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WO2018100552A1 - Fabrication de matériaux de graphène à l'aide d'un réacteur à cavitation - Google Patents

Fabrication de matériaux de graphène à l'aide d'un réacteur à cavitation Download PDF

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Publication number
WO2018100552A1
WO2018100552A1 PCT/IB2017/057581 IB2017057581W WO2018100552A1 WO 2018100552 A1 WO2018100552 A1 WO 2018100552A1 IB 2017057581 W IB2017057581 W IB 2017057581W WO 2018100552 A1 WO2018100552 A1 WO 2018100552A1
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WIPO (PCT)
Prior art keywords
reactor
graphene
fluid
vortex
ultrasound
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Application number
PCT/IB2017/057581
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English (en)
Inventor
Don Edward Kress
Kamalul Arifin Yusof
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Cetamax Ventures Ltd.
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Publication of WO2018100552A1 publication Critical patent/WO2018100552A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2405—Stationary reactors without moving elements inside provoking a turbulent flow of the reactants, such as in cyclones, or having a high Reynolds-number

Definitions

  • the present disclosure relates generally to the manufacture of graphene materials, including tube-shaped graphene sheet materials and graphene-enhanced polymer composites.
  • Graphene is an atomic-scale, crystalline allotrope of carbon with carbon atoms densely packed in a regular two-dimensional hexagonal lattice structure. Certain graphene materials exhibit beneficial material properties, including extremely high electrical conductivity, heat conductivity, and strength to weight ratios, as well as unique optical characteristics.
  • One conventional technique for producing graphene involves "exfoliation" of bulk graphite to pull flakes away from the bulk graphite. Some techniques achieve exfoliation through reduction of a graphite oxide material. However, resulting flakes fail to exhibit the same degree of beneficial material properties as defect-free unoxidized graphene.
  • Another technique utilizes sonication of a bulk graphite material, followed by centrifugation. While this technique achieves relatively high concentrations of graphene, restacking of individual graphene units into solid graphite forms is a recurrent issue.
  • the present disclosure relates to the manufacture of graphene materials, including tube-shaped graphene sheet materials and graphene-enhanced polymer composites.
  • the present disclosure describes embodiments which manufacture graphene materials by utilizing one or more vortex reactors to control fluid dynamics and provide desired processing conditions to enable effective formation of the graphene materials.
  • a vortex reactor includes a reactor body having a first end and a second end.
  • the reactor body includes one or more inlet ports disposed near the first end.
  • the one or more inlet ports are configured to direct a reactor fluid into the reactor body.
  • the one or more inlet ports can be tangentially oriented with respect to an inner surface of the reactor body so that the fluid mixture directed into the reactor body follows a vortical path as it rises within the reactor body toward the second end.
  • a base plate is attached to the reactor body at the first end. Disposed within the base plate are an ultrasound horn or array of ultrasound horns. One or more ultrasound horns are configured to impart ultrasound energy into the reactor body.
  • an exfoliation zone is provided between the one or more inlet ports and the ultrasound horn or array.
  • the exfoliation zone can receive a graphite material and can function as a holding reservoir where the graphite material is maintained during operation of the reactor.
  • Ultrasound energy from the ultrasound horn or array is directed at the graphite material to form graphene flakes via ultrasonic exfoliation, and at least a portion of the graphene flakes then migrate into the vortical path of the fluid mixture as it passes through the reactor.
  • a fluid mixture of two immiscible fluids is directed into the reactor.
  • the vortical motion of the fluid aids in separating the fluids into an outer fluid and an inner fluid with an interface formed between the separated fluids.
  • Graphene flakes aggregate at the interface and self-assemble into graphene sheets.
  • the three-dimensional shape of the interface causes the resulting graphene sheets to form a tube-shaped structure.
  • the tube-shaped graphene sheet may be collected and processed in one or more further downstream processes.
  • a vortex reactor further includes an outlet pipe that extends upwards from the first end of the reactor body toward the second end.
  • a guide cone is coupled to the upper end of the outlet pipe.
  • One or more injectors may also be positioned to enable delivery of a polymerizing agent and/or additive into the reactor within the vicinity of the guide cone.
  • a mixture of two immiscible fluids and graphene flakes follows the outer vortical path upwards until reaching an apex near the second end of the reactor. The mixture then moves radially inward and crests over the guide cone and then down into the outlet pipe.
  • energy imparted by the second ultrasound horn or array and fluid dynamics at the apex cause the immiscible fluids to form an emulsion (preferably water in oil).
  • the graphene within the mixture aggregates at the plurality of interfacial regions between the immiscible fluids of the emulsion.
