting the pressure inside the high-pressure resistant reaction device 21; the high pressure resistant reaction device 21 is a high pressure resistant reaction kettle; the decompression container 22 is a decompression kettle; the liquid medium conveying device comprises a liquid storage tank 23 for storing the liquid medium, a first centrifugal compression pump 24 for pressurizing the liquid medium and providing conveying power, and a liquid flow control valve 25 for controlling the flow of the liquid conveyed into the pressure-resistant reaction device; the gas medium conveying device comprises a gas storage tank 26 for storing a gas medium, a second centrifugal compression pump 27 for compressing the gas medium and providing conveying power, a heat exchanger 28 for heating the gas medium, and a flow control valve 29 for controlling the flow of the gas conveyed into the high pressure resistant reaction device 21;
the grading system comprises a plurality of cyclone separators 31, and the cyclone separators 31 are communicated in sequence; the number of the cyclone separators 31 is 3 to 5; the high-layer thick graphite or graphene collected by the cyclone separator 31 of the first stage is introduced into the airflow grinding system for grinding; the high-layer thick graphite or graphene collected by the cyclone separator 31 of the second stage is introduced into the supercritical stripping system for stripping; the outer layer of the cyclone separator 31 is provided with a heating nest.
On the basis of the above, the device can be improved by one or more of the following steps:
a drying system for drying graphite is added;
a medium recovery system for recovering the medium separated by the last stage cyclone separator is added; the medium recovery system comprises a centrifugal pump 41 and a condenser 42, wherein the centrifugal pump 41 is a power device, the medium passing through the condenser 2 realizes gas-liquid separation, the gas medium can be conveyed to the gas storage tank 26, and the liquid medium can be conveyed to the solvent collection tank 43 for storage and standby.
Examples
The embodiment provides an apparatus for mass production of thin-layer graphene, and referring to fig. 1, the apparatus includes:
the airflow grinding system is used for grinding the graphite; the supercritical stripping system is used for stripping the ground graphite in a supercritical state to obtain coarse graphene; the grading system is used for grading the coarse graphene to obtain thin-layer graphene meeting the requirement of the layer number;
the gas flow grinding system comprises a gas flow grinder 11 and a compressed gas source device for injecting compressed gas into the gas flow grinder 11; the compressed air source device comprises: a gas storage device 12; the gas compression device 13 is used for compressing the gas in the gas storage device 12 and conveying the gas to the jet mill 11; an air flow control device 14 for controlling the flow of air delivered into the jet mill 11; the gas flow grinder 11 is a fluidized bed type gas flow grinder; the gas storage device 12 is a compressed gas tank; the gas compression device 13 is a centrifugal compression pump; the airflow control device 14 is a flow control valve;
the supercritical stripping system comprises a high-pressure resistant reaction device 21 with a stirring device, a pressure reduction container 22, a gas medium conveying device, a liquid medium conveying device, a temperature detection device and a pressure detection device; the gas medium conveying device is used for compressing and heating gas and pumping the compressed and heated gas into the high-pressure resistant reaction device 21; the liquid medium conveying device is used for compressing liquid and driving the compressed liquid into the high pressure resistant reaction device 21; the high-pressure resistant reaction device 21 is used for stirring the graphite ground by the gas flow grinding system in a supercritical state of a gas medium and a liquid medium; the decompression container 22 is used for decompressing the high-pressure-resistant reaction device 21 after stirring is finished; the temperature detection device is used for detecting the temperature inside the high-pressure resistant reaction device 21; the pressure detection device is used for detecting the pressure inside the high-pressure resistant reaction device 21; the high pressure resistant reaction device 21 is a high pressure resistant reaction kettle; the decompression container 22 is a decompression kettle; the liquid medium conveying device comprises a liquid storage tank 23 for storing the liquid medium, a first centrifugal compression pump 24 for pressurizing the liquid medium and providing conveying power, and a liquid flow control valve 25 for controlling the flow of the liquid conveyed into the pressure-resistant reaction device; the gas medium conveying device comprises a gas storage tank 26 for storing a gas medium, a second centrifugal compression pump 27 for compressing the gas medium and providing conveying power, a heat exchanger 28 for heating the gas medium, and a flow control valve 29 for controlling the flow of the gas conveyed into the high pressure resistant reaction device 21;
the grading system comprises a plurality of cyclone separators 31, and the cyclone separators 31 are communicated in sequence; the number of the cyclone separators 31 is 3 to 5; the high-layer thick graphite or graphene collected by the cyclone separator 31 of the first stage is introduced into the airflow grinding system for grinding; the high-layer thick graphite or graphene collected by the cyclone separator 31 of the second stage is introduced into the supercritical stripping system for stripping; the outer layer of the cyclone separator 31 is provided with a heating nest;
the equipment also comprises a drying system for drying the graphite;
the equipment also comprises a medium recovery system for recovering the medium separated by the last stage of cyclone separator; the medium recovery system comprises a centrifugal pump 41 and a condenser 42, wherein the centrifugal pump 41 is a power device, the medium passing through the condenser 2 realizes gas-liquid separation, the gas medium can be conveyed to the gas storage tank 26, and the liquid medium can be conveyed to the solvent collection tank 43 for storage and standby.
