WO2017190570A1 - Large-scale clean preparation method for graphene - Google Patents

Large-scale clean preparation method for graphene Download PDF

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WO2017190570A1
WO2017190570A1 PCT/CN2017/078376 CN2017078376W WO2017190570A1 WO 2017190570 A1 WO2017190570 A1 WO 2017190570A1 CN 2017078376 W CN2017078376 W CN 2017078376W WO 2017190570 A1 WO2017190570 A1 WO 2017190570A1
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graphene
graphite
nozzle
chamber
suspension
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PCT/CN2017/078376
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French (fr)
Chinese (zh)
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陈庆
曾军堂
廖大应
陈兵
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成都新柯力化工科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/04—Specific amount of layers or specific thickness

Definitions

  • the invention relates to a method for preparing graphene, in particular to a method for large-scale clean preparation of graphene.
  • Graphene is a planar structural material composed of a single atomic thickness of carbon atoms bonded by sp2 bonds.
  • the carbon-carbon bond length is about 0.142 nm, and there are three ⁇ bonds in each crystal lattice.
  • the p orbitals of all carbon atoms. Both are perpendicular to the sp 2 hybrid plane and form a delocalized ⁇ bond throughout the graphene side by side. In theory, this has a perfect hexagonal mesh structure and exhibits excellent electronic stability, thermal conductivity, optical properties, and mechanical properties. Since the discovery of graphene, due to its excellent performance and huge market application prospects, it has led to research booms in the fields of physics and materials science, making graphene have a very broad development prospect.
  • the preparation methods of graphene mainly include mechanical exfoliation method, epitaxial growth method, graphite oxide reduction method, chemical vapor deposition and the like. Since the preparation process of the graphite oxide reduction method is relatively simple, it is widely used by researchers. However, graphene synthesized by this method has many defects and oxidized groups, which limits its application in electronic devices.
  • the mechanical stripping method can best preserve the properties of graphene, and the preparation method is simple, and the preparation process is environmentally friendly and non-polluting.
  • the graphene preparation method widely used in the scientific research field is more and more popular in actual production.
  • the spray drying method is a method for preparing a nano dry powder by continuous atmospheric pressure, which uses a special device to spray the liquid material into a mist, which is dried in contact with hot air.
  • the method has the advantages of fast drying speed, high product purity, good quality, good uniformity, fluidity and solubility. If the spray drying method is applied to the production of graphene, the defects of the current mechanical stripping method will be overcome, and a graphene product with high purity and uniformity can be obtained. And the production process is clean and environmentally friendly.
  • Chinese Patent Application No. 201410846369.4 discloses an apparatus for producing graphene by spray drying and microwave, and a production process thereof, which comprises graphite in H 2 Under the action of strong acid and strong oxidant such as SO 4 and HNO 3 , or under electrochemical peroxidation, hydrolyzed to form an aqueous solution of graphite oxide with a concentration of 0.1-50%; the raw material of the aqueous graphite oxide solution is dried by a peristaltic pump through an atomizer. In the indoor, the atomized state material is dissociated by microwave, and the material is reduced into flocculent and easy-flying graphene.
  • strong acid and strong oxidant such as SO 4 and HNO 3
  • electrochemical peroxidation hydrolyzed to form an aqueous solution of graphite oxide with a concentration of 0.1-50%
  • the raw material of the aqueous graphite oxide solution is dried by a peristaltic pump through an atomizer.
  • the atomized state material
  • the graphene after reduction is collected with the flowing air into the cyclone collecting device, and the material is loaded into the packaging bag through the wind shutoff discharge device.
  • this method still uses a strong oxidizing agent to treat graphite, destroying the surface electronic topography of graphene, grafting a group such as a hydroxyl group or a carboxyl group, increasing the electrical resistance of graphene, and the use of a strong oxidizing agent also causes environmental pollution, and Bring safety hazards to the preparation staff.
  • Chinese Patent Application No. 201510777025.7 discloses a preparation method of large-sized graphene oxide or graphene, which under the action of intercalating agent and expanding agent, fully releases interlayer space to weaken interlayer interaction force, and obtain The graphene aggregates are dried by a spray drying method to obtain a graphene material.
  • the raw material of the invention is cheap, the process is simple and easy to control, the solid-liquid separation is fast and efficient, and the industrialized large-scale production is facilitated, and the destruction of the crystal structure of the graphene oxide by high-energy ultrasonic waves, high-speed shearing or fluid pulverization is also avoided.
  • the method needs to wait for the graphite intercalation to be completed, and after the stripping is completed, it is spray-dried, that is, it cannot be continuously produced, and the production efficiency of graphene is lowered, so that the application is limited.
  • the spray drying method is mostly used in the final step of graphene production, that is, the graphene solution which has been stripped is dried to prepare graphene powder.
  • the strong oxidant is treated with graphite
  • the surface of the prepared graphene is grafted with a polar group, which is harmful to human health and causes environmental pollution, destroys the lattice integrity of the graphene, and reduces the conductivity of the system. Therefore, from the perspective of industrial demand, we need a large-scale, high-efficiency, zero-pollution integrated spray drying method for preparing graphene.
  • the spray drying method is mostly used in the final step of graphene production, that is, the graphene solution which has been stripped is dried to prepare graphene powder. Moreover, if the strong oxidant is treated with graphite, the surface of the prepared graphene is grafted with polar groups, which is harmful to human health and causes environmental pollution, destroying the lattice integrity of graphene and reducing the lattice integrity. The electrical conductivity of the system. Therefore, from the perspective of industrial demand, we need a large-scale, high-efficiency, zero-pollution integrated spray drying method for preparing graphene.
  • the spray drying method is mostly used for drying graphene solution to prepare graphene powder. Moreover, if the strong oxidant is treated with graphite, the surface of the prepared graphene is grafted with a polar group, which is harmful to human health and causes environmental pollution, destroys the lattice integrity of the graphene, and reduces the conductivity of the system. If the stripping process of graphene or the chemical reduction process of graphene can also be carried out in a spray dryer, continuous mass production of graphene can be achieved.
  • the invention provides a method for large-scale clean preparation of graphene, fully utilizes a spray drying device, integrates mechanical stripping and powder drying into a spray dryer, thereby realizing continuous, stable and environmentally clean preparation of graphene materials, and nanometer graphite.
  • the olefin powder or micro-graphene powder is restricted in the drying chamber to ensure the health and life safety of the operator, which makes the graphene production chain clean and environmentally friendly, further promoting the industrial production of graphene dry powder.
  • the present invention adopts the following technical solutions:
  • a method for large-scale clean preparation of graphene is as follows:
  • the feed port is in communication with the feed chamber, and at least one ultrasonic probe is disposed inside the feed chamber, and the ultrasonic power is set to 100.
  • the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, in the feed chamber
  • At least one air compressor is disposed inside, and the dispersion suspension is pressurized by the air compressor, and the dispersion suspension accelerates forward flow, and the delivery chamber is connected with the drying chamber, and the dispersion is suspended after ultrasonic treatment. Liquid flowing from the feed chamber into the drying chamber;
  • At least one ultrasonic probe is provided at the nozzle of the spray device, the ultrasonic power is set to be 100-500 KW, and a mechanical force is provided to cause ultrasonication of the graphite at the nozzle.
  • the graphite raw material is at least one of flake graphite, expanded graphite, highly oriented graphite, pyrolytic graphite, and graphite oxide, and the graphite raw material has an average particle diameter of less than 1 mm;
  • the foaming agent Is at least one of sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogencarbonate, ammonium phosphate;
  • the surfactant is twelve At least one of sodium alkyl sulfate, sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, and 1-pyridyl acid.
  • the air flow rate in the air compressor described in the step (2) is 3-10 m/s.
  • the gas in step (3) is one or more of nitrogen, argon and carbon dioxide.
  • the nozzle has a size of 5 to 10 mm.
  • a graphene collector is provided at the end of the drying chamber to collect graphene.
  • the existing spray drying method produces graphene.
  • the spray drying method is mostly used for drying graphene solution to prepare graphene powder. Dust pollution is serious during the production process, and continuous production of graphene cannot be achieved.
  • the strong oxidant is treated with graphite, the surface of the prepared graphene is grafted with a polar group, which is harmful to human health and causes environmental pollution, destroys the lattice integrity of the graphene, and reduces the conductivity of the system.