  • polymerization of the polymerizable fluid forms a porous polymer that traps the other fluid within the cavities/pores of the resulting structure, with the graphene remaining at the interface as a coating of the cavities/pores.
  • the other fluid may then be evaporated leaving a porous graphene polymer composite material.
  • Figure 1 illustrates an exemplary embodiment of a reactor configured to generate a single vortex
  • Figure 2 illustrates an exemplary embodiment of a reactor configured to generate dual vortices
  • Figure 3 illustrates an exemplary embodiment of a reactor having a collection assembly for collecting different components from different radial separation zones
  • Figures 4 and 5 illustrate exemplary embodiments of a vortex reactor configured to generate tube-shaped graphene sheets
  • Figure 6 illustrates an exemplary embodiment of a process flow for producing tube-shaped graphene sheets using, for example, a vortex reactor as in Figure 4 or Figure 5;
  • Figure 7 illustrates an exemplary embodiment of a vortex reactor configured to generate a graphene-enhanced polymer composite
  • Figure 8 illustrates an exemplary embodiment of a process flow for producing graphene-enhanced polymer composites using the vortex reactor of Figure 7;
  • Figure 9 illustrates an alternative embodiment of a process flow for producing graphene sheets using, for example, a vortex reactor as in Figure 4 or Figure 5.
  • the present disclosure relates to devices, systems, and methods for producing graphene sheets and/or graphene-enhanced composite materials using one or more vortex reactors. At least some of the vortex reactor embodiments described herein may be utilized to effectively manufacture graphene sheet materials and/or graphene-enhanced composite materials by providing a vortical tubular interface between two immiscible fluids where graphene flakes can self-assemble to form a graphene sheet material.
  • Graphene sheets generated using the embodiments described herein can have a thickness of less than or equal to about four or five carbon atoms, and may also be referred to as “few layer graphene” or “FLG.” It is at these thicknesses that the beneficial properties of graphene emerge, whereas thicknesses greater than about five carbon atoms typically cause the material to lose beneficial properties of graphene and begin to exhibit more graphite-like properties.
  • Flakes of graphene may be trapped at an interface between two immiscible fluids where a resulting graphene sheet may be formed.
  • U.S. Patent Application Publication No. 2014/0305571 which is incorporated herein by reference in its entirety, describes a process whereby graphene flakes are introduced into a phase separated system. The kinetics of the system cause the graphene to self-assemble at the interface between two immiscible fluids, where the flakes layer together to form graphene sheets.
  • the embodiments described herein beneficially provide one or more of effective formation, processing, collection, or yield of such graphene sheets by utilizing at least one vortex reactor to form a vortical tubular interface between two immiscible fluids to enable effective self-assembly of the graphene sheets at the interface.
  • Some embodiments also include one or more components for generating graphene flakes from a graphite source material. The graphene flakes are generated in-situ within the vortex reactor where they can subsequently self-assemble into graphene sheets as they pass through the reactor.
  • graphene may be utilized to form stabilized composite materials by mixing the graphene in an emulsion of immiscible fluids, allowing the graphene to stabilize the emulsion by aggregating at the various fluid interfaces of the emulsion, and polymerizing one of the fluids to form a matrix having cavities lined with graphene.
  • Such a process is described by U.S. Patent Application Publication No. 2015/0348669, which is incorporated herein by reference in its entirety.
  • At least some of the vortex reactor embodiments described herein enable effective generation of such graphene-enhanced composite materials by providing one or more of effective mixing, emulsion formation, fluid interface control, or other fluid dynamics enhancements.
  • Figure 1 illustrates an embodiment of a vortex reactor 100 configured to form a single vortex during operation of the reactor.
  • the illustrated embodiment includes one or more inlet ports 102 disposed at a first end 104 of vortex reactor 100.
  • the illustrated inlet ports 102 open into a reactor body 108 configured to contain a reactor fluid mixture which is directed into vortex reactor 100 through the inlet ports 102.
  • the reactor body 108 has a circular cross-section.
  • Other embodiments can include a triangular, square, rectangular, or other polygonal shaped cross-section, or an ellipsoid or ovoid cross-section.
  • the illustrated reactor body 108 has a cylindrical shape with substantially uniform diameter along its height.
  • the reactor body 108 can have a non-uniform diameter along its height, such as a conical shape with a diameter at a second end 106 that is narrower than a diameter at a first end 104 (or vice versa).
  • inlet ports 102 are oriented so as to receive the reactor fluid mixture at an angle that is tangential or substantially tangential to an inner surface of the reactor body 108.
