CN103663440B - 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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- CN103663440B CN103663440B CN201310614323.5A CN201310614323A CN103663440B CN 103663440 B CN103663440 B CN 103663440B CN 201310614323 A CN201310614323 A CN 201310614323A CN 103663440 B CN103663440 B CN 103663440B
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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 a kind of manufacturing technology of dynamic lithium battery MCMB, particularly a kind of aerosolization method and device 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, to embed characteristic outstanding; Within 1992, MCMB is applied in lithium ion battery by Japanese Yamamura 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 having competition potential.
In production, 1973, Japanese scholars Honda and Yamada obtained MCMB by thermal polymerization, and the method is because technique is simple, be easy to control and be applied to suitability for industrialized production, but owing to reuniting, the yield of thermal polymerization is lower, is generally 20-35%.After Chinese patent CN02116840.7 and CN101811694A discloses asphalt stock and catalyst mix, utilize thermal polymerization to prepare the method for MCMB under certain temperature and pressure, the highest yield of display is 39%.
The copolycondensation preparation method of existing MCMB, need not under pretreated condition, prepare the uniform MCMB of spherolite by medium temperature coal pitch and ethylene bottom oil copolycondensation, yield be 20-30%.Because thermal polymerization production efficiency is lower, and need to consume a large amount of solvent repetitive scrubbing in preparation MCMB process, cause current MCMB cost high, in addition, the factors such as the homogeneity of MCMB particle diameter and surface quality difference have a strong impact on end-use performance.Though emulsion method and suspension method can improve the yield of MCMB, need medium that high high-temp stability is good and tensio-active agent, production process is complicated, and process regulation difficulty is large, and cost is high, there is 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, low cost, eco-friendly technology of preparing efficient in the urgent need to one.
Summary of the invention:
The invention provides a kind of aerosolization method and the device of preparing MCMB, solve the problems such as existing cathode material of lithium ion battery 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 preparing intermediate-phase carbon carbon microspheres, comprise mesophase pitch melting electric furnace, Spiral extrusion conveyor, spray chamber, and gas atomization head, one end of described Spiral extrusion conveyor 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, powder collector is set bottom described spray chamber, 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 provided with strainer further, and strainer is connected with pressure control system by pipeline.
As the preferred embodiments of the present invention, described Spiral extrusion conveyor 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 described gas jet diameter is 1-2 times of ejector nozzle.
A kind of preparation method of the MCMB based on above-mentioned gas atomization device, spray through Spiral extrusion conveyor after the presoma of MCMB is heated to molten state in mesophase pitch melting electric furnace, 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 cure treatment, after charing handler graphitization processing, mechanism sieves, collect, wherein, the method of cure treatment is: in oxidizing atmosphere, after room temperature is to 160-270 DEG C, 220-350 DEG C is heated to the heat-up rate of 0.1-0.3 DEG C/min, insulation 0.5-10 hour, MCMB surface forms stable C-O-C oxo bridge structure, the method of described charing process is: under nitrogen or argon gas condition, 1-3 DEG C/min is warming up to 350-650 DEG C, insulation 1-4 hour, continues to be warming up to 800-1200 DEG C of insulation 1-4 hour, furnace cooling with 1-5 DEG C/min, the method of described graphitization processing is: under an argon atmosphere, rises to 2000-2400 DEG C after being warming up to 1200 DEG C with 10-50 DEG C/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 that non-oxidized gas or oxygen and non-oxidized gas are formed, 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 DEG C, and spray chamber pressure is 0.6-1.6atm.
As the preferred embodiments of the present invention, in described cure treatment 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 elects naphthalene system synthetic mesophase asphalt phase as, one or more grindings purified in coal tar mesophase pitch or modification coal measures mesophase pitch are rear crosses 100 mesh sieves and obtains.
Compared with prior art, beneficial effect of the present invention is: (1) MCMB yield is high, good sphericity, and even particle size distribution, size are controlled; (2) technology controlling and process is simple, is easy to suitability for industrialized production, low cost of manufacture; (3) participate in without the need to organic solvent, 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 grain size distribution 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 μm, and median size is 16.6 μm.