  • the stripping process of graphene or the chemical reduction process of graphene can also be carried out in a spray dryer, continuous mass production of graphene can be achieved.
  • the invention provides a method for large-scale clean preparation of graphene, fully utilizes a spray drying device, integrates mechanical stripping and powder drying into a spray dryer, thereby realizing continuous, stable and environmentally clean preparation of graphene materials, and nanometer graphite.
  • the olefin powder or micro-graphene powder is restricted in the drying chamber to ensure the health and life safety of the operator, making the graphene production chain clean and environmentally friendly, and promoting the industrial production of the graphene dry powder.
  • the shear stripping is completed in one step, and the dispersion is uniformized, thereby not only retaining the layer structure of the graphene to the utmost extent, but also continuously and stably preparing the graphene material without destroying the surface electrical topology symmetry of the graphene, further The quality of the finished graphene is guaranteed.
  • the present invention proposes a graphene prepared by a method for large-scale clean preparation of graphene as shown in Table 1.
  • the invention integrates mechanical peeling and powder drying in a spray dryer to realize continuous, stable and environmentally clean preparation of graphene materials, and to limit nano graphene powder or micro graphene powder in a drying chamber.
  • the treatment ensures the health and safety of the operators, making the graphene production chain clean and environmentally friendly, and promoting the industrial production of graphene dry powder.
  • the invention provides an ultrasonic device at the nozzle, provides higher energy for the graphite system through the cavitation of the ultrasonic, increases the probability of the graphite being intercalated, increases the intercalation effect of the foaming agent, and then increases the decomposition of the blowing agent at a high temperature.
  • the spacing between the graphite layers, the graphite is stripped to obtain graphene, and the surface electrical symmetry of the graphene is not destroyed, further ensuring the quality of the finished graphene.
  • the graphene microchip material prepared by the method of the invention does not cause environmental pollution and meets environmental protection requirements.
  • Figure 1 is a schematic view showing the outline of a scaled clean preparation graphene device.
  • 1-feed port 2-feed chamber; 3-drying chamber; 4-air compressor; 5,6-ultrasonic probe; 7-nozzle.
  • the feed port is in communication with the feed chamber, and an ultrasonic probe is disposed inside the feed chamber, and the ultrasonic power is set to 100 KW.
  • the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one space is disposed inside the transfer chamber.
  • a gas addition nozzle is arranged on the top of the drying chamber, the gas pressure is 0.18 MPa, the chamber temperature is 100 ° C, the heating nitrogen temperature is 200 ° C, and a nozzle having a size of 5 mm is disposed at the top of the drying chamber.
  • the dispersed suspension flows through the nozzle, enters the drying chamber and is atomized by the heated gas.
  • the sodium carbonate is decomposed by heat to release gas, and the distance between the graphite layers is increased.
  • the graphite is rapidly stripped under high-speed airflow, further
  • One skilled in the art can provide at least one ultrasonic probe at the nozzle of the spray device as needed to provide mechanical force to ultrasonically cavitation the graphite at the nozzle.
  • an ultrasonic probe is disposed at the nozzle of the spray device, and the ultrasonic power is set to 100 KW.
  • a graphene collector was placed at the end of the drying chamber to collect graphene.
  • the obtained graphene had a peeling rate of 90%, a graphene particle diameter of 1.8 ⁇ m, a thickness of 0.3 nm, and a uniform lateral size distribution.
  • the feed port is in communication with the feed chamber, and an ultrasonic probe is disposed inside the feed chamber, and the ultrasonic power is set to 100 KW.
  • the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one space is disposed inside the transfer chamber.
  • the obtained graphene had a peeling rate of 90%, a graphene particle diameter of 1.3 ⁇ m, a thickness of 0.5 nm, and a uniform lateral size distribution.
  • the feed port is connected to the feed chamber, and two ultrasonic probes are arranged inside the feed chamber, and the ultrasonic power is set to 200 KW.
  • the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one air pressure is disposed inside the feed chamber.
  • the air flow rate in the air compressor is 6m/s
  • the dispersion suspension is pressurized by the air compressor
  • the dispersion suspension accelerates forward flow
  • the feed chamber communicates with the drying chamber
  • the dispersion is suspended after sonication.
  • the liquid flows from the feed chamber into the drying chamber.
  • a gas addition nozzle is arranged on the top of the drying chamber, the gas pressure is 0.3 MPa, the chamber temperature is 100 ° C, the heating nitrogen temperature is 200 ° C, and a nozzle having a size of 5 mm is disposed at the top of the drying chamber.
  • the dispersed suspension flows through the nozzle, enters the drying chamber and is atomized by the heated gas.
  • the sodium carbonate is decomposed by heat to release gas, and the distance between the graphite layers is increased.
  • the graphite is rapidly stripped under high-speed airflow, further
  • One skilled in the art can provide at least one ultrasonic probe at the nozzle of the spray device as needed to provide mechanical force to ultrasonically cavitation the graphite at the nozzle.
  • an ultrasonic probe is disposed at the nozzle of the spray device, and the ultrasonic power is set to 300 KW.
  • a graphene collector was placed at the end of the drying chamber to collect graphene.
  • the obtained graphene had a peeling rate of 90%, a graphene particle diameter of 2.4 ⁇ m, a thickness of 0.3 nm, and a uniform lateral size distribution.
  • the feed port is connected to the feed chamber, and two ultrasonic probes are arranged inside the feed chamber, and the ultrasonic power is set to 200 KW.
  • the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one air pressure is disposed inside the feed chamber.
  • a gas addition nozzle is arranged at the top of the drying chamber, the gas pressure is 0.4 MPa, the chamber temperature is 150 ° C, the heating nitrogen temperature is 300 ° C, and a nozzle of a size of 10 mm is disposed at the top of the drying chamber, and is dispersed.
  • the turbid liquid flows through the nozzle, enters the drying chamber and is atomized by the heated gas.
  • the sodium carbonate and sodium hydrogencarbonate are decomposed by heat to release the gas, and the distance between the graphite layers is increased. After atomization foaming, the graphite is fast under high-speed airflow.
  • Speed stripping further, one skilled in the art can provide at least one ultrasonic probe at the spray device nozzle as needed to provide mechanical force to ultrasonically cavitation of graphite at the nozzle.
  • an ultrasonic probe is disposed at the nozzle of the spray device, and the ultrasonic power is set to 300 KW.
  • a graphene collector was placed at the end of the drying chamber to collect graphene.
  • the obtained graphene had a peeling rate of 90%, a graphene particle diameter of 2.6 ⁇ m, a thickness of 0.3 nm, and a uniform lateral size distribution.
  • the feed port is connected to the feed chamber, and two ultrasonic probes are arranged inside the feed chamber, and the ultrasonic power is set to 500 KW.
  • the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one air pressure is disposed inside the feed chamber.
  • one skilled in the art can provide at least one ultrasonic probe at the nozzle of the spray device as needed to provide mechanical force to ultrasonically cavitation the graphite at the nozzle.
  • two ultrasonic probes are disposed at the nozzle of the spray device, and the ultrasonic power is set to 500 KW.
  • a graphene collector was placed at the end of the drying chamber to collect graphene.
  • the obtained graphene had a peeling rate of 90%, a graphene particle diameter of 0.8 ⁇ m, a thickness of 0.3 nm, and a uniform lateral size distribution.
  • the invention provides a method for large-scale clean preparation of graphene, fully utilizes a spray drying device, integrates mechanical stripping and powder drying into a spray dryer, thereby realizing continuous, stable and environmentally clean preparation of graphene materials, and nanometer graphite.
  • the olefin powder or micro-graphene powder is restricted in the drying chamber to ensure the health and life safety of the operator, which makes the graphene production chain clean and environmentally friendly, further promoting the industrial production of graphene dry powder.

