CN105585006A - A graphite expanding and heating device and a process thereof - Google Patents
A graphite expanding and heating device and a process thereof Download PDFInfo
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- CN105585006A CN105585006A CN201410570925.XA CN201410570925A CN105585006A CN 105585006 A CN105585006 A CN 105585006A CN 201410570925 A CN201410570925 A CN 201410570925A CN 105585006 A CN105585006 A CN 105585006A
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- rotating cylinder
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Abstract
The invention relates to a graphite expanding and heating device and a process thereof. The device comprises a rotary cylinder (1). A top cover (2) is disposed on the rotary cylinder (1). A base cover (3) is disposed below the rotary cylinder (1). The upper part of the rotary cylinder (1) is provided with a plasma generator (8). A flexible stirring shaft (11) is disposed in the rotary cylinder (1). A second motor (15) is disposed at the outside of the rotary cylinder (1), and is connected to the rotary cylinder (1) through a gear transmission mechanism (14). According to the device and the process, graphite scales are directly prepared into suspension and subjected to high-temperature expansion and a heating manner is improved, thus ensuring final graphite expansion and desulphurization effects, increasing the production efficiency and the yield of expanded graphite, and providing guarantees for subsequent large-scale production of graphene.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene, specifically relate to graphite expansion heater and process thereof in a kind of Graphene production process, belong to materials science field.
Background technology
Material with carbon element be on a kind of earth compared with general and special material, it can form the diamond that hardness is larger, also can form softer graphite. Over nearly 20 years, carbon nanomaterial is the Disciplinary Frontiers of scientific and technical innovation always, and the fullerene of finding for 1985 and the CNT (CNTs) of finding for 1991 have all caused huge repercussion, have risen research boom.
2004, the Geim group of Manchester university obtained New Two Dimensional atomic crystal---the Graphene of individual layer or thin layer first by mechanical stripping method. The discovery of Graphene, has enriched material with carbon element family, has formed the integral framework from the Graphene of the CNTs of the fullerene of zero dimension, one dimension, two dimension to three-dimensional diamond and graphite. Graphene is with sp by carbon atom2The monoatomic layer that hydridization connects forms, and its basic structural unit is benzene hexatomic ring the most stable in organic material, and its theoretic throat is only 0.35nm, is the thinnest two-dimensional material of finding at present. Graphene is to form the elementary cell of other graphite materials, can warpage becomes the fullerene of zero dimension, curls into the CNTs of one dimension or is stacked to three-dimensional graphite. This special construction has contained abundant and peculiar physical phenomenon, makes Graphene show the physicochemical properties of many excellences, if the intensity of Graphene is to have measured and monitored the growth of standing timber the highlyest in material, reaches 130GPa, is more than 100 times of steel; Its carrier mobility reaches 1.5 × 104cm2V-1s-1, be current 2 times of the known indium antimonide material with high mobility, exceed 10 times of commercial silicon chip mobility, under given conditions (as cryogenic quenching etc.), its mobility even can be up to 2.5 × 105cm2V-1s-1, the thermal conductivity of Graphene can reach 5 × 103Wm-1K-1, be adamantine 3 times; In addition, Graphene also has the special natures such as room temperature quantum hall effect (Halleffect) and room-temperature ferromagnetic. The performance that these are excellent and unique nanostructured, make Graphene become the focus of extensive concern in recent years. Nano composite material based on Graphene shows many premium properties in fields such as energy storage, liquid crystal device, electronic device, biomaterial, sensing material and catalyst carriers, has broad application prospects.
What the preparation of Graphene adopted the earliest is mechanical stripping method, after utilizing tape-stripping graphite, transfer to again on silicon chip, can make the Graphene of the low defect of high-quality by mechanical stripping method, therefore this method has a wide range of applications in the research in Condensed Matter Physics field. But the Graphene general size making by mechanical stripping method is all smaller and controllability is poor, has hindered its application in practical devices.
