CN103880002B - A kind of continuous prodution graphene powder full scale plant and method thereof - Google Patents
A kind of continuous prodution graphene powder full scale plant and method thereof Download PDFInfo
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention discloses a kind of continuous prodution graphene powder full scale plant and method thereof.This device comprises stationary tank, flow valve, several processor for ultrasonic wave, microwave reaction kettle, vibration screen, tempering tank, reservoir, topping-up pump, spray-drying tower and cyclone centrifugal device.It prepares Graphene method is carry out adjustment sheet surface tension by the proportioning of control dispersion agent, then obtains by the synergy of continuous ultrasound and microwave the Graphene that is uniformly dispersed after mixing with graphite; Add slurry and prepare slurry to graphene dispersing solution, adopt Frequency Conversion Technique of Centrifugal Spraying Drying Equipment to carry out spraying dry, granulation to slurry.The present invention adopts continuous ultrasound-microwave combination to achieve Graphene scale operation, is combined the granulation that can realize Graphene, decreases environmental pollution with spraying dry, convenient transport and use.
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 continuous prodution graphene powder full scale plant and method thereof.
Background technology
Graphene (Graphene) is a kind of individual layer sheetlike material be made up of carbon atom, because the advantages such as its high strength, high heat conductance, high conductivity and high-specific surface area receive the extensive attention of investigator.At present, the method preparing Graphene both at home and abroad mainly contains several as follows:
(1) micromechanics stripping method; The Graphene quality that this method obtains is high, but can only obtain a limited number of graphene film, and based on being only applicable to, the electrical properties of Graphene is probed in research.
(2) epitaxial growth method; This method preparation condition is harsh, all requires to carry out under high temperature high vacuum or certain condition such as particular atmosphere and single crystalline substrate, and obtained Graphene is not easily separated from substrate, can not prepare Graphene on a large scale.
(3) oxidation-reduction method; The method be at present comparatively common low-cost high-efficiency prepare the chemical process of large-area graphene layer material, but the Graphene obtained contains a large amount of oxy radicals and defect, its conductivity is lower, and reductive agent major part is poisonous, makes preparation process there is 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 synthesize a large amount of Graphenes, but the surface of the Graphene synthesized is all with a large amount of positive ion negative ions or organism.Aforesaid method respectively has limitation part, therefore people urgently wish to develop a kind of environmental friendliness, technique simple, can the less Graphene method of large-scale production place defect and device.
Liquid phase ultrasonic stripping method is by the crushing effect of ultrasonic wave to powder, in organic solvent graphite flake layer is peeled off to the method (J.Mater.Chem.19,3367-3369,2009) preparing Graphene.Organic solvent not only provides preparation place, and can be played the effect promoting graphite linings separation, dispersion, protection, isolation Graphene by control condition.The method not only can carry out large volume preparation, and simultaneously owing to not introducing chemical process, Graphene crystalline structure have also been obtained better protecting, the Graphene of availability excellence.But it is high to there is energy consumption in this method, inefficient defect.And microwave liquid phase stripping method prepares Graphene, energy consumption is low, and product size is evenly distributed, and energy stable suspersion is in reaction solution.
China Patent No. CN103253659A discloses " a kind of ultrasonic wave peels off the method for preparing graphite alkene ", this method is by powdered graphite and intercalator Homogeneous phase mixing in organic solvent by a certain percentage, recycling ultrasound bath carries out stripping certain hour, centrifugation, namely obtains grapheme material after filtration.It is high that Graphene prepared by 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 how solving 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 continuous prodution graphene powder full scale plant and method thereof; there is the advantage of uninterrupted continuous production, and equipment is simple, operation simple and feasible; easily be automated and suitability for industrialized production, and the problem of high-quality graphene large-scale production can be solved.
For achieving the above object, solution of the present invention is:
A kind of continuous prodution graphene powder full scale plant, it comprises the stationary tank, multi-mode microwave reactor, reservoir, spray-drying tower and the cyclone centrifugal device that are connected successively by pipeline, is respectively equipped with flow valve between each several part; Reservoir is connected with tempering tank, between reservoir and spray-drying tower, is provided with topping-up pump; In stationary tank, tempering tank and reservoir, rapid stirring oar is installed respectively; Microwave reaction kettle at different levels is 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 kettle at different levels, is 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 within 20kHz-80kHz.