Abstract

Provided is a large-scale clean preparation method for graphene, comprising: (i) preparing graphite raw material, water, foaming agent and surfactant into a suspension and stirring the suspension at a rotating speed of 300-500rpm to disperse the graphite raw material uniformly to obtain a dispersed suspension; (ii) feeding the dispersed suspension into a feed inlet (1) of a spraying device, the feed inlet communicating with a conveying chamber (2), the conveying chamber being internally provided with at least one ultrasonic probe (5); the dispersed suspension being subjected to ultrasonic treatment so that the foaming agent enters layers of graphite; the conveying chamber being internally provided with at least one air compressor (4) for pressurizing the dispersed suspension to accelerate the dispersed suspension to flow forward; the conveying chamber communicating with a drying chamber (3), and the dispersed suspension after treatment flowing into the drying chamber; and (iii) arranging a gas heating nozzle and at least one nozzle (7) at the top of the drying chamber; the dispersed suspension flowing through the nozzle and entering the drying chamber to be atomized by heated gas; the foaming agent being decomposed by heat so that interlayer spacing of graphite is increased; and after atomization and foaming, obtaining the graphene stripped off under a high-speed air flow. Preferably, at least one ultrasonic probe (6) is arranged at the nozzle. According to the method, two processes, i.e., mechanical stripping and drying, are integrated into a spray dryer and an ultrasonic device is arranged at the nozzle, thus providing graphite with a higher energy, increase the intercalating probability and improving the intercalating effect of the foaming agent. Hence, product quality is ensured and, environmental protection and no-pollution are achieved.

Description

一种规模化清洁制备石墨烯的方法Method for large-scale clean preparation of graphene 技术领域Technical field
本发明涉及一种制备石墨烯的方法，具体涉及一种规模化清洁制备石墨烯的方法。The invention relates to a method for preparing graphene, in particular to a method for large-scale clean preparation of graphene.
背景技术Background technique
2004年，英国曼彻斯特大学的两位科学家使用微机械剥离的方法发现了石墨烯，并于2010年获得了诺贝尔物理学奖。石墨烯为一种由sp2键结合而成的单一原子厚度的碳原子构成的平面结构材料，碳-碳键长约为0.142nm，每个晶格内有三个σ键，所有碳原子的p轨道均与sp2杂化平面垂直，且以肩并肩的方式形成一个离域π键贯穿整个石墨烯。理论上，这种具有完美六角网状构造，呈现优异的电子稳定性、导热性、光性能、力学性能。自石墨烯被发现后，由于其优异的性能和巨大的市场应用前景引发了物理和材料科学等领域的研究热潮，使石墨烯拥有十分广阔的发展前景。In 2004, two scientists at the University of Manchester in the United Kingdom discovered graphene using micromechanical stripping and won the Nobel Prize in Physics in 2010. Graphene is a planar structural material composed of a single atomic thickness of carbon atoms bonded by sp2 bonds. The carbon-carbon bond length is about 0.142 nm, and there are three σ bonds in each crystal lattice. The p orbitals of all carbon atoms. Both are perpendicular to the sp 2 hybrid plane and form a delocalized π bond throughout the graphene side by side. In theory, this has a perfect hexagonal mesh structure and exhibits excellent electronic stability, thermal conductivity, optical properties, and mechanical properties. Since the discovery of graphene, due to its excellent performance and huge market application prospects, it has led to research booms in the fields of physics and materials science, making graphene have a very broad development prospect.
大规模制备获得稳定存在的石墨烯是石墨烯产业化的前提条件。目前，石墨烯的制备方法主要有，机械剥离法、外延生长法、氧化石墨还原法、化学气相沉积等方法。由于氧化石墨还原法的制备过程相对简单，其被研究者大量的使用。但通过该法合成的石墨烯的缺陷和氧化基团较多，限制了其在电子器件方面的应用。机械剥离法能够最佳地保存石墨烯的性质，并且制备方法简单，制备过程环保无污染，在科研领域是广泛使用的石墨烯制备方法，在实际的生产中也越来越备受青睐。比如曼彻斯特大学的海姆利用胶带从碳素材料上分离得到石墨烯。虽然这种剥离石墨烯的方法简单，但是只能产出数量有限的石墨烯。因此，现在迫切需要开发出一种可以大规模化生产石墨烯的制备方法。喷雾干燥法为连续式常压制备纳米干粉的一种方法，其采用特殊设备将液料喷成雾状，使其与热空气接触而被干燥。该方法具有干燥速度快，产品纯度高，质量好，具有良好的均匀度、流动性和溶解性。如果将喷雾干燥法应用于石墨烯的生产，将克服目前机械剥离法的缺陷，并且获得纯度高、均匀度好的石墨烯产品 ，而且生产过程清洁环保。Large-scale preparation to obtain stable graphene is a prerequisite for the industrialization of graphene. At present, the preparation methods of graphene mainly include mechanical exfoliation method, epitaxial growth method, graphite oxide reduction method, chemical vapor deposition and the like. Since the preparation process of the graphite oxide reduction method is relatively simple, it is widely used by researchers. However, graphene synthesized by this method has many defects and oxidized groups, which limits its application in electronic devices. The mechanical stripping method can best preserve the properties of graphene, and the preparation method is simple, and the preparation process is environmentally friendly and non-polluting. The graphene preparation method widely used in the scientific research field is more and more popular in actual production. For example, Heim of the University of Manchester used tape to separate graphene from carbonaceous materials. Although this method of stripping graphene is simple, only a limited amount of graphene can be produced. Therefore, there is an urgent need to develop a preparation method capable of producing graphene on a large scale. The spray drying method is a method for preparing a nano dry powder by continuous atmospheric pressure, which uses a special device to spray the liquid material into a mist, which is dried in contact with hot air. The method has the advantages of fast drying speed, high product purity, good quality, good uniformity, fluidity and solubility. If the spray drying method is applied to the production of graphene, the defects of the current mechanical stripping method will be overcome, and a graphene product with high purity and uniformity can be obtained. And the production process is clean and environmentally friendly.
为了实现清洁环保地大规模剥离石墨获得石墨烯，现有技术中，中国发明专利申请号201410846369.4公开了一种利用喷雾干燥及微波生产石墨烯的设备及其生产工艺，该方法将石墨在H2SO4、HNO3等强酸和强氧化剂的作用下，或电化学过氧化作用下，经水解后形成浓度为0.1-50％的氧化石墨水溶液；氧化石墨水溶液原料由蠕动泵经雾化器进入干燥室内，雾化状态的物料经微波解离，物料还原为絮状易飞扬的石墨烯，还原之后的石墨烯随流动空气进入旋风收集装置收集，物料通过关风卸料器装入包装袋内。然而，该方法仍然使用强氧化剂处理石墨，破坏了石墨烯的表面电子态拓扑结构，接枝了羟基或羧基等基团，增加石墨烯的电阻，而且强氧化剂的使用也会造成环境污染，并给制备工作人员带来安全隐患。In order to achieve clean and environmentally large scale stripping of graphite to obtain graphene, in the prior art, Chinese Patent Application No. 201410846369.4 discloses an apparatus for producing graphene by spray drying and microwave, and a production process thereof, which comprises graphite in H 2 Under the action of strong acid and strong oxidant such as SO 4 and HNO 3 , or under electrochemical peroxidation, hydrolyzed to form an aqueous solution of graphite oxide with a concentration of 0.1-50%; the raw material of the aqueous graphite oxide solution is dried by a peristaltic pump through an atomizer. In the indoor, the atomized state material is dissociated by microwave, and the material is reduced into flocculent and easy-flying graphene. The graphene after reduction is collected with the flowing air into the cyclone collecting device, and the material is loaded into the packaging bag through the wind shutoff discharge device. However, this method still uses a strong oxidizing agent to treat graphite, destroying the surface electronic topography of graphene, grafting a group such as a hydroxyl group or a carboxyl group, increasing the electrical resistance of graphene, and the use of a strong oxidizing agent also causes environmental pollution, and Bring safety hazards to the preparation staff.
中国发明专利申请号201510777025.7公开了一种大尺寸氧化石墨烯或石墨烯的制备方法，该发明石墨在插层剂和膨胀剂的作用下，充分释放层间空间以削弱层间相互作用力，得到石墨烯聚集体，再采用喷雾干燥法对石墨烯干燥处理，获得石墨烯材料。本发明原料廉价，过程简单、易控，固液分离快速高效，便于工业化大规模生产，同时也避免了高能超声波、高速剪切或流体粉碎对氧化石墨烯晶体结构的破坏。然而，该方法在生产过程中，需要等待石墨插层完毕，剥离完毕后在经过喷雾干燥，即不能够连续化生产，降低石墨烯的生产效率，使得应用受到局限。Chinese Patent Application No. 201510777025.7 discloses a preparation method of large-sized graphene oxide or graphene, which under the action of intercalating agent and expanding agent, fully releases interlayer space to weaken interlayer interaction force, and obtain The graphene aggregates are dried by a spray drying method to obtain a graphene material. The raw material of the invention is cheap, the process is simple and easy to control, the solid-liquid separation is fast and efficient, and the industrialized large-scale production is facilitated, and the destruction of the crystal structure of the graphene oxide by high-energy ultrasonic waves, high-speed shearing or fluid pulverization is also avoided. However, in the production process, the method needs to wait for the graphite intercalation to be completed, and after the stripping is completed, it is spray-dried, that is, it cannot be continuously produced, and the production efficiency of graphene is lowered, so that the application is limited.