The method for producing graphene by using the equipment provided by the embodiment comprises the following steps:
s1, adding natural graphite into an airflow grinding machine, and then pumping compressed air with the pressure of 0.8MPa to fluidize the natural graphite and mutually collide the natural graphite to realize airflow grinding, wherein the airflow grinding process conditions are as follows: pressure 0.8MPa, gas flow 3000m3And h, grinding time is 16h, the rotating speed of a grader is 10000rpm, and a functionalized coarse product is obtained after grinding is finished, is micron-sized non-few-layer graphene, has granularity close to 2 microns, is uniformly dispersed and is not easy to agglomerate.
S2, supercritical stripping: introducing the functionalized crude product prepared in the step (1) into a high-pressure-resistant reaction kettle, introducing a preheated medium, and changing the physical and chemical properties of the supercritical fluid by adjusting the temperature or pressure of a high-pressure-resistant reaction device or the addition of the medium so as to match the critical pressure and the critical temperature of the functionalized crude product; when the pressure value reaches a preset pressure value, enabling the medium to enter a supercritical state, stirring, opening a pressure reducing valve to enable the material to enter a pressure reducing container, and reducing the pressure to normal pressure or lower to obtain coarse graphene; before the pressure reducing valve is opened, the pressure in the pressure reducing container is adjusted to be 0.06MPa, and after the pressure reduction of the material is finished, the pressure is adjusted to be normal pressure; the temperature in the pressure reduction vessel is maintained at a temperature equal to or higher than the boiling point of the liquid medium.
S3, grading: classifying the coarse graphene prepared in the step (2) for 4 times by using a 4-stage cyclone separator to obtain thin graphene with 1-5 layers, wherein the granularity is not more than 2 microns; carrying out airflow grinding on the thick graphite or graphene collected in the 1 st-stage cyclone separator again; and carrying out supercritical stripping on the thick graphite or graphene collected in the 2 nd-stage cyclone separator again; during the classification process, the cyclone is heated to maintain the temperature of the cyclone above the boiling point of the liquid medium.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention in its corresponding aspects.
Claims (10)
1. The equipment for producing the thin-layer graphene in a large scale is characterized by comprising the following steps:
the airflow grinding system is used for grinding the graphite;
the supercritical stripping system is used for stripping the ground graphite in a supercritical state to obtain coarse graphene; and
and the grading system is used for grading the coarse graphene to obtain the thin-layer graphene meeting the requirement of the layer number.
2. The apparatus according to claim 1, characterized in that said gas-flow grinding system comprises a gas-flow grinder (11) and a compressed gas source apparatus for feeding compressed gas into the gas-flow grinder (11); wherein the compressed air source apparatus comprises:
a gas storage device (12);
the gas compression device (13) is used for compressing the gas in the gas storage device (12) and conveying the gas to the gas flow grinding machine (11); and
an air flow control device (14) for controlling the flow of air delivered into the air flow mill (11).
3. The apparatus according to claim 2, characterized in that the gas-flow mill (11) is a fluidized-bed gas-flow mill;
the gas storage device (12) is a compressed gas tank;
the gas compression device (13) is a centrifugal compression pump;
the gas flow control device (14) is a flow control valve.
4. The apparatus according to claim 1, wherein the supercritical stripping system comprises a high pressure resistant reaction device (21) with a stirring device, a pressure reducing vessel (22), a gaseous medium conveying device, a liquid medium conveying device, a temperature detecting device and a pressure detecting device;
the gas medium conveying device is used for compressing and heating gas and pumping the compressed and heated gas into the high-pressure resistant reaction device (21);
the liquid medium conveying device is used for compressing liquid and driving the compressed liquid into the high-pressure resistant reaction device (21);
the high-pressure resistant reaction device (21) is used for stirring the graphite ground by the airflow grinding system in a supercritical state of a gas medium and a liquid medium;
the decompression container (22) is used for decompressing the high-pressure-resistant reaction device (21) after stirring is finished;
the temperature detection device is used for detecting the temperature inside the high-pressure resistant reaction device (21);
the pressure detection device is used for detecting the pressure inside the high-pressure resistant reaction device (21).
5. The apparatus according to claim 4, characterized in that the high pressure resistant reaction device (21) is a high pressure resistant reaction vessel;
the decompression container (22) is a decompression kettle;
the liquid medium conveying device comprises a liquid storage tank (23) for storing the liquid medium, a first centrifugal compression pump (24) for pressurizing the liquid medium and providing conveying power, and a liquid flow control valve (25) for controlling the flow of the liquid conveyed into the high-pressure-resistant reaction device (21);
the gas medium conveying device comprises a gas storage tank (26) for storing the gas medium, a second centrifugal compression pump (27) for compressing the gas medium and providing conveying power, a heat exchanger (28) for heating the gas medium, and a flow control valve (29) for controlling the flow of the gas conveyed into the high-pressure resistant reaction device (21).
6. The apparatus according to claim 1 to, characterized in that the classification system comprises a plurality of cyclones (31), the plurality of cyclones (31) being in communication in series.
7. The apparatus according to claim 6, characterized in that the number of cyclones (31) is 3 to 5.
8. The apparatus according to claim 6, characterized in that the high-layer thick graphite or graphene collected by the cyclone separator (31) of the first stage is introduced into the gas stream grinding system for grinding; and
the high-layer thick graphite or graphene collected by the cyclone separator (31) of the second stage is introduced into the supercritical stripping system for stripping.
9. The apparatus according to claim 6, characterized in that the outer layer of the cyclone separator (31) is provided with a heating nest.
10. The apparatus of claim 1, further comprising a drying system for drying graphite.
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