CN103880002A - Industrial device for continuously producing graphene powder and method thereof - Google Patents
Industrial device for continuously producing graphene powder and method thereof Download PDFInfo
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Abstract
The invention discloses an industrial device for continuously producing graphene powder and a method thereof. The device comprises a liquid storage tank, a flow valve, a plurality of ultrasonic processors, a microwave reaction kettle, a vibrating screen, a mixing tank, a reservoir, a booster pump, a spray drying tower and a cyclone centrifuge. The method for preparing graphene comprises the following steps: adjusting the surface tension by controlling the proportion of a dispersant, thus obtaining evenly dispersed grapheme through the synergistic effect of continuous ultrasonic and micro waves after evenly mixing with graphite; adding a bonding solution to graphene dispersion liquid to prepare slurry; carrying out spray drying and pelleting on the slurry by adopting centrifugal spray drying equipment. Large-scale production of the graphene is achieved by adopting a continuous ultrasonic-micro wave combined mode, pelleting of the graphene can be achieved by combining with spray drying, the environmental pollution is reduced, and transportation and application are facilitated.
Description
Technical field
The invention belongs to technical field of nano material, relate to a kind of preparation of industrialization Graphene method, be specifically related to a kind of serialization and produce graphene powder full scale plant and method thereof.
Background technology
Graphene (Graphene) is a kind of individual layer sheet structured material being made up of carbon atom, because the advantages such as its high strength, high heat conductance, high conductivity and high-specific surface area have been subject to investigator's extensive attention.At present, the method for preparing Graphene both at home and abroad mainly contains several as follows:
(1) micromechanics stripping method; The Graphene quality that this method makes is high, but can only obtain a limited number of graphene films, is only applicable to probe into as fundamental research the electrical properties of Graphene.
(2) epitaxial growth method; This method preparation condition harshness, all requires to carry out under the conditions such as high temperature high vacuum or certain particular atmosphere and single crystalline substrate, and the Graphene making be difficult for separate from substrate, can not prepare on a large scale Graphene.
(3) oxidation-reduction method; The method be at present comparatively common low-cost high-efficiency prepare the chemical process of big area Graphene layer material, but the Graphene obtaining contains a large amount of oxy radicals and defect, its conductivity is lower, and reductive agent major part is poisonous, makes preparation process have environmental pollution.
(4) chemical Vapor deposition process; This method can meet the requirement that high-quality graphene is prepared in mass-producing, but cost is higher, complex process.
(5) electrolytic process; This method can be synthesized a large amount of Graphenes, but the surface of the Graphene synthesizing is all with a large amount of positive ion negative ion or organism.Aforesaid method respectively has limitation part, therefore people urgently wish to develop a kind of environmental friendliness, technique simple, can less Graphene method and the device of large-scale production place defect.
Liquid phase ultrasonic stripping method is the crushing effect to powder by ultrasonic wave, in organic solvent, graphite flake layer is peeled off to the method (J.Mater.Chem.19,3367-3369,2009) of preparing Graphene.Organic solvent not only provides preparation place, and can be played and be promoted graphite linings to separate, disperse, protect, isolate the effect of Graphene by control condition.The method not only can be carried out large volume preparation, and simultaneously owing to not introducing chemical process, Graphene crystalline structure has also obtained better protecting, the Graphene of availability excellence.But this method exists energy consumption high, inefficient defect.And microwave liquid phase stripping method is prepared Graphene, energy consumption is low, and product size is evenly distributed, and can stable suspersion in reaction solution.
China Patent No. CN 103253659 A disclose " a kind of ultrasonic wave is peeled off the method for preparing graphite alkene ", this method is evenly mixed powdered graphite and intercalator by a certain percentage in organic solvent, recycling ultrasound bath is peeled off certain hour, centrifugation, obtains grapheme material after filtration.It is high that the prepared Graphene of this method has quality, and excellent performance, defect are few, but the method is periodical operation, and energy consumption is high, therefore cannot scale operation.
To sum up, the problem that how to solve high-quality graphene large-scale production becomes the hot issue of people's research.
Summary of the invention
The object of the invention is to propose a kind of serialization and produce graphene powder full scale plant and method thereof; there is uninterrupted continuous production, and equipment is simple, operation simple and feasible; easily be automated and suitability for industrialized production, and can solve the problem of high-quality graphene large-scale production.