  • the orientation of the inlet ports 102 causes the incoming fluid to form a vortex as it advances into reactor body 108.
  • the generated vortex causes the fluid mixture to be subjected to centripetal and centrifugal forces along the trajectory of the vortex.
  • reactor 100 can include a pump, turbine and/or impeller assembly, or other fluid movement means configured to form and/or strengthen the vortex.
  • the illustrated embodiment includes two inlet ports 102 disposed at the first end 104.
  • Other embodiments may include one inlet port or may include more than two inlet ports.
  • the first end 104 and the associated inlet ports 102 are disposed at the bottom of a vertically oriented reactor body 108, and the vortex that results from reactor operation therefore rises vertically toward the second end 106.
  • one or more inlet ports may be disposed on an upper end of a vertically oriented reactor body, allowing for a downflow vortex during operation of the reactor.
  • a reactor body may be oriented horizontally, or diagonally, and one or more inlet ports can be configured to provide a horizontally or diagonally moving vortex. The orientation of the reactor 100 with respect to gravity may therefore be configured according to preferences and/or particular application needs.
  • the one or more inlet ports 102 are configured to deliver fluid at an angle that is tangential to the inner surface of the reactor body 108.
  • the illustrated inlet ports 102 are angled to be substantially perpendicular to a longitudinal axis of the reactor 100 (i.e., are not angled upwards toward second end 106 or downwards toward the first end 102).
  • one or more of the inlet ports 102 are configured to deliver fluid at an upward angle or downward angle (e.g., at an angle opening toward second end 106 or toward first end 102).
  • the angle at which an inlet port is directed can be adjusted to provide one or more desired features to fluid flow within the reactor 100.
  • relatively higher inlet angles can generate a vortex that has a lower angular velocity and which rises to the second end 106 in less relative time.
  • relatively lower inlet angles can generate a vortex that has a higher angular velocity and which rises toward the second end 106 in more relative time.
  • Such angles can advantageously alter the fluid dynamics within the reactor to provide desired pressures, mixing effects, and/or other fluid flow dynamics.
  • the tangentially arranged inlet ports 102 may be configured so that at least one inlet port is asymmetrically aligned with at least one other inlet port to provide beneficial mixing of inflowing reactor fluid in at least the initial inflow region of the reactor 100.
  • Such asymmetrical alignment provides a more turbulent initial flow, allowing advantageous mixing and/or graphene flake dispersion to occur in at least the initial inflow region (e.g., region near the inlet ports 102) of the reactor 100.
  • the fluid will self- organize into a relatively more structured vortical flow beneficial for creating an interface for controlling graphene flake movement and associated graphene sheet formation.
  • the illustrated vortex reactor 100 also includes a bleed opening 110 disposed at or near second end 106.
  • bleed opening 110 can be disposed at or near first end 104 (e.g., in downflow configurations).
  • bleed opening 110 is configured to bleed off air or other gases and/or liquids that may be present in reactor body 108 prior to advancing a reactor fluid mixture into the reactor 100.
  • Bleed opening 110 may be formed as a hole, slit, valve, or other suitable controllable fluid passageway.
  • the bleed opening 110 is configured as a valve, such as a one-way valve allowing the passage of fluid out of the reactor but not into the reactor.
  • the bleed opening 110 is configured as a valve allowing the passage of air or other gas out of the reactor but preventing the passage of liquid out of the reactor.
  • the illustrated reactor 100 includes a vortex outlet 114 disposed at the second end 106.
  • the vortex outlet 114 can extend from second end 106 a distance into reactor body 108 (e.g., as a pipe or conduit extending into reactor body 108).
  • the vortex outlet 114 is substantially aligned with the longitudinal axis of reactor 100, though other embodiments may include an off-center vortex outlet 114.
  • the reactor 100 omits internal baffles and/or other obstructing structures, allowing fluid flow through the reactor to self-organize into a vortex.
  • the illustrated reactor 100 also includes a set of wall ports 130.
  • One or more of such wall ports 130 may be utilized as outlet ports for conducting a portion of the fluid mixture out of the reactor.
  • one or more of such wall ports 130 may be utilized for introducing solids, fluids, or mixtures into the reactor at one or more desired locations along the vortical fluid path within the reactor body 108.
  • Figure 2 illustrates an embodiment of a vortex reactor 200 configured to generate dual vortices during operation of the reactor 200. Except where specifically described otherwise, components of the vortex reactor 200 may be configured as counterpart components of the vortex reactor 100 of Figure 1.