Graphene has occurred again in oxidation-reduction method, chemical vapour deposition technique, epitaxial growth method, has utilized the graphite intercalation stripping method of particular active agent and adopt the high temperature denitrogenation of graphene oxide and chemical reduction method etc. subsequently.
Oxidation-reduction method is that graphite first obtains edge through oxidation and also has carboxyl, hydroxyl, the graphite oxide (graphiteoxide) that interlayer contains the oxy radical such as epoxy and carbonyl, this process can make graphite layers distance expand 0.78nm to from 0.34nm, the graphene oxide (grapheneoxide) of being peeled off (peeling off as ultrasonic) and obtained again monoatomic layer thickness by external force, further reduction can prepare Graphene. Graphene prepared by this method is single-layer graphene film independently, and its output is high, is widely used. Wherein the method for oxidation of graphite mainly contains Hummers, Brodie and tri-kinds of methods of Staudenmaier, they are all to process original graphite with inorganic strong protonic acid (as the concentrated sulfuric acid, fuming nitric aicd or their mixture), little strong acid molecule is inserted to graphite layers, then use strong oxidizer (as KMnO4、KClO4Deng) it is oxidized, comparatively serious to graphite linings structural deterioration in this process; And reducing agent in the time that graphene oxide is carried out to electronation mainly contains sodium borohydride, hydrazine etc., they can be reduced into Graphene by graphene oxide effectively, remove the various oxy radicals between carbon-coating, but the Graphene obtaining easily produces defect, and strong acid, strong oxidizer and the reducing agent environmental issue in oxidation and reduction, used are outstanding, have some problems in large-scale industrial application.
The Graphene that adopts vapour deposition process to prepare has more complete crystal structure, and for the research of Graphene Electronic Performance provides important base material, but prepared Graphene output is lower, and cost is high, is difficult to large-scale production.
Epitaxial growth method is prepared Graphene by the pyrolysis of carborundum, its operating condition harshness.
The Graphene monolithic that utilizes surfactant to make, may affect because of the introducing of activating agent the intrinsic character of Graphene.
In sum, all there is problem to a certain degree in current Graphene preparation method, thereby how to invent research and the application of the stable Graphene substrate of peeling off of a kind of scale preparation to grapheme material and have great significance.
Applicant has invented a kind of new method of preparing on a large scale Graphene after scrutinizing, and it has, and cost is low, green, pollution-free, Graphene high quality. The first step of the method is that graphite scale is carried out to high-temperature expansion. Expanded graphite is generally that natural flake graphite is soaked in the solution of intercalator and oxidant, and under the effect of strong oxidizer, intercalator inserts graphite layers, then, through depickling, washing, dry, becomes expansible graphite. Then expansible graphite is placed under the high temperature of 800 ~ 1000 DEG C, its volume expands rapidly, expands and reaches more than 100 times, becomes a kind of vermiform material, is referred to as expanded graphite. Expanded graphite is made up of at the small scale of 30 ~ 80 μ m a large amount of thickness, and these small scales are made up of thinner graphite microplate, and wherein the thickness of graphite microplate is that 10 ~ 90nm, diameter are that 0.2 ~ 20 μ m, apparent density are 0.015g/cm3. Because intercalator in this technique is generally the concentrated sulfuric acid, oxidant is generally fuming nitric aicd, potassium bichromate, potassium permanganate, perchloric acid, trichloroacetic acid and their mixture thereof etc., because this technique acid consumption is large, in production process, there is the pollution of the pernicious gas such as SOx, NOx or heavy metal ion, and in product, there is sulphur residual, in application, equipment is had to corrosion. And expansible graphite adopts the mode of combustion gas, fuel oil or Resistant heating to carry out high-temperature expansion to graphite conventionally in above-mentioned technique, the heating rate of these modes is slower, generally in 100 DEG C/s left and right, if graphite scale will be heated to the expansion temperature of 1000 DEG C of left and right, need about 10 seconds, expansible graphite is expanded under this working condition, desulfurized effect is undesirable, and graphite is oxidizable, the row yielding of expanded graphite reduces, and production efficiency is lower, is unfavorable for large-scale production.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, a kind of graphite expansion heater and process thereof are provided, it carries out high-temperature expansion after directly graphite scale being mixed with to suspension, and improve mode of heating, final graphite expansion and desulfurized effect are ensured, production efficiency and the row yielding of expanded graphite are improved, for the large-scale production of follow-up Graphene provides guarantee.