For achieving the above object, solution of the present invention is:
Graphene powder full scale plant is produced in a kind of serialization, and it comprises the stationary tank being connected successively by pipeline, multistage microwave reaction kettle, reservoir, spray-drying tower and cyclone centrifugal device, is respectively equipped with flow valve between each several part; On reservoir, be connected with tempering tank, between reservoir and spray-drying tower, be provided with topping-up pump; Rapid stirring oar is installed respectively in stationary tank, tempering tank and reservoir; Microwave reaction kettles at different levels are provided with processor for ultrasonic wave, and microwave reaction kettle is temperature control microwave hydrothermal reaction kettle, separately between the pipeline opening of microwave reaction kettles at different levels, are provided with vibration screen, and vibration screen both sides are provided with the blade of horizontal rapid stirring.
Described processor for ultrasonic wave is energy gathering type ultrasound probe, and ultrasonic frequency is in 20kHz-80kHz.
A method for graphene powder is produced in serialization, and the method step comprises:
Step 1: graphite, dispersion agent are placed in to stationary tank, stir, the proportioning of controlling dispersion agent obtains the graphite premix that surface tension is 30-50mN/m, prepares slurry simultaneously in tempering tank;
Step 2: control flow valve, above-mentioned premix is flowed into microwave reaction kettle by pipeline, take to control the output rating of energy gathering type ultrasound probe number, ultrasonic frequency, microwave reaction kettle, obtain graphene dispersing solution in reservoir;
Step 3: control the flow valve of tempering tank, slurry is mixed with graphene dispersing solution, obtain Graphene slurry;
Step 4: adopt centrifugal spray drying mode, reach granulation object by adjusting rotary speed in cyclone centrifugal device, thereby obtain Graphene particle.
Graphite in described step 1 is expanded graphite or graphite oxide.
Dispersion agent in described step 1 is selected from water, ammoniacal liquor, ethanol, Virahol, acetone, ethylene glycol, N-Methyl pyrrolidone, dimethyl formamide, tetrahydrofuran (THF), dimethyl formamide, orthodichlorobenzene, acetonitrile, 1, a kind of or at least two or more combination in 2-ethylene dichloride and sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Trisodium Citrate, preferably from polar solvent, special further preferably ammoniacal liquor, ethanol, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Trisodium Citrate, a kind of or at least two or more combination of N-Methyl pyrrolidone.
Graphite concentration in graphite premix in described step 1 is 0.1-3%.
Tackiness agent in described step 1 comprises more than one the solution in hydrocarbon, thermoplastic resin and thermosetting resin.
In described step 2, control energy gathering type ultrasound probe ultrasonic frequency for graphite raw material being carried out to ultrasonic mechanically peel with frequency or mixing with any power; Described with being same ultrasonic wave frequently, be mixed down two or more ultrasonic wave.
Microwave heating has selectivity, instantaneity, high efficiency, controls suitable microwave condition and can promote the pulverizing of graphite to peel off.Microwave is a kind of non-ionising radiation energy that is caused molecular motion by ion migration and dipole rotation, when being subject to microwave electromagnetic field action, polar molecule just can produce instantaneous polarization, and do at a terrific speed reversal of pole campaign, thereby produce key motion, tear phase mutual friction, collision between particle, promote better contact and the reaction of molecular polarity part, produce rapidly a large amount of heat energy simultaneously, impel graphite to pulverize, peel off; Secondly, graphite is a kind of good microwave absorbing medium, and by microwave treatment, graphite can absorb microwave fast and produce huge heat, and graphite layers can produce huge thermal stresses, can make effectively peeling off between layers of graphite.
The synergy that the present invention makes full use of hyperacoustic mechanical dispersion effect, ultrasonic cavitation effect, microwave homogeneous heating effect and produces between them, strengthening graphite stripping process, thereby realize Graphene efficiently, fast preparation.
Feature of the present invention and beneficial effect:
(1) this device adopts continuous ultrasound mechanically peel graphite acquisition Graphene to belong to physical method, and the structure of not destroying Graphene can obtain good, the flawless Graphene of quality, and in device, adopts multiple energy gathering types probes can realize continuous large-scale production;
(2) adopt microwave simultaneously, can utilize the variation rapid heating of Electric and magnetic fields, Reaction time shorten greatly, can reduce energy consumption to a great extent, improves preparation efficiency;
(3) vibration screen that connects the install pipeline of microwave reaction kettle can be controlled the product size that every first order reaction still leads to next stage reactor, avoids the waste of energy can ensure again the quality of the product obtaining simultaneously;
(4) be combined with centrifugal spray drying, can in the process of producing, avoid environmental pollution, after Direct spraying is dry, granulation can facilitate using and transporting of later stage.