  • the illustrated embodiment includes one or more inlet ports 202 disposed at the first end 204. The inlet ports 202 open into a reactor body 208 configured to receive fluid directed through the inlet ports 202.
  • one or more of the inlet ports 202 are oriented to direct fluid at an angle that is tangential, or substantially tangential, to an inner surface of reactor body 208.
  • This configuration allows the fluid to form an outer vortex 216 as it advances through the reactor body 208 toward the second end 206.
  • the outer vortex 216 subjects the fluid within the reactor to centripetal and centrifugal forces along the trajectory of outer vortex 216.
  • the illustrated reactor 200 also includes a bleed opening 210 to function as a valve for modulating passage of fluid within the reactor body 208.
  • the illustrated reactor 200 also includes a vortex outlet 214 disposed at the first end 204 of the reactor.
  • the vortex outlet 214 extends from the first end 204 a distance into reactor body 208.
  • the illustrated vortex outlet 214 is aligned with a longitudinal axis of the reactor 200.
  • the inlet ports 202 may be arranged in a radial pattern around the vortex outlet 214.
  • the outer vortex 216 axially advances toward the second end 206.
  • the fluid mass reverses axial/longitudinal direction to travel back down to first end 204 in an inner vortex 218 as it advances toward the vortex outlet 214.
  • FIG 3 illustrates an embodiment of a vortex reactor 801 having a second end 806 configured to separate different fractions of the fluid mass according to different radial zones in which the different fractions accumulate.
  • the vortical motion of the fluid as it moves toward the second end 806 will cause lower density fractions to concentrate closer to the axis of the vortex, while fractions of progressively greater density will concentrate at positions extending radially outward from the axis.
  • a series of outlet members 822 are arranged at different radial separation zones, and may be positioned to separately receive different fractions of the fluid mass passing through the reactor 801.
  • the illustrated configuration may be utilized with any of the reactor embodiments described herein to enable effective collection and separation of the different components formed in a graphene sheet production process.
  • the vortical motion of the fluid mixture aids in effectively separating the two fluids as they rise from the first end to the second end, enabling the formation of a tubular fluid interface, with the less dense fluid disposed radially closer to the axis and the other denser fluid disposed radially closer to the periphery.
  • the generated graphene flake material is provided within the reactor, the generated graphene flakes will accumulate at the interface and self-assemble to form a continually rising tubular graphene sheet.
  • the separate outlet members 822 can be radially positioned to coincide with the different separation regions of the fluid mass. For example, one outlet member may coincide with the more peripheral fluid, another outlet member may coincide with the more central fluid, and another outlet member may coincide with the interface between the two fluids where the generated graphene sheet structure is disposed.
  • the outlet members 822 may be configured as outlet tubes, channels, conduits, or the like.
  • an outlet member may be formed as or may include a substrate for associating with the corresponding fraction of the fluid mass as it contacts the outlet member.
  • the outlet member corresponding to the interface position may be formed as or may include a substrate configured to associate with and aid in the collecting of the generated graphene sheet.
  • the substrate is a hydrophilic material such as a hydrophilic glass.
  • the outlet members 822 are positioned at different radial zones and at different elevations within the reactor 801. Positioning the outlet members 822 at different elevations and/or at different tangential angles to the longitudinal axis enables the outlet members 822 to function with minimal disturbance to the vortical flow within the reactor 801.
  • the illustrated embodiment also includes a central outlet 821 where the least dense fraction of the fluid mixture may exit.
  • Figure 4 illustrates an exemplary embodiment of a vortex reactor 400 which may be utilized to effectively manufacture a tube-shaped graphene sheet material.
  • a section of the reactor wall has been cutout to better illustrate an interior portion of the reactor 400.
  • the illustrated reactor 400 may include similar components and may be configured in a manner similar to that of foregoing reactor embodiments, and in particular in a manner similar to the single vortex reactor of Figure 1.
  • the illustrated reactor 400 is configured as a single vortex reactor having an array of one or more inlet ports 402 oriented to generate upwardly rising vortical motion in the incoming fluid.
  • a mixture of two immiscible fluids is directed into the reactor 400 through inlet ports 402.
  • a first fluid is water and a second fluid is a suitable solvent immiscible with water.
  • the first fluid is water and the second fluid is a suitable immiscible oil.
  • Fluids utilized in the reactor may be selected based on preferences and/or particular application needs.
  • the immiscible fluid mixture includes water and heptane. Much of the following description is given in the context of a water and heptane embodiment. However, it will be understood that the same concepts apply to alternative embodiments utilizing alternative fluid mixtures.