根据上述，喷雾干燥法多用于石墨烯生产的最后一步，即将已经剥离的石墨烯溶液干燥制备石墨烯粉末。而且如果强氧化剂对石墨处理，使制备的石墨烯表面接枝极性基团，危害人体健康并且导致环境污染，破坏了石墨烯的晶格完整性，降低了体系的导电能力。因此，从产业需求的角度考虑，我们更需要一种规模化、高效率、零污染地一体化喷雾干燥制备石墨烯的方法。According to the above, the spray drying method is mostly used in the final step of graphene production, that is, the graphene solution which has been stripped is dried to prepare graphene powder. Moreover, if the strong oxidant is treated with graphite, the surface of the prepared graphene is grafted with a polar group, which is harmful to human health and causes environmental pollution, destroys the lattice integrity of the graphene, and reduces the conductivity of the system. Therefore, from the perspective of industrial demand, we need a large-scale, high-efficiency, zero-pollution integrated spray drying method for preparing graphene.
技术问题technical problem
喷雾干燥法多用于石墨烯生产的最后一步，即将已经剥离的石墨烯溶液干燥制备石墨烯粉末。而且如果强氧化剂对石墨处理，使制备的石墨烯表面接枝极性基团，危害人体健康并且导致环境污染，破坏了石墨烯的晶格完整性，降低了 体系的导电能力。因此，从产业需求的角度考虑，我们更需要一种规模化、高效率、零污染地一体化喷雾干燥制备石墨烯的方法。The spray drying method is mostly used in the final step of graphene production, that is, the graphene solution which has been stripped is dried to prepare graphene powder. Moreover, if the strong oxidant is treated with graphite, the surface of the prepared graphene is grafted with polar groups, which is harmful to human health and causes environmental pollution, destroying the lattice integrity of graphene and reducing the lattice integrity. The electrical conductivity of the system. Therefore, from the perspective of industrial demand, we need a large-scale, high-efficiency, zero-pollution integrated spray drying method for preparing graphene.
问题的解决方案Problem solution
技术解决方案Technical solution
针对目前利用喷雾干燥法生产石墨烯的技术路线，喷雾干燥法多用于将石墨烯溶液干燥制备石墨烯粉末。而且如果强氧化剂对石墨处理，使制备的石墨烯表面接枝极性基团，危害人体健康并且导致环境污染，破坏了石墨烯的晶格完整性，降低了体系的导电能力。如果在喷雾干燥机中也可以进行石墨烯的剥离过程，或者石墨烯的化学还原过程，这样就可以实现石墨烯的连续化大规模生产。本发明提出一种规模化清洁制备石墨烯的方法，充分利用了喷雾干燥设备，将机械剥离与粉末干燥集成在喷雾干燥机中，从而实现连续稳定、环保清洁地制备石墨烯材料，将纳米石墨烯粉或微米石墨烯粉限制在干燥腔室中处理，保证了操作人员的身体健康和生命安全，使得石墨烯生产链清洁环保，进一步推动了石墨烯干粉的产业化生产。In view of the current technical route for producing graphene by spray drying, the spray drying method is mostly used for drying graphene solution to prepare graphene powder. Moreover, if the strong oxidant is treated with graphite, the surface of the prepared graphene is grafted with a polar group, which is harmful to human health and causes environmental pollution, destroys the lattice integrity of the graphene, and reduces the conductivity of the system. If the stripping process of graphene or the chemical reduction process of graphene can also be carried out in a spray dryer, continuous mass production of graphene can be achieved. The invention provides a method for large-scale clean preparation of graphene, fully utilizes a spray drying device, integrates mechanical stripping and powder drying into a spray dryer, thereby realizing continuous, stable and environmentally clean preparation of graphene materials, and nanometer graphite. The olefin powder or micro-graphene powder is restricted in the drying chamber to ensure the health and life safety of the operator, which makes the graphene production chain clean and environmentally friendly, further promoting the industrial production of graphene dry powder.
为解决上述问题，本发明采用以下技术方案：In order to solve the above problems, the present invention adopts the following technical solutions:
一种规模化清洁制备石墨烯的方法，具体方法如下：A method for large-scale clean preparation of graphene, the specific method is as follows:
(1)将10-25重量份石墨原料、50-60重量份水、1.5-15重量份发泡剂、1.5-5重量份表面活性剂配制成分散悬浊液，以300-500rpm的转速搅拌分散10-25min，至所述石墨原料在溶剂中分散均匀，得到分散悬浊液；(1) 10-25 parts by weight of graphite raw material, 50-60 parts by weight of water, 1.5-15 parts by weight of a foaming agent, 1.5-5 parts by weight of a surfactant are formulated into a dispersion suspension, and stirred at 300-500 rpm. Dispersing for 10-25 min until the graphite raw material is uniformly dispersed in a solvent to obtain a dispersed suspension;
(2)将步骤(1)得到的分散悬浊溶液加入喷雾装置进料口，所述进料口与输料室连通，在所述输料室内部设置至少一个超声探头，设置超声功率为100-500KW，在分散悬浊溶液从所述进料口进入输料室后，分散悬浊液经过超声处理，让发泡剂进入石墨层间，降低石墨层间作用力，在所述输料室内部设置至少一个空压机，通过所述空压机对分散悬浊液加压，分散悬浊液加速向前流动，所述输料室与干燥室相连通，经超声处理后的分散悬浊液从所述输料室流动进入所述干燥腔室；(2) adding the dispersed suspension solution obtained in the step (1) to the feed port of the spray device, the feed port is in communication with the feed chamber, and at least one ultrasonic probe is disposed inside the feed chamber, and the ultrasonic power is set to 100. -500 KW, after the dispersed suspension solution enters the feed chamber from the feed port, the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, in the feed chamber At least one air compressor is disposed inside, and the dispersion suspension is pressurized by the air compressor, and the dispersion suspension accelerates forward flow, and the delivery chamber is connected with the drying chamber, and the dispersion is suspended after ultrasonic treatment. Liquid flowing from the feed chamber into the drying chamber;
(3)在所述干燥腔室顶设置气体加喷口，保持气压为0.1-0.5MPa，腔体温度为100-150℃，加热气体温度为200-400℃，所述干燥腔室顶端设置至少一个喷嘴， 经分散悬浊液流经所述喷嘴，进入所述干燥腔室后被加热气体雾化，发泡剂受热分解释放出气体，石墨层间距增加，经过雾化发泡，石墨在高速气流下被快速剥离，获得石墨烯。(3) providing a gas addition nozzle at the top of the drying chamber, maintaining a gas pressure of 0.1-0.5 MPa, a chamber temperature of 100-150 ° C, a heating gas temperature of 200-400 ° C, and setting at least one of the top ends of the drying chamber Nozzle, The dispersed suspension flows through the nozzle, enters the drying chamber, and is atomized by the heated gas. The foaming agent is decomposed by heat to release gas, and the distance between the graphite layers is increased. After atomization foaming, the graphite is subjected to high-speed airflow. Rapid stripping to obtain graphene.
优选地，所述喷雾装置喷嘴处设置至少一个超声探头，设置超声功率为100-500KW，提供机械力，以使石墨在所述喷嘴处超声空化。Preferably, at least one ultrasonic probe is provided at the nozzle of the spray device, the ultrasonic power is set to be 100-500 KW, and a mechanical force is provided to cause ultrasonication of the graphite at the nozzle.
优选地，所述的石墨原料为鳞片石墨、膨胀石墨、高取向石墨、热裂解石墨、氧化石墨中的至少一种，所述石墨原料的平均粒径为小于1毫米；所述的发泡剂为碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氯化铵、硫酸铵、硫酸氢铵、碳酸铵、碳酸氢铵、磷酸铵中的至少一种；所述的表面活性剂为十二烷基硫酸钠、十二烷基苯磺酸钠、聚乙烯吡咯烷酮、1-吡啶酸中的至少一种。Preferably, the graphite raw material is at least one of flake graphite, expanded graphite, highly oriented graphite, pyrolytic graphite, and graphite oxide, and the graphite raw material has an average particle diameter of less than 1 mm; the foaming agent Is at least one of sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogencarbonate, ammonium phosphate; the surfactant is twelve At least one of sodium alkyl sulfate, sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, and 1-pyridyl acid.
