CN103663440A - Gas atomization method and device for preparing mesocarbon microbeads - Google Patents
Gas atomization method and device for preparing mesocarbon microbeads Download PDFInfo
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- CN103663440A CN103663440A CN201310614323.5A CN201310614323A CN103663440A CN 103663440 A CN103663440 A CN 103663440A CN 201310614323 A CN201310614323 A CN 201310614323A CN 103663440 A CN103663440 A CN 103663440A
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Abstract
The invention discloses a gas atomization method and device for preparing mesocarbon microbeads. A technological process comprises preparation of mesophase pitch, extruding and drawing, gas atomization, cooling, powder collection and screening, oxidization and carbonization, graphitization and the like. The device comprises an electric mesophase pitch smelting furnace, a screw extruding and conveying machine, an atomization chamber and a gas atomization head, wherein one end of the screw extruding and conveying machine is connected with the electric mesophase pitch smelting furnace, and the other end extends into the atomization chamber and is connected with the gas atomization head; the gas atomization head is fixed at the top of the atomization chamber through an atomization head fixing device; a gas channel of the gas atomization head is connected with an atmospheric pressure control system; a powder collector is arranged at the bottom of the atomization chamber; and a temperature control pipeline is arranged on the inner wall of the atomization chamber and connected with a temperature control system.
Description
Technical field
The invention belongs to graphite negative material of lithium ion battery field, relate to the manufacturing technology of MCMB for a kind of dynamic lithium battery, particularly a kind of aerosolization method and device of preparing MCMB.
Background technology
MCMB (Mesocarbon microbead, MCMB) has unique spherical laminate structure, and chemical stability and excellent heat stability, thermal conductivity and excellent conductivity, embedding characteristic are given prominence to; Within 1992, Japanese Yamamura is applied to MCMB in lithium ion battery first, and along with the use of technical progress and clear energy sources, the demand of power lithium-ion battery will increase gradually; The high quality specific storage that MCMB shows, low irreversible specific discharge capacity and lower volume rate of fall-off become the excellent negative material that has competition potential.
Aspect production, 1973, Japanese scholars Honda and Yamada obtained MCMB by thermopolymerization legal system, the method because technique is simple, be easy to control and be applied to suitability for industrialized production, but due to reunion, the legal yield of hot polymerization is lower, is generally 20-35%.Chinese patent CN02116840.7 and CN101811694A disclose after asphalt stock and catalyst mix, utilize thermopolymerization legal system for the method for MCMB under certain temperature and pressure, show that the highest yield is 39%.
The copolycondensation preparation method of existing MCMB, under needn't pretreated condition, prepares the uniform MCMB of spherolite by medium temperature coal pitch and ethylene bottom oil copolycondensation, and yield is 20-30%.Because the legal production efficiency of hot polymerization is lower, and need to consume a large amount of solvent repetitive scrubbings in preparation MCMB process, cause current MCMB cost high, in addition, the homogeneity of MCMB particle diameter and surface quality are poor etc., and factor has a strong impact on end-use performance.Though emulsion method and suspension method can improve the yield of MCMB, need medium and tensio-active agent that high high-temp stability is good, production process is complicated, and process regulation difficulty is large, and cost is high, has the problem of solvent contamination simultaneously, industrial applications difficulty.Along with the MCMB increase of demand and expansion of Application Areas in power lithium battery negative pole, in the urgent need to a kind of efficient, low-cost, eco-friendly technology of preparing.
Summary of the invention:
The invention provides a kind of aerosolization method and device of preparing MCMB, solve the problems such as existing negative electrode for lithium ion battery material MCMB production efficiency is low, cost is high, preparation process environment is unfriendly.
The technical solution adopted in the present invention is as follows:
A kind of gas atomization device of preparing intermediate-phase carbon carbon microspheres, comprise mesophase pitch melting electric furnace, screw extrusion transfer roller, spray chamber, and gas atomization head, one end of described screw extrusion transfer roller is connected with mesophase pitch melting electric furnace, one end is stretched into spray chamber and is connected with gas atomization head in addition, described gas atomization head is anchored on spray chamber top by atomising head stationary installation, the gas passage of described gas atomization head is connected with atmosphere pressures Controlling System, described spray chamber bottom arranges powder collector, the inwall of described spray chamber is provided with temperature control pipeline, temperature control pipeline is connected with temperature controlling system.