  • the volumetric ratio of fluids used will determine at what radial distance from the longitudinal axis the interface between the two fluids will form. For example, a greater proportion of the fluid which migrates to the periphery will move the interface radially inward, while a greater proportion of the fluid which migrates radially inward will push the interface radially outward.
  • the ratio of the fluids of the fluid mixture may therefore be adjusted to the preferred ratio in order to achieve desired interface size, shape, and position.
  • the fluid mixture may be directed to the reactor 400 in a pre-mixed form.
  • the reactor 400 may be operated to provide the mixing of the separate fluids.
  • one inlet port or set of inlet ports may be utilized to direct the first fluid into the reactor 400 while another inlet port or set of inlet ports may be utilized to direct the second fluid into the reactor 400.
  • the fluid mixture is directed into the reactor 400 and vortical flow results. Centripetal and centrifugal forces aid in separating the separate phases of the fluid mixture.
  • the denser phase e.g., water
  • the less dense phase e.g., heptane
  • graphene flakes within the system will aggregate at the interface, enabling the formation of a tube-shaped graphene sheet material.
  • the graphene flakes are generated in-situ within the reactor 400.
  • the illustrated embodiment includes an exfoliation zone 432 disposed near the first end 404 above one or more ultrasound horns 434, where graphene flakes are generated from a mass of graphite particles disposed within the exfoliation zone 432.
  • the graphite particles may be directed into the exfoliation zone 432 through one of the inlet ports 402 (either through a shared port with one or both fluids or through a dedicated port).
  • the exfoliation zone 432 is provided as a space between the inlet ports 402 and the base plate 436 in which the ultrasound horn or array 434 is disposed. This space provides a holding area for the graphite where it can receive ultrasound sonication without being overly caught up in the vortical fluid motion.
  • the exfoliation zone 434 has a height that is about 30%, 20%, 10%, 5%, or 1% of the overall height of the reactor body 408, or has a height that is within a range defined by any two of the foregoing percentages.
  • the reactor 400 includes an ultrasound horn or array 434 of ultrasound horns for imparting sufficient ultrasound energy to the graphite particles within the exfoliation zone 432.
  • the ultrasound energy imparted to the graphite particles forms graphene flakes via ultrasonic exfoliation.
  • the ultrasound horn or array 434 is arranged in a base plate 436 of the reactor.
  • Alternative embodiments may position one or more ultrasound horns at different locations, such as within the wall of the reactor.
  • the graphite particles swirl around within the exfoliation zone 432 just above the ultrasound horn or array 434.
  • the graphene flakes As the graphene flakes are formed, they will tend to aggregate at the interface between the phases of immiscible fluids as the immiscible fluids coalesce into separate phases while rising in the reactor 400 toward the second end 406. The formed graphene sheet and the separate fluids may then be collected from the reactor.
  • Figure 5 illustrates another embodiment of a vortex reactor 500 which may be utilized in a graphene sheet production process.
  • the embodiment shown in Figure 5 is similar to the embodiment shown in Figure 4.
  • the reactor wall of the illustrated reactor 500 has a conical shape, with the diameter at the second end 506 being smaller than at the first end 504.
  • Alternative embodiments may have a conical shape with the smaller diameter disposed at the first end 504.
  • the smaller diameter end be disposed at the second end 504. This configuration causes the angular velocity of the fluid mixture to beneficially increase as the fluid mixture rises in the reactor, thereby enhancing phase separation effects and associated graphene sheet aggregation.
  • FIG. 6 illustrates an exemplary process flow 600 by which a tubular-shaped graphene sheet material may be produced.
  • the process flow 600 includes a vortex reactor 601.
  • the vortex reactor 601 may represent any of the vortex reactor embodiments described herein.
  • the vortex reactor 601 is similar to a vortex reactor as shown in Figure 4 or 5.
  • the illustrated embodiment combines a water stream 638 and a heptane stream 640 to form the reaction fluid mixture 642.
  • a suitable pump 644 drives flow of the fluid mixture into the reactor 601, where it is combined with a graphite stream 646 at the initial inflow region of the reactor 601 (i.e., the exfoliation zone 648).
  • the illustrated ultrasound horn or array of horns 634 impart ultrasound energy to the graphite material at a level sufficient to generate graphene flakes via ultrasonic exfoliation of the graphite material.
  • operation of the vortex reactor 601 outputs a process stream 650 including the generated tube-shaped graphene sheet along with the water and heptane.
  • the process stream 650 is then routed to one or more downstream processes 652.
  • the generated graphene sheet material is cut, sliced, and/or otherwise formed into a threaded shape, which may be wound, spooled, or otherwise stored as a graphene thread or string product.