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 Spiral extrusion conveyor, 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 inlet passages, 16 gas jets, 17 ejector nozzle interfaces.
Embodiment
A kind of aerosolization method and device preparing MCMB provided by the invention, technological process as shown in Figure 1, mainly comprises the modulation of presoma pitch, atomization process, cure treatment, charing, greying.Its concrete steps are as follows:
(1) modulation of presoma pitch
By one or more grindings in naphthalene system synthetic mesophase asphalt phase, purification coal tar mesophase pitch or modification coal measures mesophase pitch, as the presoma of preparation MCMB after mistake 100 mesh sieves.
(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 Spiral extrusion conveyor, 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 inlet 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, Spiral extrusion conveyor 4 is with ejector nozzle and be connected with spray chamber 5 by mesophase pitch melting electric furnace 1, the output terminal of Spiral extrusion conveyor 4 stretches into spray chamber 5, is connected with gas atomization 13; Gas atomization 13 is anchored on spray chamber 5 top by atomising head stationary installation 6; The gas passage of gas atomization 13 is connected by pipeline with atmosphere pressures Controlling System 2, and 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 outside spray chamber 5; Powder collector 11 is set bottom spray chamber 5; 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, and the pipeline that described strainer is connected with pressure control system is provided with pressure control valve 8; Temperature control pipeline 7 is spirane structure, is arranged at spray chamber inwall, is connected with temperature controlling system 12.
Atomization process: step (1) described presoma is placed in mesophase pitch melting electric furnace 1 and is heated to 280-420 DEG C, and be incubated 0.5-12 hour, obtain continuous mesophase spherule molten mass; This mesophase spherule molten mass is sprayed by the Spiral extrusion conveyor 4 with ejector nozzle; Open gas control valve 3, aerosolization atmosphere pressures Controlling System 2 connects gas atomization 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, final importing powder collector 11, powder collector 11 completes separation of air from dust; Pressure control system 10 maintains spray chamber 5 pressure equilibrium 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, the non-oxidizing gas such as Ar gas or oxygen and N
2, the non-oxidizing gas such as Ar gas composition mixed oxidization gas; The content of oxidizing atmosphere in total atmosphere is 0-30%;
The temperature of described spray chamber controls to be completed by temperature controlling system 12, is 15-60 DEG C;
The pressure range of described spray chamber is 0.6-1.6atm;
The setting of Spiral extrusion conveyor can prevent line clogging and material from regurgitating, and plays conveying and the effect of extruding drawing-off, make the mesophase pitch before being atomized form fibre-like weave construction in rotary course to melting mesophase pitch.Transfer roller discharge port can match difform ejector nozzle, and the present invention selects diameter to be the tubulose ejector nozzle of 4mm, 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 (shown in, atomising head comprises two gas jets, axial angle between two nozzles is 30-90 °, the present invention selects angle to be 90 °, the diameter of gas jet is generally 1-2 times of ejector nozzle diameter, the gas jet diameter 1.5 that the present invention selects, doubly to ejector nozzle, is 6mm.Injector spacing is 15mm.
(3) cure treatment technique
The cure treatment of MCMB carries out on vertical oxidized still, and oxidizing atmosphere can for being air, oxygen, ozone, nitrogen peroxide, sulphur trioxide etc., and this patent is for the air of low cost.First from room temperature to 160-270 DEG C, then 220-350 DEG C is heated to the heat-up rate of 0.1-0.5 DEG C/min, and be incubated 0.5-10 hour, make that mesophase pitch microsphere is fully oxidized, dehydrogenation, the chemical reaction such as crosslinked and cyclisation, form stable C-O-C oxo bridge structure on MCMB surface, ensure that MCMB, in carbonization process, melting, distortion and cracking phenomena does not occur.