As the preferred embodiments of the present invention, described spray chamber is further provided with strainer, and strainer is connected with pressure control system by pipeline.
As the preferred embodiments of the present invention, described screw extrusion transfer roller is with ejector nozzle, and the load of this ejector nozzle is 1.0-3.5kg/min.
As the preferred embodiments of the present invention, described gas atomization head includes two gas jets, and the axial angle between two nozzles is 30-90 °.
As the preferred embodiments of the present invention, described gas atomization head includes two gas jets, and the 1-2 that described gas jet diameter is ejector nozzle doubly.
A kind of preparation method of the MCMB based on above-mentioned gas atomization device, the presoma of MCMB being heated in mesophase pitch melting electric furnace to molten state sprays by screw extrusion transfer roller, gas jet on gas atomization head ejects high pressure gas with the mesophase pitch atomization of liquid to molten state, mesophase pitch liquid sedimentation solidifies, finally enter into powder collector, the MCMB that powder collector is collected is through melt processed not, after charing handler graphitization processing, mechanism's screening, collect, wherein, the method of melt processed is not: in oxidizing atmosphere, from room temperature, be warming up to after 160-270 ℃, heat-up rate with 0.1-0.3 ℃/min is heated to 220-350 ℃, insulation 0.5-10 hour, MCMB surface forms stable C-O-C oxo bridge structure, the method that described charing is processed is: under nitrogen or argon gas condition, 1-3 ℃/min is warming up to 350-650 ℃, and insulation 1-4 hour continues to be warming up to 800-1200 ℃ of insulation 1-4 hour, furnace cooling with 1-5 ℃/min, the method of described graphitization processing is: under argon gas atmosphere, rise to 2000-2400 ℃ after being warming up to 1200 ℃ with 10-50 ℃/min temperature rise rate, insulation 0.5-2 hour, furnace cooling.
As the preferred embodiments of the present invention, in atomization treating processes, atmosphere pressures is 0.3-9Mpa, high pressure gas are the mixed oxidization gas of non-oxidized gas or oxygen and non-oxidized gas formation, described non-oxidized gas is nitrogen or argon gas, in mixed oxidization gas, oxidizing atmosphere content is 0-30%.
As the preferred embodiments of the present invention, the temperature of described spray chamber is 15-60 ℃, and spray chamber pressure is 0.6-1.6atm.
As the preferred embodiments of the present invention, in described not melt processed method, described oxidizing atmosphere is air, oxygen, ozone, nitrogen peroxide or sulphur trioxide atmosphere.
As the preferred embodiments of the present invention, the presoma of MCMB is elected naphthalene as and is associated into mesophase pitch, purifies after one or more in coal tar mesophase pitch or modification coal measures mesophase pitch grind and cross 100 mesh sieves and obtain.
Compared with prior art, beneficial effect of the present invention is: (1) MCMB yield is high, good sphericity, and size distribution is even, size is controlled; (2) technology controlling and process is simple, is easy to suitability for industrialized production, low cost of manufacture; (3) without organic solvent, participate in, source of pollution are few, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention;
Fig. 2 is the structural representation of gas atomization device of the present invention:
Fig. 3 is the structural representation of aerosolization head of the present invention;
Fig. 4 is the vertical view of Fig. 3;
Fig. 5 is the size distribution figure of the embodiment of the present invention 2 acquired results; As can be seen from the figure, the pore size distribution range of carbon microspheres is 10-25 μ m, and median size is 16.6 μ m.
Fig. 6 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 2 acquired results, and as can be seen from the figure, after greying, carbon microspheres keeps spherical characteristic preferably, surface uniform flawless.
Wherein, 1 mesophase pitch melting electric furnace, 2 aerosolization atmosphere pressures Controlling System, 3 gas control valves, 4 screw extrusion transfer rollers, 5 spray chambers, 6 atomising head stationary installations, 7 temperature control pipelines, 8 pressure control valves, 9 strainers, 10 pressure control systems, 11 powder collectors, 12 temperature controlling systems, 13 gas atomization heads; 14 extruding transfer roller interfaces, 15 gas admission passages, 16 gas jets, 17 ejector nozzle interfaces.