  • a threaded shape Such a product may be utilized by weaving into fabric or other useful material, for example.
  • the tube-shaped graphene sheet material may be sliced (e.g., in a helical fashion) to form a ribbon shape.
  • the ribbon may then be wound onto a spool or otherwise suitably arranged for use as a graphene ribbon product.
  • the illustrated one or more downstream processes 652 include water and/or heptane recycling process steps to generate a recovered water stream 654 and a recovered heptane stream 656. As shown, water and heptane makeup may be added as needed to maintain desired mass balances, fluid ratios, and process flow operability.
  • the vortex reactor 601 may be operated in a continuous fashion with continuous collection of generated graphene sheet material.
  • the reactor 601 is operated in a semi-batch mode, with fluids continuously fed and recycled as needed while a tubular-shaped graphene sheet is formed and then ejected, with the process repeated as desired.
  • Other embodiments may include operation in batch mode.
  • heptane may be replaced or combined with another non-polar liquid, such as another non-polar organic solvent
  • water may be replaced or combined with another polar liquid, such as an alcohol, ammonia, acetone, etcetera.
  • FIG 9 illustrates an alternative process flow 900 by which a graphene sheet material may be produced.
  • the vortex reactor 901 may represent any of the vortex reactor embodiments described herein.
  • the vortex reactor 901 is similar to a vortex reactor as shown in Figure 4 or 5.
  • the illustrated embodiment combines a water stream 938 and a heptane stream 940 to form the reaction fluid mixture 942.
  • a suitable pump 944 drives flow of the fluid mixture into the reactor 901, where it is combined with a graphite stream 946 at the initial inflow region of the reactor 901 (i.e., the exfoliation zone 948).
  • the illustrated ultrasound horn 934 imparts ultrasound energy to the graphite material at a level sufficient to generate graphene flakes via ultrasonic exfoliation of the graphite material.
  • Other embodiments may include additional ultrasound horns.
  • a plurality of ultrasound horns may be arranged in an array near the exfoliation zone 948.
  • the mixer 949 is configured to provide sufficient shearing or mixing to form an unstable emulsion (i.e., an emulsion that will phase separate) of graphene coated spheres.
  • Any mixing device capable of forming the emulsion may be utilized.
  • a suitable mixer is a high-shear mixer having a vortex induction mechanism as disclosed in U.S. Patent Application Publication No. 2016/0346758, which is incorporated herein by reference in its entirety.
  • the emulsion is then routed from the mixer 949 to a trough 951.
  • the trough 951 may be any suitable structure that allows phase separation of the emulsion as the fluid moves, in laminar flow, from the inlet side to the outlet side of the trough 951.
  • van der Waals attraction will cause the graphene sheets enveloping the fluid spheres to spread out at the interface layer and self-assemble into a continuous sheet.
  • the trough 951 functions as an "extruder" of the coalesced graphene sheet.
  • process conditions such as flow rate through the trough 951 are calibrated to produce a graphene sheet having a width substantially equal to the width of the trough 951.
  • the graphene sheet may be collected on a suitable receiving substrate.
  • a spool 953 is positioned near the trough 951 to wind and collect the graphene sheet.
  • Other embodiments may additionally or alternatively utilize other collection means, such as a scraper plate, collection tray, rotating disk device, or the like.
  • the collected graphene sheet may also be cut into a threaded or ribbon shape.
  • the process 900 may also include water and/or heptane recycling steps to generate a recovered water stream 954 and a recovered heptane stream 956.
  • Water and/or heptane makeup may be added as needed to maintain desired mass balances, fluid ratios, and process flow operability.
  • the process 900 may be operated in a continuous fashion with continuous collection of generated graphene sheet material. Other implementations may be operated in batch or semi-batch mode. Further, as described above, other embodiments may utilize other suitable combinations of immiscible fluids.
  • heptane may be replaced or combined with another non- polar liquid, such as another non-polar organic solvent, and water may be replaced or combined with another polar liquid, such as an alcohol, ammonia, acetone, etcetera
  • FIG. 7 illustrates a vortex reactor 700 configured as a dual vortex reactor.
  • the illustrated reactor has a substantially cylindrical shape, though it may have an alternative shape, such as a conical shape similar to the embodiment of Figure 5 or other reactor body shape described herein.
  • the reactor 700 includes an inlet port assembly 702 disposed at a first end 704.
  • the inlet port assembly 702 is configured to form an outer vortex when a fluid mixture is directed into the reactor.
  • the outer vortex rises to the second end 706 of the reactor, where it then passes radially inward into a guide cone 758 and is directed downward in an inner vortex through an outlet pipe 714 that exits the reactor at the first end 704.