(4) charring process
Step 3 gained oxidation MCMB is placed in atmosphere charring furnace, under nitrogen or argon gas condition, is warming up to 350-650 DEG C with 1-3 DEG C/min, insulation 1-5 hour; Continue to be warming up to 800-1200 DEG C of insulation 1-3 hour, the MCMB after furnace cooling must carbonize with 1-5 DEG C/min.
(5) graphitization processing
Step 4 gained charing MCMB is placed in atmosphere graphitizing furnace, and described atmosphere is Ar gas.Naturally rise to 2000-2400 DEG C with 10-50 DEG C/min temperature rise rate after being warming up to 1200 DEG C, and be incubated 0.5-2 hour, furnace cooling obtains MCMB after greying.
(6) sieve, collect
By screening plant to the MCMB magnitude classification after graphitization processing, collect 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:
Naphthalene system mesophase pitch is placed in hot plate, is heated to 360 DEG C, 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; The N that pressure is 9.0Mpa, temperature is 60 DEG C
2or the non-oxidized gas such as Ar enters gas atomization head; Gas atomization head gas jet is sprayed to mesophase pitch, and mesophase pitch droplet cools balling-up in spray chamber, and now the temperature of spray chamber is 50 DEG C, and pressure is 0.6atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in vertical oxidized still, is freely warming up to 220 DEG C by room temperature, be warming up to 280 DEG C with 0.1 DEG C/min subsequently, and be incubated 4h, complete the spherular cure treatment of mesophase pitch; Microsphere after cure treatment is placed in charring furnace, is freely warming up to 300 DEG C by room temperature, be warming up to 500 DEG C with 1 DEG C/min subsequently, and be incubated 5h, continue to be warming up to 1000 DEG C with 1 DEG C/min, and be incubated 3h, obtain the MCMB after carbonizing; MCMB after charing is placed in graphitizing furnace, freely 1200 are warming up to by room temperature, 2400 DEG C are warming up to subsequently with 30 DEG C/min, and be incubated 0.5h, furnace cooling obtains greying and obtains MCMB, sieve to obtain finished product carbon microspheres to the MCMB after greying, the size distribution of finished product carbon microspheres is 45-105 μm.
Embodiment 2:
Naphthalene system mesophase pitch is placed in hot plate, is heated to 400 DEG C, 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; The mixed oxidization gas containing 15% oxygen and nitrogen or argon gas that pressure is 3.0Mpa, temperature is 60 DEG C enters gas atomization head; Gas atomization head gas jet is sprayed to mesophase pitch, and mesophase pitch droplet cools balling-up in spray chamber, and now the temperature of spray chamber is 15 DEG C, and pressure is 1.6atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in vertical oxidized still, is freely warming up to 260 DEG C by room temperature, be warming up to 350 DEG C with 0.5 DEG C/min subsequently, and be incubated 0.5h, complete the spherular cure treatment of mesophase pitch; Microsphere after cure treatment is placed in charring furnace, is freely warming up to 350 DEG C by room temperature, be warming up to 650 DEG C with 3 DEG C/min subsequently, and be incubated 1h, continue to be warming up to 1200 DEG C with 5 DEG C/min, and be incubated 1h, obtain the MCMB after carbonizing; MCMB after charing is placed in graphitizing furnace, freely 1200 are warming up to by room temperature, 2300 DEG C are warming up to subsequently with 50 DEG C/min, and be incubated 2h, furnace cooling obtains greying and obtains MCMB, sieve to obtain finished product carbon microspheres to the MCMB after greying, the size distribution of finished product carbon microspheres is 10-25 μm.