The object of the present invention is achieved like this: a kind of graphite expansion heater, it comprises rotating cylinder, described rotating cylinder top is provided with overhead guard, described rotating cylinder below is provided with end cover, described overhead guard top is provided with charging aperture, described charging aperture is connected with rotating cylinder inside by feed pipe, cover bottom, the described end is provided with discharging opening, described rotating cylinder top is provided with plasma generator, described rotating cylinder is outside equipped with plasma electrical source, between described plasma electrical source and plasma generator, be provided with plasma coupling connector, in described rotating cylinder, be provided with flexible agitating roller, described flexible agitating roller is positioned at plasma generator below, described rotating cylinder below is provided with the first motor, between described the first motor and flexible agitating roller, be connected by power transmission shaft, described rotating cylinder arranged outside has the second motor, between described the second motor and rotating cylinder, be connected by gear drive.
On described rotating cylinder inwall, be provided with multiple thermocouples from top to bottom.
Between described overhead guard and end cover and rotating cylinder, be provided with seal.
A process for graphite expansion heater, described method comprises the steps:
Step 1, choose purity more than 98%, particle diameter is the graphite scale of 20 ~ 500 μ m;
Step 2, graphite scale and dispersant are added to solvent, obtain homodisperse suspension by ultrasonic vibration, wherein the mass concentration of graphite scale is 1% ~ 25%, and the concentration of dispersant is 4.5%;
Step 3, above-mentioned suspension is added in above-mentioned graphite expansion heater, by plasma generator, suspension is heated, reaction temperature is 80 ~ 150 DEG C, reaction time is 2 ~ 5h, and plasma generator power is 150kw, continues suspension to be uniformly mixed by rotating cylinder and flexible agitating roller, ensure the uniformity of suspension, flexible agitating roller rotating speed is 300rpm/min, and the rotating speed of rotating cylinder is 30rpm/min, and rotating cylinder is contrary with flexible agitating roller direction of rotation;
Step 4, by the expanded graphite suspension that obtains after reaction from discharging opening discharge enter in road reaction vessel.
Described solvent is one or more mixtures in water, methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, DMF (DMF), 1-METHYLPYRROLIDONE (NMP), oxolane.
Described dispersant is one or more composite in polyethylene glycol, polyvinyl alcohol, sodium phosphate trimer, calgon, lauryl sodium sulfate, neopelex (SDBS), 1-pyrene formic acid, 1-pyrene sulfonic acid, methyl anyl alcohol, sodium oxalate, sodium carboxymethylcellulose pyce, polyacrylamide, Arabic gum, polyvinylpyrrolidone (PVP), sodium taurocholate, polyvinylpyrrolidone.
Compared with prior art, the present invention has following beneficial effect:
1, when graphite scale of the present invention is expanded, avoided the use of the concentrated sulfuric acid, therefore puffing process can not produce the pollution of the pernicious gas such as SOx, NOx, whole process environmental protection, in product, do not have sulphur residual, product strength improves greatly, is also difficult for equipment to produce corrosion simultaneously, has extended service life of equipment, reduce production cost, be conducive to carry out large-scale production;
2, when graphite scale of the present invention is expanded, avoided the use of the oxidant such as potassium bichromate, potassium permanganate, therefore can not produce heavy metal pollution, product antioxygenic property is good simultaneously, has effectively ensured final product quality, has improved the row yielding of expanded graphite;
3, when the present invention is expanded, graphite scale and dispersant are added and in solvent, be configured to suspension, suspension heats after ultrasonic vibration mixes, therefore the heating uniformity of graphite expansion is good, greatly reduces the expansion temperature of graphite scale, has reduced the sulfur content of product simultaneously;
4, using plasma generator of the present invention heats suspension, plasma heating technology is a kind of new technique, its principle is the clean medium that adopts certain pressure, under the effect of DC current, produce the plasma of the directed flow of power stability, this plasma forms T in central area > 5000K high temp fire core, it is simple in structure, volume is little, easy for installation, safeguard simple, electric conversion efficiency is high, firing rate is fast, heating uniformity is good, greatly improve production efficiency, can effectively ensure the desulfurized effect of final products, simultaneously by adding the Van der Waals force between heat damage graphite linings and layer, improve the allowance for expansion of graphite scale, for the preparation of follow-up Graphene provides guarantee,
5, graphite expansion heater of the present invention is by the relative rotation of rotating cylinder and flexible agitating roller, can ensure that suspension is all the time in even admixture, ensure the uniformity of graphite expansion heating, and be difficult for graphite scale to produce damage, thereby brought defect to final products.