Embodiment
A kind of aerosolization method and device of preparing MCMB provided by the invention, technological process as shown in Figure 1, mainly comprises modulation, atomization process, non-melt processed, charing, the greying of presoma pitch.Its concrete steps are as follows:
(1) modulation of presoma pitch
Naphthalene is associated into mesophase pitch, purifies one or more in coal tar mesophase pitch or modification coal measures mesophase pitch and grind, cross after 100 mesh sieves the presoma as preparation MCMB.
(2) atomisation unit and technological process
A kind of structural representation of gas atomization device of MCMB as shown in Figure 2, mainly comprises: 1 mesophase pitch melting electric furnace, 2 aerosolization atmosphere pressures Controlling System, 3 gas control valves, 4 screw extrusion transfer rollers, 5 spray chambers, 6 atomising head stationary installations, 7 temperature control pipelines, 8 pressure control valves, 9 strainers, 10 pressure control systems, 11 powder collectors, 12 temperature controlling systems, 13 gas atomization heads.Gas atomization camera function title of part: 14 extruding transfer roller interfaces, 15 gas admission passages, 16 gas jets, 17 nozzle nozzle interfaces.The structural relation of atomisation unit is: mesophase pitch melting electric furnace 1 is positioned at the upper end of spray chamber 5, screw extrusion transfer roller 4 is connected with spray chamber 5 with ejector nozzle and by mesophase pitch melting electric furnace 1, the output terminal of screw extrusion transfer roller 4 stretches into spray chamber 5, is connected with gas atomization 13; Gas atomization 13 is anchored on spray chamber 5 tops by atomising head stationary installation 6; The gas passage of gas atomization 13 is connected by pipeline with atmosphere pressures Controlling System 2, on the pipeline that atmosphere pressures Controlling System is connected with gas atomization head, is provided with gas control valve 3, and atmosphere pressures Controlling System 2 is positioned at spray chamber 5 outsides; Spray chamber 5 bottoms arrange powder collector 11; The middle and lower part of spray chamber 5 arranges strainer 9, and strainer 9 is connected with the pressure control system 10 in outside by pipeline, is provided with pressure control valve 8 on the pipeline that described strainer is connected with pressure control system; Temperature control pipeline 7 is spirane structure, is arranged at spray chamber inwall, is connected with temperature controlling system 12.
Atomization process: the described presoma of step (1) is placed in to mesophase pitch melting electric furnace 1 and is heated to 280-420 ℃, and be incubated 0.5-12 hour, obtain continuously middle phase molten mass; This centre phase molten mass is by screw extrusion transfer roller 4 ejections with ejector nozzle; Open gas control valve 3, aerosolization atmosphere pressures Controlling System 2 connects gas atomizations 12, gas jet inject high pressure gas in gas atomization 12 is with the mesophase pitch atomization of liquid to molten mass, mesophase pitch liquid sedimentation solidifies, the final powder collector 11 that imports, powder collector 11 completes separation of air from dust; Pressure control system 10 maintains spray chamber 5 pressure equilibriums and carries out gas discharge.
The atmosphere pressures of described aerosolization atmosphere pressures Controlling System is 0.3-9Mpa, and high pressure gas is N
2, non-oxidizing gas or oxygen and the N such as Ar gas
2, the mixed oxidization gas that forms of the non-oxidizing gas such as Ar gas; The content of oxidizing atmosphere in total atmosphere is 0-30%;
The temperature of described spray chamber is controlled and is completed by temperature controlling system 12, is 15-60 ℃;
The pressure range of described spray chamber is 0.6-1.6atm;
The setting of screw extrusion transfer roller can prevent that line clogging and material from regurgitating, and in rotary course, melting mesophase pitch is played to the effect of carrying with extruding drawing-off, makes the mesophase pitch before atomization form fibre-like weave construction.Transfer roller discharge port can be matched difform ejector nozzle, and it is the tubulose ejector nozzle of 4mm that the present invention selects diameter, and the load of ejector nozzle is 1.0-3.5kg/min, and preferred load is 2.5kg/min.
The structure of described gas atomization head as Fig. 3, Fig. 4 (as shown in, on atomising head, comprise two gas jets, axial angle between two nozzles is 30-90 °, it is 90 ° that the present invention selects angle, the diameter of gas jet is generally 1-2 times of ejector nozzle diameter, 1.5 times of gas jet diameters that the present invention selects, to ejector nozzle, are 6mm.Injector spacing is 15mm.