Brief description of the drawings
Fig. 1 is the schematic diagram that graphene powder full scale plant is produced in serialization of the present invention.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to following specific embodiment.
As shown in Figure 1, the present invention has disclosed a kind of serialization and has produced graphene powder full scale plant, it comprises the stationary tank 1, multistage microwave reaction kettle 4, reservoir 7, spray-drying tower 9 and the cyclone centrifugal device 10 that are connected successively by pipeline, is respectively equipped with flow valve 2 between each several part; On reservoir 7, be also connected with tempering tank 6, between reservoir 7 and spray-drying tower 9, be provided with topping-up pump 8; The interior rapid stirring oar of installing respectively of stationary tank 1, tempering tank 6 and reservoir 7; Microwave reaction kettles 4 at different levels are provided with processor for ultrasonic wave 3, microwave reaction kettle 4 is temperature control microwave hydrothermal reaction kettle, the another vibration screen 5 that is provided with between the pipeline opening of microwave reaction kettles 4 at different levels, this screen cloth can be controlled the graphite size that enters next stage microwave reaction kettle, and vibration screen both sides are provided with the blade of horizontal rapid stirring, can pulverize large-sized graphite and prevent screen plugging.This processor for ultrasonic wave is that energy gathering type ultrasound probe and ultrasonic frequency are in 20kHz-80kHz.
And utilize this full scale plant specifically to produce the method for graphene powder, its step comprises:
Step 1: by graphite, dispersion agent is placed in stationary tank, wherein graphite is expanded graphite or graphite oxide, and dispersion agent is selected from water, ammoniacal liquor, ethanol, Virahol, acetone, ethylene glycol, N-Methyl pyrrolidone, dimethyl formamide, tetrahydrofuran (THF), dimethyl formamide, orthodichlorobenzene, acetonitrile, 1, 2-ethylene dichloride and sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, a kind of or at least two or more combination in Trisodium Citrate, preferably from polar solvent, special further preferred ammoniacal liquor, ethanol, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Trisodium Citrate, the combination that N-Methyl pyrrolidone is a kind of or at least two or more, stir, the proportioning of controlling dispersion agent obtains the graphite premix that surface tension is 30-50mN/m, wherein the graphite concentration in graphite premix is 0.1-3%, simultaneously in tempering tank 6, prepare slurry, tackiness agent comprises more than one the solution in hydrocarbon, thermoplastic resin and thermosetting resin,
Step 2: control flow valve, above-mentioned premix is flowed into microwave reaction kettle 4 by pipeline, take to control the output rating of energy gathering type ultrasound probe number, ultrasonic frequency, microwave reaction kettle, obtain graphene dispersing solution in reservoir 7; Wherein control energy gathering type ultrasound probe ultrasonic frequency for graphite raw material being carried out to ultrasonic mechanically peel with frequency or mixing with any power; Described with being same ultrasonic wave frequently, be mixed down two or more ultrasonic wave;
Step 3: control the flow valve of tempering tank 6, slurry is mixed with graphene dispersing solution, obtain Graphene slurry;
Step 4: adopt centrifugal spray drying mode, reach granulation object by adjusting rotary speed in cyclone centrifugal device 10, thereby obtain Graphene particle.
Case study on implementation one
Step 1: expanded graphite, ethanol, water, Sodium dodecylbenzene sulfonate are placed in to stationary tank 1, Sodium dodecylbenzene sulfonate content 0.01%, content of graphite 1%, the proportioning of water and ethanol is 3:1, above-mentioned substance is carried out fully stirring and obtain even graphite premix, in tempering tank 6, prepare Microcrystalline Cellulose slurry, concentration is 0.01% simultaneously;
Step 2: control flow valve, above-mentioned premix is flowed into microwave reaction kettle 4 with the speed of 100L/h by pipeline, open 8 energy gathering type ultrasound probe participation work, adopt identical frequency process to peel off graphite, frequency is that low frequency 20kH, the output rating of adjusting microwave reaction kettle are 200W, in reservoir 7, obtains graphene dispersing solution;
Step 3: the flow velocity of controlling the flow valve of tempering tank 6 is 100L/h, opens rapid stirring oar, stirs slurry fully to mix with graphene dispersing solution, obtains Graphene slurry;
Step 4: it is 150 DEG C that drying machine with centrifugal spray temperature in is set, and temperature out is 80 DEG C, liquid ejection speed is 150L/h.After sample drying, in cyclone centrifugal device 10, reach granulation object by adjusting rotary speed, thereby obtain Graphene particle.