  • the fluid mixture includes two immiscible fluids, with at least one of the immiscible fluids being a polymerizable fluid. Any desired combination of polymerizable fluid and at least one additional immiscible fluid may be utilized according to particular application needs, desired end product composition, and the like.
  • the fluid mixture includes styrene and water.
  • Other suitable polymerizable monomers that may be included in at least one phase of the fluid mixture include isoprene, butyl acrylate, divinylbenzene, methyl acrylate, tetra(ethylene glycol) diacrylate, and butyl methacrylate, for example.
  • the illustrated reactor 700 includes a first ultrasound horn or array 734 of one or more ultrasound horns disposed in a base plate 736 at the first end 704.
  • a mass of graphite particles is input into the reactor at an exfoliation zone 732 disposed above a first ultrasound horn array 734.
  • Ultrasound exfoliation of the graphite causes the formation of graphene flakes, which are carried upwards in the outer vortex of the fluid while self-assembling at the interface between the separate fluids.
  • the reactor is substantially closed at the second end 706, the fluid reaching the second end 706 is directed radially inward into the guide cone 758 and then downward into the outlet pipe 714.
  • These structures assist in creating the emulsion required for manufacturing a graphene-enhanced, porous composite material.
  • a high shear zone is created which aids in dispersing fine droplets (e.g., water droplets) within the continuous phase of the monomer.
  • the relative proportions of the reactor diameter and the guide cone diameter may be adjusted to determine the angular velocity at which the emulsion is formed at the crest of the guide cone.
  • a second ultrasound horn or array 760 is positioned at the second end 706.
  • a second ultrasound horn or array 760 consists of a single ultrasound horn extending into the guide cone 758 at a distance to maximize the ultrasound energy imparted to the passing fluid vortex.
  • Alternative embodiments may include additional ultrasound horns as part of the second ultrasound array 760 and/or can vary the relative depth of the ultrasound horn with respect to the guide cone 758.
  • the fluid phases and the graphene will crest over the top edge of the guide cone 758 to be exposed to angular acceleration, shear forces, and ultrasound energy (and associated cavitation bubble formation and collapse) imparted by the second ultrasound array 760.
  • the conditions at this region of the reactor can be tailored to generate an emulsion having desired characteristics.
  • the graphene within the mixture will assemble at the interface of the formed emulsion droplets to stabilize the emulsion.
  • graphene will aggregate at the interfacial periphery of water droplets formed within another immiscible fluid (e.g., a styrene or styrene-based fluid) to form a graphene stabilized emulsion.
  • another immiscible fluid e.g., a styrene or styrene-based fluid
  • the illustrated embodiment includes a set of injectors 762 disposed at the second end 706 for injecting one or more suitable polymerizing agents into the fluid mixture at the region where the emulsion is formed.
  • injectors 762 may be utilized.
  • the polymerizing agent(s) then pass with the emulsified mass through the outlet pipe 714.
  • the emulsified mass may be sent to one or more downstream processes for generating a graphene-enhanced composite material.
  • the emulsified mass may be sent to one or more molds to allow polymerization and formation of the composite.
  • the polymerizable fluid forms a polymer having a porous structure formed by the droplets of the other fluid.
  • the graphene remains at the surface of the formed cavities, providing enhanced material properties to the composite material.
  • the fluid forming the droplets e.g., water
  • the fluid forming the droplets may be removed through drying, leaving graphene coated voids/pores behind.
  • the reactor 700 may also include one or more wall ports (not shown here, see corresponding structure of Figure 1) for introducing one or more fluids, additives, or other materials into the fluid mixture prior to emulsification and/or contact with any polymerizing agents.
  • one presently preferred embodiment utilizes a wall port to introduce an additive including poly(3,4-ethylenedioxythiophene) poly(styrene- sulfonate) ("PEDOT:PSS”) to the outer vortex of the fluid mixture.
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene) poly(styrene- sulfonate)
  • the PEDOT:PSS is left behind after polymerization to form a conductive coating on the inside surfaces of the composite voids/pores.
  • FIG. 8 illustrates an exemplary process flow 300 for producing a graphene- enhanced composite material using a vortex reactor 301.
  • the vortex reactor 301 is configured similar to the vortex reactor 700 shown in Figure 7.
  • streams of immiscible fluids which in this example include a styrene stream 340 and a water stream 338 are mixed to form the reaction fluid mixture 342.
  • a suitable pump 344 drives flow of the fluid mixture into the reactor 301, where it is combined with a graphite stream 346 at the initial inflow region of the vortex reactor 301 (i.e., the exfoliation zone 348).