(3) melt processed technique not
The not melt processed of MCMB is carried out on vertical oxidized still, and oxidizing atmosphere can be for being air, oxygen, ozone, nitrogen peroxide, sulphur trioxide etc., and it is example that this patent be take air cheaply.First from room temperature, be warming up to 160-270 ℃, then the heat-up rate with 0.1-0.5 ℃/min is heated to 220-350 ℃, and be incubated 0.5-10 hour, make that mesophase pitch microsphere is fully oxidized, the chemical reaction such as dehydrogenation, crosslinked and cyclisation, on MCMB surface, form stable C-O-C oxo bridge structure, guarantee that melting, distortion and cracking phenomena do not occur MCMB in carbonization process.
(4) charring process
Step 3 gained oxidation MCMB is placed in to atmosphere charring furnace, under nitrogen or argon gas condition, with 1-3 ℃/min, is warming up to 350-650 ℃, insulation 1-5 hour; Continuation is warming up to 800-1200 ℃ of insulation 1-3 hour with 1-5 ℃/min, and furnace cooling obtains the MCMB after charing.
(5) graphitization processing
Step 4 gained charing MCMB is placed in to atmosphere graphitizing furnace, and described atmosphere is Ar gas.Naturally after being warming up to 1200 ℃, with 10-50 ℃/min temperature rise rate, rise to 2000-2400 ℃, and be incubated 0.5-2 hour, furnace cooling obtains MCMB after greying.
(6) screening, collection
MCMB magnitude classification by screening plant after to graphitization processing, collects the particle of certain limit particle diameter, i.e. finished product MCMB.
Below by specific embodiment, the present invention is described in further details.
Embodiment 1:
By naphthalene, be that mesophase pitch is placed in and adds electrothermal stove, be heated to 360 ℃, and be incubated the mesophase pitch that 0.5h obtains melting; This mesophase pitch is delivered to ejector nozzle, and the load of nozzle is 1.0kg/min; Pressure is that 9.0Mpa, temperature are the N of 60 ℃
2or the non-oxidized gas such as Ar enters gas atomization head; A gas atomization gas jet is sprayed to mesophase pitch, and mesophase pitch droplet is cooling balling-up in spray chamber, and now the temperature of spray chamber is 50 ℃, and pressure is 0.6atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in to vertical oxidized still, by room temperature, is freely warming up to 220 ℃, with 0.1 ℃/min, be warming up to 280 ℃ subsequently, and be incubated 4h, complete the spherular not melt processed of mesophase pitch; Microsphere after melt processed is not placed in to charring furnace, by room temperature, is freely warming up to 300 ℃, with 1 ℃/min, be warming up to 500 ℃ subsequently, and be incubated 5h, continue to be warming up to 1000 ℃ with 1 ℃/min, and be incubated 3h, obtain the MCMB after charing; MCMB after charing is placed in to graphitizing furnace, by room temperature, be freely warming up to 1200, with 30 ℃/min, be warming up to 2400 ℃ subsequently, and be incubated 0.5h, furnace cooling obtains greying and obtains MCMB, MCMB after greying is sieved to obtain to finished product carbon microspheres, and the size distribution of finished product carbon microspheres is 45-105 μ m.
Embodiment 2:
By naphthalene, be that mesophase pitch is placed in and adds electrothermal stove, be heated to 400 ℃, and be incubated the mesophase pitch that 4h obtains melting; This mesophase pitch is delivered to ejector nozzle, and the load of nozzle is 2.5kg/min; Pressure is that 3.0Mpa, temperature are that the mixed oxidization gas containing 15% oxygen and nitrogen or argon gas of 60 ℃ enters gas atomization head; A gas atomization gas jet is sprayed to mesophase pitch, and mesophase pitch droplet is cooling balling-up in spray chamber, and now the temperature of spray chamber is 15 ℃, and pressure is 1.6atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in to vertical oxidized still, by room temperature, is freely warming up to 260 ℃, with 0.5 ℃/min, be warming up to 350 ℃ subsequently, and be incubated 0.5h, complete the spherular not melt processed of mesophase pitch; Microsphere after melt processed is not placed in to charring furnace, by room temperature, is freely warming up to 350 ℃, with 3 ℃/min, be warming up to 650 ℃ subsequently, and be incubated 1h, continue to be warming up to 1200 ℃ with 5 ℃/min, and be incubated 1h, obtain the MCMB after charing; MCMB after charing is placed in to graphitizing furnace, by room temperature, be freely warming up to 1200, with 50 ℃/min, be warming up to 2300 ℃ subsequently, and be incubated 2h, furnace cooling obtains greying and obtains MCMB, MCMB after greying is sieved to obtain to finished product carbon microspheres, and the size distribution of finished product carbon microspheres is 10-25 μ m.