优选地，步骤(2)中所述的空压机中的空气流速为3-10m/s。Preferably, the air flow rate in the air compressor described in the step (2) is 3-10 m/s.
优选地，步骤(3)中气体为氮气、氩气和二氧化碳中的一种或几种。Preferably, the gas in step (3) is one or more of nitrogen, argon and carbon dioxide.
优选地，所述喷嘴尺寸5～10mm。Preferably, the nozzle has a size of 5 to 10 mm.
优选地，在干燥腔室的末端设置石墨烯收集器，收集石墨烯。Preferably, a graphene collector is provided at the end of the drying chamber to collect graphene.
现有的喷雾干燥法生产石墨烯的技术路线，喷雾干燥法多用于将石墨烯溶液干燥制备石墨烯粉末。产过程粉尘污染严重，不能够实现石墨烯的连续化生产。而且如果强氧化剂对石墨处理，使制备的石墨烯表面接枝极性基团，危害人体健康并且导致环境污染，破坏了石墨烯的晶格完整性，降低了体系的导电能力。如果在喷雾干燥机中也可以进行石墨烯的剥离过程，或者石墨烯的化学还原过程，这样就可以实现石墨烯的连续化大规模生产。本发明提出一种规模化清洁制备石墨烯的方法，充分利用了喷雾干燥设备，将机械剥离与粉末干燥集成在喷雾干燥机中，从而实现连续稳定、环保清洁地制备石墨烯材料，将纳米石墨烯粉或微米石墨烯粉限制在干燥腔室中处理，保证了操作人员的身体健康和生命安全，使得石墨烯生产链清洁环保，推动了石墨烯干粉的产业化生产。进一步，在喷雾干燥机中一步完成剪切剥离，均匀化分散，不仅最大限度的保留了石墨烯的层面结构，而且可以连续稳定制备石墨烯材料，不破坏石墨烯的表面电学拓扑对称性，进一步保证了石墨烯成品的质量。The existing spray drying method produces graphene. The spray drying method is mostly used for drying graphene solution to prepare graphene powder. Dust pollution is serious during the production process, and continuous production of graphene cannot be achieved. Moreover, if the strong oxidant is treated with graphite, the surface of the prepared graphene is grafted with a polar group, which is harmful to human health and causes environmental pollution, destroys the lattice integrity of the graphene, and reduces the conductivity of the system. If the stripping process of graphene or the chemical reduction process of graphene can also be carried out in a spray dryer, continuous mass production of graphene can be achieved. The invention provides a method for large-scale clean preparation of graphene, fully utilizes a spray drying device, integrates mechanical stripping and powder drying into a spray dryer, thereby realizing continuous, stable and environmentally clean preparation of graphene materials, and nanometer graphite. The olefin powder or micro-graphene powder is restricted in the drying chamber to ensure the health and life safety of the operator, making the graphene production chain clean and environmentally friendly, and promoting the industrial production of the graphene dry powder. Further, in the spray dryer, the shear stripping is completed in one step, and the dispersion is uniformized, thereby not only retaining the layer structure of the graphene to the utmost extent, but also continuously and stably preparing the graphene material without destroying the surface electrical topology symmetry of the graphene, further The quality of the finished graphene is guaranteed.
本发明提出一种规模化清洁制备石墨烯的方法制备的石墨烯性能如表1所示。 The present invention proposes a graphene prepared by a method for large-scale clean preparation of graphene as shown in Table 1.
表1：Table 1:
Figure PCTCN2017078376-appb-000001
Figure PCTCN2017078376-appb-000001
发明的有益效果Advantageous effects of the invention
有益效果Beneficial effect
本发明一种规模化清洁制备石墨烯的方法，与现有技术相比，其突出的特点和优异的效果在于：The method for large-scale clean preparation of graphene of the invention has outstanding features and excellent effects compared with the prior art:
1、本发明通过在喷雾干燥机中集成了机械剥离与粉末干燥两种工艺，从而实现连续稳定、环保清洁地制备石墨烯材料，将纳米石墨烯粉或微米石墨烯粉限制在干燥腔室中处理，保证了操作人员的身体健康和生命安全，使得石墨烯生产链清洁环保，推动了石墨烯干粉的产业化生产。1. The invention integrates mechanical peeling and powder drying in a spray dryer to realize continuous, stable and environmentally clean preparation of graphene materials, and to limit nano graphene powder or micro graphene powder in a drying chamber. The treatment ensures the health and safety of the operators, making the graphene production chain clean and environmentally friendly, and promoting the industrial production of graphene dry powder.
2、本发明在喷嘴处设置超声装置，通过超声的空化作用为石墨体系提供更高能量，提高石墨***层的几率，增加发泡剂插层效果，而后在高温下发泡剂分解增加石墨层间间距，剥离石墨获得石墨烯，没有破坏石墨烯的表面电学拓扑对称性，进一步保证了石墨烯成品的质量。2. The invention provides an ultrasonic device at the nozzle, provides higher energy for the graphite system through the cavitation of the ultrasonic, increases the probability of the graphite being intercalated, increases the intercalation effect of the foaming agent, and then increases the decomposition of the blowing agent at a high temperature. The spacing between the graphite layers, the graphite is stripped to obtain graphene, and the surface electrical symmetry of the graphene is not destroyed, further ensuring the quality of the finished graphene.
3、本发明方法制备的石墨烯微片材料，不会造成环境污染，符合环保要求。3. The graphene microchip material prepared by the method of the invention does not cause environmental pollution and meets environmental protection requirements.
对附图的简要说明Brief description of the drawing
附图说明DRAWINGS
为进一步明确本发明中一种规模化清洁制备石墨烯的方法，通过附图进行说明。In order to further clarify a method for large-scale clean preparation of graphene in the present invention, it will be described with reference to the accompanying drawings.
附图1：规模化清洁制备石墨烯设备外形示意图。1-进料口；2-输料室；3-干燥室；4-空压机；5，6-超声探头；7-喷嘴。 Figure 1 is a schematic view showing the outline of a scaled clean preparation graphene device. 1-feed port; 2-feed chamber; 3-drying chamber; 4-air compressor; 5,6-ultrasonic probe; 7-nozzle.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
以下通过具体实施方式对本发明作进一步的详细说明，但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下，根据本领域普通技术知识和惯用手段做出的各种替换或变更，均应包含在本发明的范围内。The invention is further described in detail below by way of specific examples, but it should not be construed that the scope of the invention is limited to the following examples. Various alterations and modifications may be made without departing from the spirit and scope of the invention.
实施例1Example 1
(1)将10重量份平均粒径为小于1毫米的鳞片石墨、50重量份水、1.5重量份碳酸钠、1.5重量份十二烷基硫酸钠配制成分散悬浊液，以300rpm的转速搅拌分散10min，至所述石墨原料在溶剂中分散均匀，得到分散悬浊液。(1) 10 parts by weight of flake graphite having an average particle diameter of less than 1 mm, 50 parts by weight of water, 1.5 parts by weight of sodium carbonate, and 1.5 parts by weight of sodium lauryl sulfate as a dispersion suspension, and stirred at 300 rpm Dispersion was carried out for 10 min until the graphite raw material was uniformly dispersed in a solvent to obtain a dispersion suspension.
(2)将步骤(1)得到的分散悬浊溶液加入喷雾装置进料口，所述进料口与输料室连通，在所述输料室内部设置一个超声探头，设置超声功率为100KW，在分散悬浊溶液从进料口进入输料室后，分散悬浊液经过超声处理，让发泡剂进入石墨层间，降低石墨层间作用力，在所述输料室内部设置至少一个空压机，设置空压机中的空气流速为3m/s，通过空压机对分散悬浊液加压，分散悬浊液加速向前流动，输料室与干燥室相连通，经超声处理后的分散悬浊液从输料室流动进入干燥腔室。(2) adding the dispersed suspension solution obtained in the step (1) to the feed port of the spray device, the feed port is in communication with the feed chamber, and an ultrasonic probe is disposed inside the feed chamber, and the ultrasonic power is set to 100 KW. After the dispersed suspension solution enters the feed chamber from the feed port, the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one space is disposed inside the transfer chamber. Press, set the air flow rate in the air compressor to 3m / s, pressurize the dispersion suspension through the air compressor, the dispersion suspension accelerates forward flow, the feed chamber is connected with the drying chamber, after ultrasonic treatment The dispersed suspension flows from the feed chamber into the drying chamber.