A method for continuous prodution graphene powder, the method step comprises:
Step one: graphite, dispersion agent are placed in stationary tank, stir, the proportioning controlling dispersion agent obtains the graphite premix that surface tension is 30-50mN/m, prepares slurry in tempering tank simultaneously;
Step 2: control flow valve, above-mentioned premix is flowed into microwave reaction kettle by pipeline, takes the output rating controlling energy gathering type ultrasound probe number, ultrasonic frequency, microwave reaction kettle, in reservoir, obtains graphene dispersing solution;
Step 3: the flow valve controlling tempering tank, mixes slurry 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, thus obtain Graphene particle.
Graphite in described step one is expanded graphite or graphite oxide.
Dispersion agent in described step one 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, the combination that special preferred ammoniacal liquor further, ethanol, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Trisodium Citrate, N-Methyl pyrrolidone are a kind of or at least two or more.
Graphite concentration in graphite premix in described step one is 0.1-3%.
Tackiness agent in described step one comprises more than one the solution in hydrocarbon, thermoplastic resin and thermosetting resin.
Energy gathering type ultrasound probe ultrasonic frequency is controlled for carrying out ultrasonic mechanically peel with any power to graphite raw material with frequency or mixing in described step 2; 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 that the pulverizing of graphite is peeled off.Microwave is a kind of non-ionising radiation energy being caused molecular motion by ion migration and dipole rotation, just instantaneous polarization can be produced when polar molecule is subject to microwave electromagnetic field action, and do reversal of pole campaign at a terrific speed, thus produce key motion, tear phase mutual friction between particle, collision, promote that molecular polarity part better contacts and reacts, produce a large amount of heat energy rapidly 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, ultrasound cavitation effect, microwave homogeneous heating effect and produces between them, strengthening graphite stripping process, thus realize Graphene efficient, prepare fast.
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 not destroying Graphene can obtain good, the flawless Graphene of quality, and adopts multiple energy gathering type probe can realize continuous large-scale production in device;
(2) adopt microwave simultaneously, the change rapid heating of Electric and magnetic fields can be utilized, can Reaction time shorten greatly, energy consumption can be reduced to a great extent, improve preparation efficiency;
(3) vibration screen of the install pipeline of connection microwave reaction kettle can control 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 obtained simultaneously;
(4) be combined with centrifugal spray drying, can avoid environmental pollution in the process of producing, after Direct spraying drying, granulation can facilitate using of later stage and transport.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of continuous prodution graphene powder full scale plant of the present invention.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to following specific embodiment.
As shown in Figure 1, present invention is disclosed a kind of continuous prodution graphene powder full scale plant, it comprises the stationary tank 1, multi-mode microwave reactor 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; Reservoir 7 is also connected with tempering tank 6, between reservoir 7 and spray-drying tower 9, is provided with topping-up pump 8; In stationary tank 1, tempering tank 6 and reservoir 7, rapid stirring oar is installed respectively; Microwave reaction kettle 4 at different levels is provided with processor for ultrasonic wave 3, microwave reaction kettle 4 is temperature control microwave hydrothermal reaction kettle, separately between the pipeline opening of microwave reaction kettle 4 at different levels, be provided with vibration screen 5, this screen cloth can control the graphite size entering next stage microwave reaction kettle, and vibration screen both sides are provided with the blade of horizontal rapid stirring, large-sized graphite can be pulverized and prevent screen plugging.This processor for ultrasonic wave be energy gathering type ultrasound probe and ultrasonic frequency within 20kHz-80kHz.