  • the illustrated array of ultrasound horns 334 impart ultrasound energy to the graphite material to generate graphene flakes.
  • Operation of the reactor 301 causes the fluid mixture to flow upwards in an outer vortex and then to pass into the guide cone 358, where ultrasound energy from the ultrasound horn 360 and one or more polymerizing agents from injectors 362 are applied to the fluid mixture.
  • the resulting emulsion then passes down outlet/exit pipe 314, where it may be routed for further downstream processing.
  • Additives may be optionally injected through wall port 330.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
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  • Materials Engineering (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne des dispositifs, des systèmes et des procédés de fabrication de matériaux de graphène à l'aide d'un réacteur à vortex. Le réacteur à vortex est conçu pour recevoir un mélange fluide de deux fluides non miscibles. Lorsqu'il est dirigé dans le réacteur, le mélange fluide suit un trajet tourbillonnaire qui assure une séparation efficace des fluides et forme une interface entre les fluides. Des flocons de graphène sont générés par exfoliation ultrasonore d'un matériau de graphite et les flocons de graphène s'agrègent au niveau de l'interface pour former un matériau en feuille tubulaire de graphène.
PCT/IB2017/057581 2016-12-01 2017-12-01 Fabrication de matériaux de graphène à l'aide d'un réacteur à cavitation WO2018100552A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020021248A1 (fr) * 2018-07-24 2020-01-30 Npl Management Limited Procédé et appareil de production de matériaux
RU2752936C1 (ru) * 2020-12-04 2021-08-11 Дмитрий Игоревич Шварцман Способ получения графена
CN113697801A (zh) * 2021-10-15 2021-11-26 黑龙江省科学院高技术研究院 一种基于涡流空化技术的石墨烯制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101939087A (zh) * 2008-02-08 2011-01-05 普拉克生化公司 涡流混合器和获得过饱和溶液或浆液的方法
CN101965218A (zh) * 2008-01-31 2011-02-02 索尔博水技术公司 用于分离多相流体的方法和设备及其应用
CN203173875U (zh) * 2013-04-09 2013-09-04 中国海洋石油总公司 一种用于油田含油污水的无动力旋流反应器
CN204034664U (zh) * 2014-08-19 2014-12-24 青岛金墨自动化科技有限公司 一种氧化石墨烯真空涡流剥离装置
TW201501802A (zh) * 2013-07-10 2015-01-16 Cao Yan Huan 渦流反應裝置
CN104477882A (zh) * 2014-10-23 2015-04-01 江阴碳谷科技有限公司 一种涡流式石墨烯剥离装置、石墨烯生产系统及生产方法
WO2016193813A1 (fr) * 2015-06-01 2016-12-08 Cetamax Ventures Ltd. Systèmes et procédés de traitement de fluides

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101965218A (zh) * 2008-01-31 2011-02-02 索尔博水技术公司 用于分离多相流体的方法和设备及其应用
CN101939087A (zh) * 2008-02-08 2011-01-05 普拉克生化公司 涡流混合器和获得过饱和溶液或浆液的方法
CN203173875U (zh) * 2013-04-09 2013-09-04 中国海洋石油总公司 一种用于油田含油污水的无动力旋流反应器
TW201501802A (zh) * 2013-07-10 2015-01-16 Cao Yan Huan 渦流反應裝置
CN204034664U (zh) * 2014-08-19 2014-12-24 青岛金墨自动化科技有限公司 一种氧化石墨烯真空涡流剥离装置
CN104477882A (zh) * 2014-10-23 2015-04-01 江阴碳谷科技有限公司 一种涡流式石墨烯剥离装置、石墨烯生产系统及生产方法
WO2016193813A1 (fr) * 2015-06-01 2016-12-08 Cetamax Ventures Ltd. Systèmes et procédés de traitement de fluides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020021248A1 (fr) * 2018-07-24 2020-01-30 Npl Management Limited Procédé et appareil de production de matériaux
US20210346859A1 (en) * 2018-07-24 2021-11-11 Npl Management Limited Method of and apparatus for producing materials
RU2752936C1 (ru) * 2020-12-04 2021-08-11 Дмитрий Игоревич Шварцман Способ получения графена
CN113697801A (zh) * 2021-10-15 2021-11-26 黑龙江省科学院高技术研究院 一种基于涡流空化技术的石墨烯制备方法
CN113697801B (zh) * 2021-10-15 2022-10-25 黑龙江省科学院高技术研究院 一种基于涡流空化技术的石墨烯制备方法

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