Brief description of the drawings
Fig. 1 is the structural representation of a kind of graphite expansion heater of the present invention.
Wherein:
Rotating cylinder 1
Overhead guard 2
End cover 3
Seal 4
Charging aperture 5
Discharging opening 6
Feed pipe 7
Plasma generator 8
Plasma electrical source 9
Plasma coupling connector 10
Flexible agitating roller 11
Power transmission shaft 12
The first motor 13
Gear drive 14
The second motor 15
Thermocouple 16.
Detailed description of the invention
Referring to Fig. 1, a kind of graphite expansion heater of the present invention, it comprises rotating cylinder 1, described rotating cylinder 1 top is provided with overhead guard 2, described rotating cylinder 1 below is provided with end cover 3, between described overhead guard 2 and end cover 3 and rotating cylinder 1, be provided with seal 4, described overhead guard 2 tops are provided with charging aperture 5, described charging aperture 5 is connected with rotating cylinder 1 inside by feed pipe 7, cover 3 bottoms and be provided with discharging opening 6 at the described end, described rotating cylinder 1 top is provided with plasma generator 8, described rotating cylinder 1 is outside equipped with plasma electrical source 9, between described plasma electrical source 9 and plasma generator 8, be provided with plasma coupling connector 10, in described rotating cylinder 1, be provided with flexible agitating roller 11, described flexible agitating roller 11 is positioned at plasma generator 8 belows, described rotating cylinder 1 below is provided with the first motor 13, between described the first motor 13 and flexible agitating roller 11, be connected by power transmission shaft 12, described rotating cylinder 1 arranged outside has the second motor 15, between described the second motor 15 and rotating cylinder 1, be connected by gear drive 14, on described rotating cylinder 1 inwall, be provided with multiple thermocouples 16 from top to bottom.
Below the several embodiment that utilize above-mentioned graphite expansion heater to produce:
Embodiment 1:
The process of a kind of graphite expansion heater of the present invention, it comprises the following steps:
Step 1, choose purity more than 98%, particle diameter is the graphite scale of 20 μ m;
Step 2,50kg graphite scale and 1kg sodium taurocholate dispersant are added in 350kg distilled water, the ultrasonic vibration 2h that is 50w by frequency, obtains homodisperse suspension;
Step 3, above-mentioned suspension is added in above-mentioned graphite expansion heater, by plasma generator, suspension is heated, reaction temperature is 80 DEG C, reaction time is 5h, and plasma generator power is 150kw, continues suspension to be uniformly mixed by rotating cylinder and flexible agitating roller, ensure the uniformity of suspension, flexible agitating roller rotating speed is 300rpm/min, and the rotating speed of rotating cylinder is 30rpm/min, and rotating cylinder is contrary with flexible agitating roller direction of rotation;
Step 4, by the expanded graphite suspension that obtains after reaction from discharging opening discharge enter in road reaction vessel.