Embodiment 3:
Purification coal tar mesophase pitch is placed in and adds electrothermal stove, be heated to 280 ℃, and be incubated the mesophase pitch that 12h obtains melting; This mesophase pitch is delivered to ejector nozzle, and the load of nozzle is 1.5kg/min; Pressure is that 6.0Mpa, temperature are the N of 25 ℃
2or the non-oxidized gas such as Ar enters gas atomization head; A gas atomization gas jet is sprayed to mesophase pitch, and mesophase pitch droplet is cooling balling-up in spray chamber, and now the temperature of spray chamber is 60 ℃, and pressure is 0.9atm, and microsphere falls in powder collector; The mesophasespherule of collection is placed in to vertical oxidized still, by room temperature, is freely warming up to 160 ℃, with 0.1 ℃/min, be warming up to 220 ℃ subsequently, and be incubated 5h, complete the spherular not melt processed of mesophase pitch; Microsphere after melt processed is not placed in to charring furnace, by room temperature, is freely warming up to 220 ℃, with 1 ℃/min, be warming up to 350 ℃ subsequently, and be incubated 3h, continue to be warming up to 800 ℃ with 1 ℃/min, and be incubated 1h, obtain the MCMB after charing; MCMB after charing is placed in to graphitizing furnace, by room temperature, be freely warming up to 1200, with 10 ℃/min, be warming up to 2000 ℃ subsequently, and be incubated 2h, furnace cooling obtains greying and obtains MCMB, MCMB after greying is sieved to obtain to finished product carbon microspheres, and the size distribution of gained MCMB is 75-150 μ m.
Embodiment 4:
Purification coal tar mesophase pitch is placed in and adds electrothermal stove, be heated to 420 ℃, and be incubated the mesophase pitch that 6h obtains melting; This mesophase pitch is delivered to ejector nozzle, and the load of nozzle is 3.5kg/min; Pressure is that 0.3Mpa, temperature are that 40 ℃ of mixed oxidization gases containing 25% oxygen and nitrogen or argon gas enter gas atomization head; A gas atomization gas jet is sprayed to mesophase pitch, and mesophase pitch droplet is cooling balling-up in spray chamber, and now the temperature of spray chamber is 20 ℃, and pressure is 1.5atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in to vertical oxidized still, by room temperature, is freely warming up to 220 ℃, with 0.2 ℃/min, be warming up to 270 ℃ subsequently, and be incubated 10h, complete the spherular not melt processed of mesophase pitch; Microsphere after melt processed is not placed in to charring furnace, by room temperature, is freely warming up to 300 ℃, with 2 ℃/min, be warming up to 500 ℃ subsequently, and be incubated 2h, continue to be warming up to 950 ℃ with 2 ℃/min, and be incubated 2h, obtain the MCMB after charing; MCMB after charing is placed in to graphitizing furnace, by room temperature, be freely warming up to 1200, with 30 ℃/min, be warming up to 2200 ℃ subsequently, and be incubated 1h, furnace cooling obtains greying and obtains MCMB, MCMB after greying is sieved to obtain to finished product carbon microspheres, and the size distribution of gained MCMB is 15-45 μ m.