Above-mentioned Graphene is added in polypropylene (PP), and taking polypropylene as base material, having prepared Graphene content is the matrix material (representing with PP, 1-PP10,1-PP15,1-PP20 respectively) of difference 0%, 10%, 15,20%.
Above-mentioned materials is carried out to strength test, and each sample test 4 times, averages.Strength test the results are shown in Table 1.
The intensity contrast table of table 1 polypropylene and Graphene/polypropylene composite material thereof
Case study on implementation two
Step 1: expanded graphite, water, ethylene glycol, Trisodium Citrate are placed in to stationary tank 1, the content of sodium citrate 0.01%, content of graphite 1%, the proportioning of water and ethylene glycol is 4:1, above-mentioned substance is carried out fully stirring and obtain even graphite premix, in tempering tank 6, prepare carboxymethyl cellulose slurry, concentration is 0.01% simultaneously;
Step 2: control flow valve, above-mentioned premix is flowed into microwave reaction kettle with the speed of 150L/h by pipeline, open 8 energy gathering type ultrasound probe participation work, adopt mixing mode to peel off graphite, frequency is followed successively by 20kH, 30kH, 40kH, 50kH, 20kH, 30kH, 40kH, 50kH, the output rating of adjusting microwave reaction kettle is 300W, in reservoir 7, obtains graphene dispersing solution;
Step 3: the flow velocity of controlling the flow valve of tempering tank 6 is 150L/h, opens rapid stirring oar, stirs slurry fully to mix with graphene dispersing solution, obtains Graphene slurry;
Step 4: it is 200 DEG C that drying machine with centrifugal spray temperature in is set, and temperature out is 80 DEG C, liquid ejection speed is 200L/h.After sample drying, in cyclone centrifugal device 10, reach granulation object by adjusting rotary speed, thereby obtain Graphene particle.
Above-mentioned Graphene is added in polypropylene (PP), and taking polypropylene as base material, having prepared Graphene content is the matrix material (representing with PP, 2-PP10,2-PP15,2-PP20 respectively) of difference 0%, 10%, 15,20%.
Above-mentioned materials is carried out to strength test, and each sample test 4 times, averages.Strength test the results are shown in Table 2.
The intensity contrast table of table 2 polypropylene and Graphene/polypropylene composite material thereof
Case study on implementation three
Step 1: expanded graphite, water, N-Methyl pyrrolidone, sodium lauryl sulphate are placed in to stationary tank 1, Sodium Dodecyl Sulfate 0.01%, content of graphite 2%, the proportioning of water and N-Methyl pyrrolidone is 4:1, above-mentioned substance is carried out fully stirring and obtain even graphite premix, in tempering tank 6, prepare polyacrylic resin slurry, concentration is 0.02% simultaneously;
Step 2: control flow valve, above-mentioned premix is flowed into microwave reaction kettle with the speed of 200L/h by pipeline, open 8 energy gathering type ultrasound probe participation work, adopt mixing mode to peel off graphite, frequency is followed successively by 20kH, 30kH, 40kH, 20kH, 30kH, 40kH, 20kH, 20kH, the output rating of adjusting microwave reaction kettle is 250W, in reservoir 7, obtains graphene dispersing solution;
Step 3: the flow velocity of controlling the flow valve of tempering tank 6 is 200L/h, opens rapid stirring oar, stirs slurry fully to mix with graphene dispersing solution, obtains Graphene slurry;
Step 4: it is 180 DEG C that drying machine with centrifugal spray temperature in is set, and temperature out is 80 DEG C, liquid ejection speed is 300L/h.After sample drying, in cyclone centrifugal device 10, reach granulation object by adjusting rotary speed, thereby obtain Graphene particle.
Above-mentioned Graphene is added in polypropylene (PP), and taking polypropylene as base material, having prepared Graphene content is the matrix material (representing with PP, 3-PP10,3-PP15,3-PP20 respectively) of difference 0%, 10%, 15,20%.