And utilize this full scale plant specifically to produce the method for graphene powder, its step comprises:
Step one: 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 preferred ammoniacal liquor further, 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 controlling dispersion agent obtains the graphite premix that surface tension is 30-50mN/m, graphite concentration wherein in graphite premix is 0.1-3%, in tempering tank 6, prepare slurry, tackiness agent comprises more than one the solution in hydrocarbon, thermoplastic resin and thermosetting resin simultaneously,
Step 2: control flow valve, flows into microwave reaction kettle 4 by above-mentioned premix by pipeline, takes the output rating controlling energy gathering type ultrasound probe number, ultrasonic frequency, microwave reaction kettle, in reservoir 7, obtains graphene dispersing solution; Wherein control energy gathering type ultrasound probe ultrasonic frequency for carrying out ultrasonic mechanically peel with any power to graphite raw material with frequency or mixing; Described with being same ultrasonic wave frequently, be mixed down two or more ultrasonic wave;
Step 3: the flow valve controlling tempering tank 6, mixes slurry 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, thus obtain Graphene particle.
Case study on implementation one
Step one: expanded graphite, ethanol, water, Sodium dodecylbenzene sulfonate are placed in stationary tank 1, sodium dodecyl benzene sulfonate content 0.01%, content of graphite 1%, the proportioning of water and ethanol is 3:1, above-mentioned substance is carried out fully stir obtaining 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 low frequency 20kH, the output rating of adjustment microwave reaction kettle is 200W, in reservoir 7, obtain graphene dispersing solution;
Step 3: the flow velocity controlling the flow valve of tempering tank 6 is 100L/h, opens rapid stirring oar, is stirred by slurry and fully mix, obtain Graphene slurry with graphene dispersing solution;
Step 4: arranging drying machine with centrifugal spray temperature in is 150 DEG C, and temperature out is 80 DEG C, liquid ejection speed is 150L/h.In cyclone centrifugal device 10, reach granulation object by adjusting rotary speed after sample drying, thus obtain Graphene particle.
Being added by above-mentioned Graphene in polypropylene (PP), is namely base material with polypropylene, has prepared the matrix material (representing with PP, 1-PP10,1-PP15,1-PP20 respectively) that Graphene content is respectively 0%, 10%, 15,20%.
Above-mentioned materials is carried out strength test, and each sample test 4 times, averages.Strength test results is in table 1.
The intensity contrast table of table 1 polypropylene and Graphene/polypropylene composite material thereof
Case study on implementation two
Step one: expanded graphite, water, ethylene glycol, Trisodium Citrate are placed in 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 stir obtaining 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, mixing schemes is adopted to peel off graphite, frequency is followed successively by 20kH, 30kH, 40kH, 50kH, 20kH, 30kH, 40kH, 50kH, the output rating of adjustment microwave reaction kettle is 300W, in reservoir 7, obtain graphene dispersing solution;
Step 3: the flow velocity controlling the flow valve of tempering tank 6 is 150L/h, opens rapid stirring oar, is stirred by slurry and fully mix, obtain Graphene slurry with graphene dispersing solution;
Step 4: arranging drying machine with centrifugal spray temperature in is 200 DEG C, and temperature out is 80 DEG C, liquid ejection speed is 200L/h.In cyclone centrifugal device 10, reach granulation object by adjusting rotary speed after sample drying, thus obtain Graphene particle.
Being added by above-mentioned Graphene in polypropylene (PP), is namely base material with polypropylene, has prepared the matrix material (representing with PP, 2-PP10,2-PP15,2-PP20 respectively) that Graphene content is respectively 0%, 10%, 15,20%.
Above-mentioned materials is carried out strength test, and each sample test 4 times, averages.Strength test results is in table 2.
The intensity contrast table of table 2 polypropylene and Graphene/polypropylene composite material thereof
Case study on implementation three
Step one: expanded graphite, water, N-Methyl pyrrolidone, sodium lauryl sulphate are placed in 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 stir obtaining 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, mixing schemes is adopted to peel off graphite, frequency is followed successively by 20kH, 30kH, 40kH, 20kH, 30kH, 40kH, 20kH, 20kH, the output rating of adjustment microwave reaction kettle is 250W, in reservoir 7, obtain graphene dispersing solution;
Step 3: the flow velocity controlling the flow valve of tempering tank 6 is 200L/h, opens rapid stirring oar, is stirred by slurry and fully mix, obtain Graphene slurry with graphene dispersing solution;
Step 4: arranging drying machine with centrifugal spray temperature in is 180 DEG C, and temperature out is 80 DEG C, liquid ejection speed is 300L/h.In cyclone centrifugal device 10, reach granulation object by adjusting rotary speed after sample drying, thus obtain Graphene particle.