Embodiment 5:
Modification coal measures mesophase pitch is placed in and adds electrothermal stove, be heated to 280 ℃, and be incubated the mesophase pitch that 6h obtains melting; This mesophase pitch is delivered to ejector nozzle, and the load of nozzle is 2.0kg/min; Pressure is that 5.0Mpa, temperature are the N of 40 ℃
2or the non-oxidized gas such as Ar enters gas atomization head; A gas atomization gas jet is sprayed to mesophase pitch, and mesophase pitch droplet is cooling balling-up in spray chamber, and now the temperature of spray chamber is 40 ℃, and pressure is 1.0atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in to vertical oxidized still, by room temperature, is freely warming up to 200 ℃, with 0.2 ℃/min, be warming up to 280 ℃ subsequently, and be incubated 8h, complete the spherular not melt processed of mesophase pitch; Microsphere after melt processed is not placed in to charring furnace, by room temperature, is freely warming up to 300 ℃, with 2 ℃/min, be warming up to 450 ℃ subsequently, and be incubated 4h, continue to be warming up to 900 ℃ with 2 ℃/min, and be incubated 3h, obtain the MCMB after charing; MCMB after charing is placed in to graphitizing furnace, by room temperature, be freely warming up to 1200, with 20 ℃/min, be warming up to 2100 ℃ subsequently, and be incubated 2h, furnace cooling obtains greying and obtains MCMB, MCMB after greying is sieved to obtain to finished product carbon microspheres, and the size distribution of gained MCMB is 35-65 μ m.
Embodiment 6:
Modification coal measures mesophase pitch is placed in and adds electrothermal stove, be heated to 380 ℃, and be incubated the mesophase pitch that 6h obtains melting; This mesophase pitch is delivered to ejector nozzle, and the load of nozzle is 2.5kg/min; Pressure is that 0.5Mpa, temperature are that 50 ℃ of mixed oxidization gases containing 30% oxygen and nitrogen or argon gas enter gas atomization head; A gas atomization gas jet is sprayed to mesophase pitch, and mesophase pitch droplet is cooling balling-up in spray chamber, and now the temperature of spray chamber is 50 ℃, and pressure is 1.2atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in to vertical oxidized still, by room temperature, is freely warming up to 270 ℃, with 0.3 ℃/min, be warming up to 320 ℃ subsequently, and be incubated 2h, complete the spherular not melt processed of mesophase pitch; Microsphere after melt processed is not placed in to charring furnace, by room temperature, is freely warming up to 400 ℃, with 2 ℃/min, be warming up to 500 ℃ subsequently, and be incubated 2h, continue to be warming up to 950 ℃ with 2 ℃/min, and be incubated 2h, obtain the MCMB after charing; MCMB after charing is placed in to graphitizing furnace, by room temperature, be freely warming up to 1200, with 30 ℃/min, be warming up to 2200 ℃ subsequently, and be incubated 2h, furnace cooling obtains greying and obtains MCMB, MCMB after greying is sieved to obtain to finished product carbon microspheres, and the size distribution of gained MCMB is 35-65 μ m.
Embodiment 7:
Naphthalene is associated into mesophase pitch and is placed in and adds electrothermal stove with 7:3 weight ratio with purifying coal tar mesophase pitch, be heated to 390 ℃, and be incubated the mesophase pitch that 4h obtains melting; This mesophase pitch is delivered to ejector nozzle, and the load of nozzle is 2.5kg/min; Pressure is that 6.0Mpa, temperature are that the mixed oxidization gas containing 20% oxygen and nitrogen or argon gas of 40 ℃ enters gas atomization head; A gas atomization gas jet is sprayed to mesophase pitch, and mesophase pitch droplet is cooling balling-up in spray chamber, and now the temperature of spray chamber is 50 ℃, and pressure is 1.6atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in to vertical oxidized still, take air as oxidizing medium, by room temperature, be freely warming up to 230 ℃, with 0.2 ℃/min, be warming up to 290 ℃ subsequently, and be incubated 2h, complete the spherular not melt processed of mesophase pitch; Microsphere after melt processed is not placed in to charring furnace, by room temperature, is freely warming up to 400 ℃, with 2 ℃/min, be warming up to 600 ℃ subsequently, and be incubated 3h, continue to be warming up to 800 ℃ with 1 ℃/min, and be incubated 1h, obtain the MCMB after charing; MCMB after charing is placed in to graphitizing furnace, by room temperature, be freely warming up to 1200, with 10 ℃/min, be warming up to 2400 ℃ subsequently, and be incubated 1h, furnace cooling obtains greying and obtains MCMB, MCMB after greying is sieved to obtain to finished product carbon microspheres, and the size distribution of gained MCMB is 15-35 μ m.