Embodiment 2:
The process of a kind of graphite expansion heater of the present invention, it comprises the following steps:
Step 1, choose purity more than 98%, particle diameter is the graphite scale of 150 μ m;
Step 2,20kg graphite scale and 1kg polyvinyl alcohol dispersant are added in 400kgN-methyl pyrrolidone, the ultrasonic vibration 3h that is 50w by frequency, obtains homodisperse suspension;
Step 3, above-mentioned suspension is added in above-mentioned graphite expansion heater, by plasma generator, suspension is heated, reaction temperature is 150 DEG C, reaction time is 2h, and plasma generator power is 150kw, continues suspension to be uniformly mixed by rotating cylinder and flexible agitating roller, ensure the uniformity of suspension, flexible agitating roller rotating speed is 300rpm/min, and the rotating speed of rotating cylinder is 30rpm/min, and rotating cylinder is contrary with flexible agitating roller direction of rotation;
Step 4, by the expanded graphite suspension that obtains after reaction from discharging opening discharge enter in road reaction vessel.
Embodiment 3:
The process of a kind of graphite expansion heater of the present invention, it comprises the following steps:
Step 1, choose purity more than 98%, particle diameter is the graphite scale of 250 μ m;
Step 2,30kg graphite scale and 1kg lauryl sodium sulfate dispersant are added in 500kgN-methyl pyrrolidone, the ultrasonic vibration 3h that is 60w by frequency, obtains homodisperse suspension;
Step 3, above-mentioned suspension is added in above-mentioned graphite expansion heater, by plasma generator, suspension is heated, reaction temperature is 100 DEG C, reaction time is 3h, and plasma generator power is 150kw, continues suspension to be uniformly mixed by rotating cylinder and flexible agitating roller, ensure the uniformity of suspension, flexible agitating roller rotating speed is 300rpm/min, and the rotating speed of rotating cylinder is 30rpm/min, and rotating cylinder is contrary with flexible agitating roller direction of rotation;
Step 4, by the expanded graphite suspension that obtains after reaction from discharging opening discharge enter in road reaction vessel.
Embodiment 4:
Step 1, choose purity more than 98%, particle diameter is the graphite scale of 500 μ m;
Step 2,50kg graphite scale and 1kg polyvinylpyrrolidone dispersant are added in 500kg n-butanol, the ultrasonic vibration 3h that is 60w by frequency, obtains homodisperse suspension;
Step 3, above-mentioned suspension is added in above-mentioned graphite expansion heater, by plasma generator, suspension is heated, reaction temperature is 120 DEG C, reaction time is 3h, and plasma generator power is 150kw, continues suspension to be uniformly mixed by rotating cylinder and flexible agitating roller, ensure the uniformity of suspension, flexible agitating roller rotating speed is 300rpm/min, and the rotating speed of rotating cylinder is 30rpm/min, and rotating cylinder is contrary with flexible agitating roller direction of rotation;
Step 4, by the expanded graphite suspension that obtains after reaction from discharging opening discharge enter in road reaction vessel.
Claims (6)
1. a graphite expansion heater, it is characterized in that: it comprises rotating cylinder (1), described rotating cylinder (1) top is provided with overhead guard (2), described rotating cylinder (1) below is provided with end cover (3), described overhead guard (2) top is provided with charging aperture (5), described charging aperture (5) is connected with rotating cylinder (1) inside by feed pipe (7), described end cover (3) bottom is provided with discharging opening (6), described rotating cylinder (1) top is provided with plasma generator (8), described rotating cylinder (1) is outside equipped with plasma electrical source (9), between described plasma electrical source (9) and plasma generator (8), be provided with plasma coupling connector (10), in described rotating cylinder (1), be provided with flexible agitating roller (11), described flexible agitating roller (11) is positioned at plasma generator (8) below, described rotating cylinder (1) below is provided with the first motor (13), between described the first motor (13) and flexible agitating roller (11), be connected by power transmission shaft (12), described rotating cylinder (1) arranged outside has the second motor (15), between described the second motor (15) and rotating cylinder (1), be connected by gear drive (14).
2. a kind of graphite expansion heater according to claim 1, is characterized in that: on described rotating cylinder (1) inwall, be provided with multiple thermocouples (16) from top to bottom.