Being added by above-mentioned Graphene in polypropylene (PP), is namely base material with polypropylene, has prepared the matrix material (representing with PP, 3-PP10,3-PP15,3-PP20 respectively) that Graphene content is respectively 0%, 10%, 15,20%.
Above-mentioned materials is carried out strength test, and each sample test 4 times, averages.Strength test results is in table 3.
The intensity contrast table of table 3 polypropylene and Graphene/polypropylene composite material thereof
Conducting performance test
The product obtained by case study on implementation one is with 10%, and the amount of 15% is added in polypropylene, called after 1PP-10,1PP-15, and the product obtained by case study on implementation two is with 10%, and 15% adds in polypropylene, called after 2PP-10,2PP-15; Moral is filled in admittedly superconductive carbon black XE-2B adds in polypropylene as a comparison sample simultaneously, adds 10% called after XE-2B-PP10, adds 15% called after XE-2B-PP15.Above-mentioned sample is carried out conductive test.Test result is in table 4:
Table 4 polypropylene/graphite performance
Can find out from the above results, the Graphene sample quality prepared by the present invention is good, can be used as enhancing, conductive filler material.
Claims (9)
1. a continuous prodution graphene powder full scale plant, is characterized in that: comprise the stationary tank, multi-mode microwave reactor, reservoir, spray-drying tower and the cyclone centrifugal device that are connected successively by pipeline, be respectively equipped with flow valve between each several part; Reservoir is connected with tempering tank, between reservoir and spray-drying tower, is provided with topping-up pump; In stationary tank, tempering tank and reservoir, rapid stirring oar is installed respectively; Microwave reaction kettle at different levels is 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 kettle at different levels, is provided with vibration screen, and vibration screen both sides are provided with the blade of horizontal rapid stirring.
2. a kind of continuous prodution graphene powder full scale plant as claimed in claim 1, is characterized in that: described processor for ultrasonic wave is energy gathering type ultrasound probe, and ultrasonic frequency is within 20kHz-80kHz.
3. a method for continuous prodution graphene powder, its step comprises:
Step one: graphite, dispersion agent are placed in stationary tank, stir, the proportioning controlling dispersion agent obtains the graphite premix that surface tension is 30-50mN/m, prepares slurry in tempering tank simultaneously;
Step 2: control flow valve, above-mentioned premix is flowed into microwave reaction kettle by pipeline, takes the output rating controlling energy gathering type ultrasound probe number, ultrasonic frequency, microwave reaction kettle, in reservoir, obtains graphene dispersing solution;
Step 3: the flow valve controlling tempering tank, mixes slurry 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, thus obtain Graphene particle.
4. the method for a kind of continuous prodution graphene powder as claimed in claim 3, is characterized in that: the graphite in described step one is expanded graphite or graphite oxide.
5. the method for a kind of continuous prodution graphene powder as claimed in claim 3, it is characterized in that: the dispersion agent in described step one is selected from a kind of or at least two or more combination in 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, Trisodium Citrate.
6. the method for a kind of continuous prodution graphene powder as claimed in claim 3, is characterized in that: the dispersion agent in described step one is selected from a kind of or at least two or more combination of ammoniacal liquor, ethanol, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, Trisodium Citrate, N-Methyl pyrrolidone.
7. the method for a kind of continuous prodution graphene powder as claimed in claim 3, is characterized in that: the graphite concentration in the graphite premix in described step one is 0.1-3%.
8. the method for a kind of continuous prodution graphene powder as claimed in claim 3, is characterized in that: the tackiness agent in described step one comprises more than one the solution in hydrocarbon, thermoplastic resin and thermosetting resin.
9. the method for a kind of continuous prodution graphene powder as claimed in claim 3, is characterized in that: control energy gathering type ultrasound probe ultrasonic frequency in described step 2 for carrying out ultrasonic mechanically peel with any power to graphite raw material with frequency or mixing; Described with being same ultrasonic wave frequently, be mixed down two or more ultrasonic wave.
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