(3)在所述干燥腔室顶设置气体加喷口，保持气压为0.18MPa，腔体温度为100℃，加热氮气温度为200℃，所述干燥腔室顶端设置一个尺寸为5mm的喷嘴，经分散悬浊液流经喷嘴，进入所述干燥腔室后被加热气体雾化，碳酸钠受热分解释放出气体，石墨层间距增加，经过雾化发泡，石墨在高速气流下被快速剥离，进一步，本领域技术人员可以根据需要，在喷雾装置喷嘴处设置至少一个超声探头，提供机械力，以使石墨在所述喷嘴处超声空化。本实施例中在喷雾装置喷嘴处设置一个超声探头，设置超声功率为100KW。在干燥腔室的末端设置石墨烯收集器，收集获得石墨烯。(3) a gas addition nozzle is arranged on the top of the drying chamber, the gas pressure is 0.18 MPa, the chamber temperature is 100 ° C, the heating nitrogen temperature is 200 ° C, and a nozzle having a size of 5 mm is disposed at the top of the drying chamber. The dispersed suspension flows through the nozzle, enters the drying chamber and is atomized by the heated gas. The sodium carbonate is decomposed by heat to release gas, and the distance between the graphite layers is increased. After atomization foaming, the graphite is rapidly stripped under high-speed airflow, further One skilled in the art can provide at least one ultrasonic probe at the nozzle of the spray device as needed to provide mechanical force to ultrasonically cavitation the graphite at the nozzle. In this embodiment, an ultrasonic probe is disposed at the nozzle of the spray device, and the ultrasonic power is set to 100 KW. A graphene collector was placed at the end of the drying chamber to collect graphene.
制得的石墨烯的剥离率为90％，石墨烯粒径为1.8微米，厚度为0.3nm，横向尺寸分布均匀。The obtained graphene had a peeling rate of 90%, a graphene particle diameter of 1.8 μm, a thickness of 0.3 nm, and a uniform lateral size distribution.
实施例2 Example 2
(1)将25重量份平均粒径为小于1毫米的鳞片石墨、60重量份水、10重量份碳酸钠、5重量份十二烷基硫酸钠配制成分散悬浊液，以400rpm的转速搅拌分散10min，至所述石墨原料在溶剂中分散均匀，得到分散悬浊液。(1) 25 parts by weight of flake graphite having an average particle diameter of less than 1 mm, 60 parts by weight of water, 10 parts by weight of sodium carbonate, and 5 parts by weight of sodium lauryl sulfate as a dispersion suspension, and stirred at 400 rpm Dispersion was carried out for 10 min until the graphite raw material was uniformly dispersed in a solvent to obtain a dispersion suspension.
(2)将步骤(1)得到的分散悬浊溶液加入喷雾装置进料口，所述进料口与输料室连通，在所述输料室内部设置一个超声探头，设置超声功率为100KW，在分散悬浊溶液从进料口进入输料室后，分散悬浊液经过超声处理，让发泡剂进入石墨层间，降低石墨层间作用力，在所述输料室内部设置至少一个空压机，设置空压机中的空气流速为3m/s，通过空压机对分散悬浊液加压，分散悬浊液加速向前流动，输料室与干燥室相连通，经超声处理后的分散悬浊液从输料室流动进入干燥腔室。(2) adding the dispersed suspension solution obtained in the step (1) to the feed port of the spray device, the feed port is in communication with the feed chamber, and an ultrasonic probe is disposed inside the feed chamber, and the ultrasonic power is set to 100 KW. After the dispersed suspension solution enters the feed chamber from the feed port, the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one space is disposed inside the transfer chamber. Press, set the air flow rate in the air compressor to 3m / s, pressurize the dispersion suspension through the air compressor, the dispersion suspension accelerates forward flow, the feed chamber is connected with the drying chamber, after ultrasonic treatment The dispersed suspension flows from the feed chamber into the drying chamber.
(3)在所述干燥腔室顶设置气体加喷口，保持气压为0.2MPa，腔体温度为100℃，加热氮气温度为200℃，所述干燥腔室顶端设置一个尺寸为5mm的喷嘴，经分散悬浊液流经喷嘴，进入所述干燥腔室后被加热气体雾化，碳酸钠受热分解释放出气体，石墨层间距增加，经过雾化发泡，石墨在高速气流下被快速剥离，进一步，本领域技术人员可以根据需要，在喷雾装置喷嘴处设置至少一个超声探头，提供机械力，以使石墨在所述喷嘴处超声空化。本实施例中在喷雾装置喷嘴处设置一个超声探头，设置超声功率为300KW。在干燥腔室的末端设置石墨烯收集器，收集获得石墨烯。(3) providing a gas addition nozzle at the top of the drying chamber, maintaining a gas pressure of 0.2 MPa, a chamber temperature of 100 ° C, a heating nitrogen temperature of 200 ° C, and a nozzle having a size of 5 mm at the top of the drying chamber. The dispersed suspension flows through the nozzle, enters the drying chamber and is atomized by the heated gas. The sodium carbonate is decomposed by heat to release gas, and the distance between the graphite layers is increased. After atomization foaming, the graphite is rapidly stripped under high-speed airflow, further One skilled in the art can provide at least one ultrasonic probe at the nozzle of the spray device as needed to provide mechanical force to ultrasonically cavitation the graphite at the nozzle. In this embodiment, an ultrasonic probe is disposed at the nozzle of the spray device, and the ultrasonic power is set to 300 KW. A graphene collector was placed at the end of the drying chamber to collect graphene.
制得的石墨烯的剥离率为90％，石墨烯粒径为1.3微米，厚度为0.5nm，横向尺寸分布均匀。The obtained graphene had a peeling rate of 90%, a graphene particle diameter of 1.3 μm, a thickness of 0.5 nm, and a uniform lateral size distribution.
实施例3Example 3
(1)将25重量份平均粒径为小于1毫米的膨胀石墨、60重量份水、10重量份碳酸钠和碳酸氢钠混合物、5重量份十二烷基苯磺酸钠配制成分散悬浊液，以400rpm的转速搅拌分散15min，至膨胀石墨在溶剂中分散均匀，得到分散悬浊液。(1) 25 parts by weight of expanded graphite having an average particle diameter of less than 1 mm, 60 parts by weight of water, 10 parts by weight of sodium carbonate and sodium hydrogencarbonate mixture, and 5 parts by weight of sodium dodecylbenzenesulfonate are formulated to be dispersed and suspended. The liquid was stirred and dispersed at 400 rpm for 15 minutes until the expanded graphite was uniformly dispersed in the solvent to obtain a dispersion suspension.
(2)将步骤(1)得到的分散悬浊溶液加入喷雾装置进料口，所述进料口与输料室连通，在输料室内部设置两个超声探头，设置超声功率为200KW，在分散悬浊溶液从进料口进入输料室后，分散悬浊液经过超声处理，让发泡剂进入石墨层间，降低石墨层间作用力，在所述输料室内部设置至少一个空压机，设置 空压机中的空气流速为6m/s，通过空压机对分散悬浊液加压，分散悬浊液加速向前流动，输料室与干燥室相连通，经超声处理后的分散悬浊液从输料室流动进入干燥腔室。(2) adding the dispersed suspension solution obtained in the step (1) to the feed port of the spray device, the feed port is connected to the feed chamber, and two ultrasonic probes are arranged inside the feed chamber, and the ultrasonic power is set to 200 KW. After the dispersed suspension solution enters the feed chamber from the feed port, the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one air pressure is disposed inside the feed chamber. Machine, setting The air flow rate in the air compressor is 6m/s, the dispersion suspension is pressurized by the air compressor, the dispersion suspension accelerates forward flow, the feed chamber communicates with the drying chamber, and the dispersion is suspended after sonication. The liquid flows from the feed chamber into the drying chamber.