Above-mentioned materials is carried out to strength test, and each sample test 4 times, averages.Strength test the results are shown in Table 3.
The intensity contrast table of table 3 polypropylene and Graphene/polypropylene composite material thereof
Conducting performance test
The product that case study on implementation one is obtained adds in polypropylene with 10%, 15% amount, called after 1PP-10, and 1PP-15, the product that case study on implementation two is obtained adds in polypropylene with 10%, 15%, called after 2PP-10,2PP-15; Moral is filled in admittedly simultaneously superconductive carbon black XE-2B add in polypropylene as a comparison sample, add 10% called after XE-2B-PP10, add 15% called after XE-2B-PP15.Above-mentioned sample is carried out to conductive test.Test result is in table 4:
Table 4 polypropylene/graphite performance
Can find out from the above results, the Graphene sample quality preparing by the present invention is good, can be used as enhancing, conductive filler material.
Claims (8)
1. a graphene powder full scale plant is produced in serialization, it is characterized in that: comprise the stationary tank being connected successively by pipeline, multistage microwave reaction kettle, reservoir, spray-drying tower and cyclone centrifugal device, be respectively equipped with flow valve between each several part; On reservoir, be connected with tempering tank, between reservoir and spray-drying tower, be provided with topping-up pump; Rapid stirring oar is installed respectively in stationary tank, tempering tank and reservoir; Microwave reaction kettles at different levels are provided with processor for ultrasonic wave, and microwave reaction kettle is temperature control microwave hydrothermal reaction kettle, separately between the pipeline opening of microwave reaction kettles at different levels, are provided with vibration screen, and vibration screen both sides are provided with the blade of horizontal rapid stirring.
2. graphene powder full scale plant is produced in a kind of serialization as claimed in claim 1, it is characterized in that: described processor for ultrasonic wave is energy gathering type ultrasound probe, and ultrasonic frequency is in 20kHz-80kHz.
3. a method for graphene powder is produced in serialization, and its step comprises:
Step 1: graphite, dispersion agent are placed in to stationary tank, stir, the proportioning of controlling dispersion agent obtains the graphite premix that surface tension is 30-50mN/m, prepares slurry simultaneously in tempering tank;
Step 2: control flow valve, above-mentioned premix is flowed into microwave reaction kettle by pipeline, take to control the output rating of energy gathering type ultrasound probe number, ultrasonic frequency, microwave reaction kettle, obtain graphene dispersing solution in reservoir;
Step 3: control the flow valve of tempering tank, slurry is mixed with graphene dispersing solution, obtain Graphene slurry;
Step 4: adopt centrifugal spray drying mode, reach granulation object by adjusting rotary speed in cyclone centrifugal device, thereby obtain Graphene particle.
4. the method that graphene powder is produced in a kind of serialization as claimed in claim 3, is characterized in that: the graphite in described step 1 is expanded graphite or graphite oxide.
5. the method that graphene powder is produced in a kind of serialization as claimed in claim 3, it is characterized in that: the dispersion agent in described step 1 is selected from water, ammoniacal liquor, ethanol, Virahol, acetone, ethylene glycol, N-Methyl pyrrolidone, dimethyl formamide, tetrahydrofuran (THF), dimethyl formamide, orthodichlorobenzene, acetonitrile, 1, 2-ethylene dichloride and sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, a kind of or at least two or more combination in Trisodium Citrate, preferably from polar solvent, special further preferred ammoniacal liquor, ethanol, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Trisodium Citrate, the combination that N-Methyl pyrrolidone is a kind of or at least two or more.
6. the method that graphene powder is produced in a kind of serialization as claimed in claim 3, is characterized in that: the graphite concentration in the graphite premix in described step 1 is 0.1-3%.
7. the method for graphene powder is produced in a kind of serialization as claimed in claim 3, it is characterized in that: the tackiness agent in described step 1 comprises more than one the solution in hydrocarbon, thermoplastic resin and thermosetting resin.
8. the method that graphene powder is produced in a kind of serialization as claimed in claim 3, is characterized in that: in described step 2, control energy gathering type ultrasound probe ultrasonic frequency for graphite raw material being carried out to ultrasonic mechanically peel with frequency or mixing with any power; Described with being same ultrasonic wave frequently, be mixed down two or more ultrasonic wave.
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