Referring to shown in Fig. 5, is the size distribution figure of the embodiment of the present invention 2 acquired results, and as we know from the figure, the pore size distribution range of gained carbon microspheres is 10-25 μ m, and median size is 16.6 μ m.
Referring to shown in Fig. 6, is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 2 acquired results, and as we know from the figure, after greying, carbon microspheres keeps spherical characteristic preferably, surface uniform flawless.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention only limits to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by submitted to claims.
Claims (10)
1. a gas atomization device of preparing MCMB, it is characterized in that: comprise mesophase pitch melting electric furnace (1), screw extrusion transfer roller (4), spray chamber (5), and gas atomization head (13), one end of described screw extrusion transfer roller (4) is connected with mesophase pitch melting electric furnace (1), one end is stretched into spray chamber (5) and is connected with gas atomization head (13) in addition, described gas atomization head (13) is anchored on spray chamber top by atomising head stationary installation (6), the gas passage of described gas atomization head is connected with atmosphere pressures Controlling System (2), described spray chamber bottom arranges powder collector (11), the inwall of described spray chamber is provided with temperature control pipeline (7), temperature control pipeline (7) is connected with temperature controlling system (12).
2. gas atomization device as claimed in claim 1, is characterized in that: described spray chamber is further provided with strainer (9), and strainer (9) is connected with pressure control system (10) by pipeline.
3. gas atomization device as claimed in claim 1, is characterized in that: described screw extrusion transfer roller is with ejector nozzle, and the load of this ejector nozzle is 1.0-3.5kg/min.
4. gas atomization device as claimed in claim 1, is characterized in that: described gas atomization head includes two gas jets, and the axial angle between two nozzles is 30-90 °.
5. gas atomization device as claimed in claim 3, is characterized in that: described gas atomization head includes two gas jets, and the 1-2 that described gas jet diameter is ejector nozzle doubly.
6. the preparation method of the MCMB based on gas atomization device claimed in claim 1, it is characterized in that: the presoma of MCMB is heated in mesophase pitch melting electric furnace to molten state and sprays by screw extrusion transfer roller, gas jet on gas atomization head ejects high pressure gas with the mesophase pitch atomization of liquid to molten state, the sedimentation of mesophase pitch melting microsphere is solidified, finally enter into powder collector, the MCMB that powder collector is collected is through melt processed not, after charing processing and graphitization processing, screening, collect, wherein, the method of melt processed is not: in oxidizing atmosphere, from room temperature, be warming up to after 160-270 ℃, heat-up rate with 0.1-0.3 ℃/min is heated to 220-350 ℃, insulation 0.5-10 hour, MCMB surface forms stable C-O-C oxo bridge structure, the method that described charing is processed is: under nitrogen or argon gas condition, 1-3 ℃/min is warming up to 350-650 ℃, and insulation 1-4 hour continues to be warming up to 800-1200 ℃ of insulation 1-4 hour, furnace cooling with 1-5 ℃/min, the method of described graphitization processing is: under argon gas atmosphere, rise to 2000-2400 ℃ after being warming up to 1200 ℃ with 10-50 ℃/min temperature rise rate, insulation 0.5-2 hour, furnace cooling.
7. preparation method as claimed in claim 6, it is characterized in that: in atomization treating processes, atmosphere pressures is 0.3-9Mpa, high pressure gas are the mixed oxidization gas of non-oxidized gas or oxygen and non-oxidized gas formation, described non-oxidized gas is nitrogen or argon gas, in mixed oxidization gas, oxidizing atmosphere content is for being less than or equal to 30%.
8. preparation method as claimed in claim 6, is characterized in that: the temperature of described spray chamber is 15-60 ℃, and spray chamber pressure is 0.6-1.6atm.
9. preparation method as claimed in claim 6, is characterized in that: in described not melt processed method, described oxidizing atmosphere is air, oxygen, ozone, nitrogen peroxide or sulphur trioxide atmosphere.
10. preparation method as claimed in claim 6, is characterized in that: the presoma of MCMB is elected naphthalene as and is associated into mesophase pitch, purifies after one or more in coal tar mesophase pitch or modification coal measures mesophase pitch grind and cross 100 mesh sieves and obtain.