(3)在所述干燥腔室顶设置气体加喷口，保持气压为0.3MPa，腔体温度为100℃，加热氮气温度为200℃，所述干燥腔室顶端设置一个尺寸为5mm的喷嘴，经分散悬浊液流经喷嘴，进入所述干燥腔室后被加热气体雾化，碳酸钠受热分解释放出气体，石墨层间距增加，经过雾化发泡，石墨在高速气流下被快速剥离，进一步，本领域技术人员可以根据需要，在喷雾装置喷嘴处设置至少一个超声探头，提供机械力，以使石墨在所述喷嘴处超声空化。本实施例中在喷雾装置喷嘴处设置一个超声探头，设置超声功率为300KW。在干燥腔室的末端设置石墨烯收集器，收集获得石墨烯。(3) a gas addition nozzle is arranged on the top of the drying chamber, the gas pressure is 0.3 MPa, the chamber temperature is 100 ° C, the heating nitrogen temperature is 200 ° C, and a nozzle having a size of 5 mm is disposed at the top of the drying chamber. The dispersed suspension flows through the nozzle, enters the drying chamber and is atomized by the heated gas. The sodium carbonate is decomposed by heat to release gas, and the distance between the graphite layers is increased. After atomization foaming, the graphite is rapidly stripped under high-speed airflow, further One skilled in the art can provide at least one ultrasonic probe at the nozzle of the spray device as needed to provide mechanical force to ultrasonically cavitation the graphite at the nozzle. In this embodiment, an ultrasonic probe is disposed at the nozzle of the spray device, and the ultrasonic power is set to 300 KW. A graphene collector was placed at the end of the drying chamber to collect graphene.
制得的石墨烯的剥离率为90％，石墨烯粒径为2.4微米，厚度为0.3nm，横向尺寸分布均匀。The obtained graphene had a peeling rate of 90%, a graphene particle diameter of 2.4 μm, a thickness of 0.3 nm, and a uniform lateral size distribution.
实施例4Example 4
(1)将25重量份平均粒径为小于1毫米的膨胀石墨、60重量份水、10重量份碳酸钠和碳酸氢钠混合物、5重量份十二烷基苯磺酸钠配制成分散悬浊液，以400rpm的转速搅拌分散15min，至膨胀石墨在溶剂中分散均匀，得到分散悬浊液。(1) 25 parts by weight of expanded graphite having an average particle diameter of less than 1 mm, 60 parts by weight of water, 10 parts by weight of sodium carbonate and sodium hydrogencarbonate mixture, and 5 parts by weight of sodium dodecylbenzenesulfonate are formulated to be dispersed and suspended. The liquid was stirred and dispersed at 400 rpm for 15 minutes until the expanded graphite was uniformly dispersed in the solvent to obtain a dispersion suspension.
(2)将步骤(1)得到的分散悬浊溶液加入喷雾装置进料口，所述进料口与输料室连通，在输料室内部设置两个超声探头，设置超声功率为200KW，在分散悬浊溶液从进料口进入输料室后，分散悬浊液经过超声处理，让发泡剂进入石墨层间，降低石墨层间作用力，在所述输料室内部设置至少一个空压机，设置空压机中的空气流速为6m/s，通过空压机对分散悬浊液加压，分散悬浊液加速向前流动，输料室与干燥室相连通，经超声处理后的分散悬浊液从输料室流动进入干燥腔室。(2) adding the dispersed suspension solution obtained in the step (1) to the feed port of the spray device, the feed port is connected to the feed chamber, and two ultrasonic probes are arranged inside the feed chamber, and the ultrasonic power is set to 200 KW. After the dispersed suspension solution enters the feed chamber from the feed port, the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one air pressure is disposed inside the feed chamber. Machine, set the air flow rate in the air compressor to 6m / s, pressurize the dispersion suspension through the air compressor, the dispersion suspension accelerates forward flow, the feed chamber is connected with the drying chamber, after ultrasonic treatment The dispersed suspension flows from the feed chamber into the drying chamber.
(3)在所述干燥腔室顶设置气体加喷口，保持气压为0.4MPa，腔体温度为150℃，加热氮气温度为300℃，干燥腔室顶端设置一个尺寸为10mm的喷嘴，经分散悬浊液流经喷嘴，进入所述干燥腔室后被加热气体雾化，碳酸钠和碳酸氢钠受热分解释放出气体，石墨层间距增加，经过雾化发泡，石墨在高速气流下被快 速剥离，进一步，本领域技术人员可以根据需要，在喷雾装置喷嘴处设置至少一个超声探头，提供机械力，以使石墨在所述喷嘴处超声空化。本实施例中在喷雾装置喷嘴处设置一个超声探头，设置超声功率为300KW。在干燥腔室的末端设置石墨烯收集器，收集获得石墨烯。(3) A gas addition nozzle is arranged at the top of the drying chamber, the gas pressure is 0.4 MPa, the chamber temperature is 150 ° C, the heating nitrogen temperature is 300 ° C, and a nozzle of a size of 10 mm is disposed at the top of the drying chamber, and is dispersed. The turbid liquid flows through the nozzle, enters the drying chamber and is atomized by the heated gas. The sodium carbonate and sodium hydrogencarbonate are decomposed by heat to release the gas, and the distance between the graphite layers is increased. After atomization foaming, the graphite is fast under high-speed airflow. Speed stripping, further, one skilled in the art can provide at least one ultrasonic probe at the spray device nozzle as needed to provide mechanical force to ultrasonically cavitation of graphite at the nozzle. In this embodiment, an ultrasonic probe is disposed at the nozzle of the spray device, and the ultrasonic power is set to 300 KW. A graphene collector was placed at the end of the drying chamber to collect graphene.
制得的石墨烯的剥离率为90％，石墨烯粒径为2.6微米，厚度为0.3nm，横向尺寸分布均匀。The obtained graphene had a peeling rate of 90%, a graphene particle diameter of 2.6 μm, a thickness of 0.3 nm, and a uniform lateral size distribution.
实施例5Example 5
(1)将25重量份平均粒径为小于1毫米的膨胀石墨、60重量份水、10重量份碳酸钠和碳酸氢钠混合物、5重量份十二烷基苯磺酸钠配制成分散悬浊液，以500rpm的转速搅拌分散15min，至膨胀石墨在溶剂中分散均匀，得到分散悬浊液。(1) 25 parts by weight of expanded graphite having an average particle diameter of less than 1 mm, 60 parts by weight of water, 10 parts by weight of sodium carbonate and sodium hydrogencarbonate mixture, and 5 parts by weight of sodium dodecylbenzenesulfonate are formulated to be dispersed and suspended. The liquid was stirred and dispersed at 500 rpm for 15 minutes until the expanded graphite was uniformly dispersed in the solvent to obtain a dispersion suspension.
(2)将步骤(1)得到的分散悬浊溶液加入喷雾装置进料口，所述进料口与输料室连通，在输料室内部设置两个超声探头，设置超声功率为500KW，在分散悬浊溶液从进料口进入输料室后，分散悬浊液经过超声处理，让发泡剂进入石墨层间，降低石墨层间作用力，在所述输料室内部设置至少一个空压机，设置空压机中的空气流速为10m/s，通过空压机对分散悬浊液加压，分散悬浊液加速向前流动，输料室与干燥室相连通，经超声处理后的分散悬浊液从输料室流动进入干燥腔室。(2) adding the dispersed suspension solution obtained in the step (1) to the feed port of the spray device, the feed port is connected to the feed chamber, and two ultrasonic probes are arranged inside the feed chamber, and the ultrasonic power is set to 500 KW. After the dispersed suspension solution enters the feed chamber from the feed port, the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, and at least one air pressure is disposed inside the feed chamber. Machine, set the air flow rate in the air compressor to 10m / s, pressurize the dispersion suspension through the air compressor, the dispersion suspension accelerates forward flow, the feed chamber is connected with the drying chamber, after ultrasonic treatment The dispersed suspension flows from the feed chamber into the drying chamber.