3. a kind of graphite expansion heater according to claim 1 and 2, is characterized in that: between described overhead guard (2) and end cover (3) and rotating cylinder (1), be provided with seal (4).
4. a process for graphite expansion heater as claimed in claim 1, is characterized in that described method comprises the steps:
Step 1, choose purity more than 98%, particle diameter is the graphite scale of 20 ~ 500 μ m;
Step 2, graphite scale and dispersant are added to solvent, obtain homodisperse suspension by ultrasonic vibration, wherein the mass concentration of graphite scale is 1% ~ 25%, and the concentration of dispersant is 4.5%;
Step 3, above-mentioned suspension is added in above-mentioned graphite expansion heater, by plasma generator, suspension is heated, reaction temperature is 80 ~ 150 DEG C, reaction time is 2 ~ 5h, and plasma generator power is 150kw, continues suspension to be uniformly mixed by rotating cylinder and flexible agitating roller, ensure the uniformity of suspension, flexible agitating roller rotating speed is 300rpm/min, and the rotating speed of rotating cylinder is 30rpm/min, and rotating cylinder is contrary with flexible agitating roller direction of rotation;
Step 4, by the expanded graphite suspension that obtains after reaction from discharging opening discharge enter in road reaction vessel.
5. the process of a kind of graphite expansion heater according to claim 4, it is characterized in that: described solvent is one or more mixtures in water, methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, DMF (DMF), 1-METHYLPYRROLIDONE (NMP), oxolane.
6. the process of a kind of graphite expansion heater according to claim 4, is characterized in that: described dispersant is one or more composite in polyethylene glycol, polyvinyl alcohol, sodium phosphate trimer, calgon, lauryl sodium sulfate, neopelex (SDBS), 1-pyrene formic acid, 1-pyrene sulfonic acid, methyl anyl alcohol, sodium oxalate, sodium carboxymethylcellulose pyce, polyacrylamide, Arabic gum, polyvinylpyrrolidone (PVP), sodium taurocholate, polyvinylpyrrolidone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410570925.XA CN105585006A (en) | 2014-10-24 | 2014-10-24 | A graphite expanding and heating device and a process thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410570925.XA CN105585006A (en) | 2014-10-24 | 2014-10-24 | A graphite expanding and heating device and a process thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531246A (en) * | 2018-06-15 | 2018-09-14 | 集美大学 | A kind of preparation method and compounded lubricating oil of graphene oxide compounded lubricating oil |
| CN109801754A (en) * | 2018-12-29 | 2019-05-24 | 安徽天康(集团)股份有限公司 | A kind of copper core mica tape mineral insulation ripple copper sheath power cable |
| CN115651696A (en) * | 2022-10-24 | 2023-01-31 | 昆明姜雨科技有限公司 | Desulfurizing agent for liquefied petroleum gas and preparation method thereof |
-
2014
- 2014-10-24 CN CN201410570925.XA patent/CN105585006A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531246A (en) * | 2018-06-15 | 2018-09-14 | 集美大学 | A kind of preparation method and compounded lubricating oil of graphene oxide compounded lubricating oil |
| CN108531246B (en) * | 2018-06-15 | 2021-02-02 | 集美大学 | Preparation method of graphene oxide composite lubricating oil and composite lubricating oil |
| CN109801754A (en) * | 2018-12-29 | 2019-05-24 | 安徽天康(集团)股份有限公司 | A kind of copper core mica tape mineral insulation ripple copper sheath power cable |
| CN109801754B (en) * | 2018-12-29 | 2020-08-21 | 安徽天康(集团)股份有限公司 | Copper core mica tape mineral insulation corrugated copper sheath power cable |
| CN115651696A (en) * | 2022-10-24 | 2023-01-31 | 昆明姜雨科技有限公司 | Desulfurizing agent for liquefied petroleum gas and preparation method thereof |
| CN115651696B (en) * | 2022-10-24 | 2023-07-18 | 滨州乾坤化工机械有限公司 | Desulfurizing agent for liquefied petroleum gas and preparation method thereof |
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