Priority Applications (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047860A (en) * | 2014-12-19 | 2015-11-11 | 上海杉杉科技有限公司 | Battery cathode TiO2/intermediate-phase microsphere composite material and preparation method thereof |
| CN107910553A (en) * | 2017-10-30 | 2018-04-13 | 北京万源工业有限公司 | Mesocarbon microspheres method of modifying and its application as cell negative electrode material |
| CN109037603A (en) * | 2018-06-13 | 2018-12-18 | 福建翔丰华新能源材料有限公司 | Novel method for preparing asphalt-based spherical porous doping modified hard carbon negative electrode material |
| CN111732098A (en) * | 2020-07-01 | 2020-10-02 | 河南开炭新材料设计研究院有限公司 | Preparation method of asphalt-based carbon microspheres for lithium battery negative electrode material |
| CN112086650A (en) * | 2019-06-12 | 2020-12-15 | 清华大学 | Fuel cell, expanded graphite plate and preparation method of expanded graphite plate |
| CN114684817A (en) * | 2021-11-12 | 2022-07-01 | 中国神华煤制油化工有限公司 | Method and apparatus for preparing spherical negative active material, negative electrode for lithium battery, and lithium battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684984A (en) * | 2008-09-28 | 2010-03-31 | 赵君哲 | Spray drying method and device thereof |
| WO2011047181A2 (en) * | 2009-10-14 | 2011-04-21 | The Administrators Of The Tulane Educational Fund | Novel multifunctional materials for in-situ environmental remediation of chlorinated hydrocarbons |
| CN102179217A (en) * | 2011-03-10 | 2011-09-14 | 江苏国正新材料科技有限公司 | Preparation method of hyper-energy active electrical carbon hollow micro ball |
-
2013
- 2013-11-25 CN CN201310614323.5A patent/CN103663440B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101684984A (en) * | 2008-09-28 | 2010-03-31 | 赵君哲 | Spray drying method and device thereof |
| WO2011047181A2 (en) * | 2009-10-14 | 2011-04-21 | The Administrators Of The Tulane Educational Fund | Novel multifunctional materials for in-situ environmental remediation of chlorinated hydrocarbons |
| CN102179217A (en) * | 2011-03-10 | 2011-09-14 | 江苏国正新材料科技有限公司 | Preparation method of hyper-energy active electrical carbon hollow micro ball |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105047860A (en) * | 2014-12-19 | 2015-11-11 | 上海杉杉科技有限公司 | Battery cathode TiO2/intermediate-phase microsphere composite material and preparation method thereof |
| CN105047860B (en) * | 2014-12-19 | 2019-08-06 | 上海杉杉科技有限公司 | Battery cathode titanium dioxide carbonaceous mesophase spherules composite material and preparation method |
| CN107910553A (en) * | 2017-10-30 | 2018-04-13 | 北京万源工业有限公司 | Mesocarbon microspheres method of modifying and its application as cell negative electrode material |
| CN109037603A (en) * | 2018-06-13 | 2018-12-18 | 福建翔丰华新能源材料有限公司 | Novel method for preparing asphalt-based spherical porous doping modified hard carbon negative electrode material |
| CN109037603B (en) * | 2018-06-13 | 2020-02-14 | 福建翔丰华新能源材料有限公司 | Novel method for preparing asphalt-based spherical porous doping modified hard carbon negative electrode material |
| CN112086650A (en) * | 2019-06-12 | 2020-12-15 | 清华大学 | Fuel cell, expanded graphite plate and preparation method of expanded graphite plate |
| CN112086650B (en) * | 2019-06-12 | 2021-07-02 | 清华大学 | Fuel cell, expanded graphite plate and preparation method of expanded graphite plate |
| CN111732098A (en) * | 2020-07-01 | 2020-10-02 | 河南开炭新材料设计研究院有限公司 | Preparation method of asphalt-based carbon microspheres for lithium battery negative electrode material |
| CN114684817A (en) * | 2021-11-12 | 2022-07-01 | 中国神华煤制油化工有限公司 | Method and apparatus for preparing spherical negative active material, negative electrode for lithium battery, and lithium battery |
| CN114684817B (en) * | 2021-11-12 | 2023-08-25 | 中国神华煤制油化工有限公司 | Method and device for preparing spherical anode active material, lithium battery anode and lithium battery |
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