(3)在所述干燥腔室顶设置气体加喷口，保持气压为0.5MPa，腔体温度为150℃，加热氮气温度为400℃，干燥腔室顶端设置一个尺寸为10mm的喷嘴，经分散悬浊液流经喷嘴，进入所述干燥腔室后被加热气体雾化，碳酸钠和碳酸氢钠受热分解释放出气体，石墨层间距增加，经过雾化发泡，石墨在高速气流下被快速剥离，进一步，本领域技术人员可以根据需要，在喷雾装置喷嘴处设置至少一个超声探头，提供机械力，以使石墨在所述喷嘴处超声空化。本实施例中在喷雾装置喷嘴处设置两个超声探头，设置超声功率为500KW。在干燥腔室的末端设置石墨烯收集器，收集获得石墨烯。(3) Providing a gas addition nozzle at the top of the drying chamber, maintaining a gas pressure of 0.5 MPa, a chamber temperature of 150 ° C, a heating nitrogen temperature of 400 ° C, and a nozzle of a size of 10 mm at the top of the drying chamber, dispersed and suspended The turbid liquid flows through the nozzle, enters the drying chamber and is atomized by the heated gas. The sodium carbonate and sodium hydrogencarbonate are decomposed by heat to release the gas, and the distance between the graphite layers is increased. After atomization foaming, the graphite is quickly stripped under high-speed airflow. Further, one skilled in the art can provide at least one ultrasonic probe at the nozzle of the spray device as needed to provide mechanical force to ultrasonically cavitation the graphite at the nozzle. In this embodiment, two ultrasonic probes are disposed at the nozzle of the spray device, and the ultrasonic power is set to 500 KW. A graphene collector was placed at the end of the drying chamber to collect graphene.
制得的石墨烯的剥离率为90％，石墨烯粒径为0.8微米，厚度为0.3nm，横向尺寸分布均匀。The obtained graphene had a peeling rate of 90%, a graphene particle diameter of 0.8 μm, a thickness of 0.3 nm, and a uniform lateral size distribution.
工业实用性 Industrial applicability
本发明提出一种规模化清洁制备石墨烯的方法，充分利用了喷雾干燥设备，将机械剥离与粉末干燥集成在喷雾干燥机中，从而实现连续稳定、环保清洁地制备石墨烯材料，将纳米石墨烯粉或微米石墨烯粉限制在干燥腔室中处理，保证了操作人员的身体健康和生命安全，使得石墨烯生产链清洁环保，进一步推动了石墨烯干粉的产业化生产。 The invention provides a method for large-scale clean preparation of graphene, fully utilizes a spray drying device, integrates mechanical stripping and powder drying into a spray dryer, thereby realizing continuous, stable and environmentally clean preparation of graphene materials, and nanometer graphite. The olefin powder or micro-graphene powder is restricted in the drying chamber to ensure the health and life safety of the operator, which makes the graphene production chain clean and environmentally friendly, further promoting the industrial production of graphene dry powder.

Claims (7)

  1. 一种规模化清洁制备石墨烯的方法，具体方法如下：A method for large-scale clean preparation of graphene, the specific method is as follows:
    (1)将10-25重量份石墨原料、50-60重量份水、1.5-15重量份发泡剂、1.5-5重量份表面活性剂配制成分散悬浊液，以300-500rpm的转速搅拌分散10-25min，至所述石墨原料在溶剂中分散均匀，得到分散悬浊液；(1) 10-25 parts by weight of graphite raw material, 50-60 parts by weight of water, 1.5-15 parts by weight of a foaming agent, 1.5-5 parts by weight of a surfactant are formulated into a dispersion suspension, and stirred at 300-500 rpm. Dispersing for 10-25 min until the graphite raw material is uniformly dispersed in a solvent to obtain a dispersed suspension;
    (2)将步骤(1)得到的分散悬浊溶液加入喷雾装置进料口，所述进料口与输料室连通，在所述输料室内部设置至少一个超声探头，设置超声功率为100-500KW，在分散悬浊溶液从所述进料口进入输料室后，分散悬浊液经过超声处理，让发泡剂进入石墨层间，降低石墨层间作用力，在所述输料室内部设置至少一个空压机，通过所述空压机对分散悬浊液加压，分散悬浊液加速向前流动，所述输料室与干燥室相连通，经超声处理后的分散悬浊液从所述输料室流动进入所述干燥腔室；(2) adding the dispersed suspension solution obtained in the step (1) to the feed port of the spray device, the feed port is in communication with the feed chamber, and at least one ultrasonic probe is disposed inside the feed chamber, and the ultrasonic power is set to 100. -500 KW, after the dispersed suspension solution enters the feed chamber from the feed port, the dispersion suspension is subjected to ultrasonic treatment to allow the foaming agent to enter between the graphite layers to reduce the interaction between the graphite layers, in the feed chamber At least one air compressor is disposed inside, and the dispersion suspension is pressurized by the air compressor, and the dispersion suspension accelerates forward flow, and the delivery chamber is connected with the drying chamber, and the dispersion is suspended after ultrasonic treatment. Liquid flowing from the feed chamber into the drying chamber;
    (3)在所述干燥腔室顶设置气体加喷口，保持气压为0.1-0.5MPa，腔体温度为100-150℃，加热气体温度为200-400℃，所述干燥腔室顶端设置至少一个喷嘴，经分散悬浊液流经所述喷嘴，进入所述干燥腔室后被加热气体雾化，发泡剂受热分解释放出气体，石墨层间距增加，经过雾化发泡，石墨在高速气流下被快速剥离，获得石墨烯。(3) providing a gas addition nozzle at the top of the drying chamber, maintaining a gas pressure of 0.1-0.5 MPa, a chamber temperature of 100-150 ° C, a heating gas temperature of 200-400 ° C, and setting at least one of the top ends of the drying chamber The nozzle flows through the nozzle through the dispersed suspension, enters the drying chamber and is atomized by the heating gas, and the foaming agent is decomposed by heat to release gas, and the spacing of the graphite layer is increased, and after atomization foaming, the graphite is in a high-speed airflow. The underside is quickly stripped to obtain graphene.
  2. 根据权利要求1所述一种规模化清洁制备石墨烯的方法，其特征在于：所述喷雾装置喷嘴处设置至少一个超声探头，设置超声功率为100-500KW，提供机械力，以使石墨在所述喷嘴处超声空化。A method for large-scale clean preparation of graphene according to claim 1, wherein at least one ultrasonic probe is disposed at the nozzle of the spray device, and the ultrasonic power is set to be 100-500 KW, and mechanical force is provided to make the graphite in place. Ultrasonic cavitation at the nozzle.
  3. 根据权利要求1所述一种规模化清洁制备石墨烯的方法，其特征在于：所述的石墨原料为鳞片石墨、膨胀石墨、高取向石墨、热裂解石墨、氧化石墨中的至少一种，所述石墨原料的平均粒径为小于1毫米；所述的发泡剂为碳酸钠、碳酸钾、碳酸氢钠、碳酸氢 钾、氯化铵、硫酸铵、硫酸氢铵、碳酸铵、碳酸氢铵、磷酸铵中的至少一种；所述的表面活性剂为十二烷基硫酸钠、十二烷基苯磺酸钠、聚乙烯吡咯烷酮、1-吡啶酸中的至少一种。The method for preparing a graphene according to claim 1, wherein the graphite material is at least one of flake graphite, expanded graphite, highly oriented graphite, pyrolytic graphite, and graphite oxide. The graphite material has an average particle diameter of less than 1 mm; the foaming agent is sodium carbonate, potassium carbonate, sodium hydrogencarbonate or hydrogen carbonate. At least one of potassium, ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogencarbonate, ammonium phosphate; the surfactant is sodium lauryl sulfate, sodium dodecylbenzenesulfonate At least one of polyvinylpyrrolidone and 1-pyridyl acid.
  4. 根据权利要求1所述一种规模化清洁制备石墨烯的方法，其特征在于：步骤(2)中所述的空压机中的空气流速为3-10m/s。A method for large-scale clean preparation of graphene according to claim 1, wherein the air flow rate in the air compressor described in the step (2) is 3-10 m/s.
  5. 根据权利要求1所述一种规模化清洁制备石墨烯的方法，其特征在于：步骤(3)中气体为氮气、氩气和二氧化碳中的一种或几种。A method for preparing graphene by mass cleaning according to claim 1, wherein the gas in the step (3) is one or more of nitrogen, argon and carbon dioxide.
  6. 根据权利要求1所述一种规模化清洁制备石墨烯的方法，其特征在于：所述喷嘴尺寸5～10mm。A method for preparing graphene by mass cleaning according to claim 1, wherein the nozzle has a size of 5 to 10 mm.
  7. 根据权利要求1所述一种规模化清洁制备石墨烯的方法，其特征在于：在干燥腔室的末端设置石墨烯收集器，收集石墨烯。 A method for large-scale clean preparation of graphene according to claim 1, wherein a graphene collector is disposed at an end of the drying chamber to collect graphene.
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