Embodiment 3:
Purification coal tar mesophase pitch is placed in hot plate, is heated to 280 DEG C, 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; The N that pressure is 6.0Mpa, temperature is 25 DEG C
2or the non-oxidized gas such as Ar enters gas atomization head; Gas atomization head gas jet is sprayed to mesophase pitch, and mesophase pitch droplet cools balling-up in spray chamber, and now the temperature of spray chamber is 60 DEG C, and pressure is 0.9atm, and microsphere falls in powder collector; The mesophasespherule of collection is placed in vertical oxidized still, is freely warming up to 160 DEG C by room temperature, be warming up to 220 DEG C with 0.1 DEG C/min subsequently, and be incubated 5h, complete the spherular cure treatment of mesophase pitch; Microsphere after cure treatment is placed in charring furnace, is freely warming up to 220 DEG C by room temperature, be warming up to 350 DEG C with 1 DEG C/min subsequently, and be incubated 3h, continue to be warming up to 800 DEG C with 1 DEG C/min, and be incubated 1h, obtain the MCMB after carbonizing; MCMB after charing is placed in graphitizing furnace, freely 1200 are warming up to by room temperature, 2000 DEG C are warming up to subsequently with 10 DEG C/min, and be incubated 2h, furnace cooling obtains greying and obtains MCMB, sieve to obtain finished product carbon microspheres to the MCMB after greying, the size distribution of gained MCMB is 75-150 μm.
Embodiment 4:
Purification coal tar mesophase pitch is placed in hot plate, is heated to 420 DEG C, 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 0.3Mpa, temperature is that 40 DEG C of mixed oxidization gases containing 25% oxygen and nitrogen or argon gas enter gas atomization head; Gas atomization head gas jet is sprayed to mesophase pitch, and mesophase pitch droplet cools balling-up in spray chamber, and now the temperature of spray chamber is 20 DEG C, and pressure is 1.5atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in vertical oxidized still, is freely warming up to 220 DEG C by room temperature, be warming up to 270 DEG C with 0.2 DEG C/min subsequently, and be incubated 10h, complete the spherular cure treatment of mesophase pitch; Microsphere after cure treatment is placed in charring furnace, is freely warming up to 300 DEG C by room temperature, be warming up to 500 DEG C with 2 DEG C/min subsequently, and be incubated 2h, continue to be warming up to 950 DEG C with 2 DEG C/min, and be incubated 2h, obtain the MCMB after carbonizing; MCMB after charing is placed in graphitizing furnace, freely 1200 are warming up to by room temperature, 2200 DEG C are warming up to subsequently with 30 DEG C/min, and be incubated 1h, furnace cooling obtains greying and obtains MCMB, sieve to obtain finished product carbon microspheres to the MCMB after greying, the size distribution of gained MCMB is 15-45 μm.
Embodiment 5:
Modification coal measures mesophase pitch is placed in hot plate, is heated to 280 DEG C, 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; The N that pressure is 5.0Mpa, temperature is 40 DEG C
2or the non-oxidized gas such as Ar enters gas atomization head; Gas atomization head gas jet is sprayed to mesophase pitch, and mesophase pitch droplet cools balling-up in spray chamber, and now the temperature of spray chamber is 40 DEG C, and pressure is 1.0atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in vertical oxidized still, is freely warming up to 200 DEG C by room temperature, be warming up to 280 DEG C with 0.2 DEG C/min subsequently, and be incubated 8h, complete the spherular cure treatment of mesophase pitch; Microsphere after cure treatment is placed in charring furnace, is freely warming up to 300 DEG C by room temperature, be warming up to 450 DEG C with 2 DEG C/min subsequently, and be incubated 4h, continue to be warming up to 900 DEG C with 2 DEG C/min, and be incubated 3h, obtain the MCMB after carbonizing; MCMB after charing is placed in graphitizing furnace, freely 1200 are warming up to by room temperature, 2100 DEG C are warming up to subsequently with 20 DEG C/min, and be incubated 2h, furnace cooling obtains greying and obtains MCMB, sieve to obtain finished product carbon microspheres to the MCMB after greying, the size distribution of gained MCMB is 35-65 μm.
Embodiment 6:
Modification coal measures mesophase pitch is placed in hot plate, is heated to 380 DEG C, 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 0.5Mpa, temperature is that 50 DEG C of mixed oxidization gases containing 30% oxygen and nitrogen or argon gas enter gas atomization head; Gas atomization head gas jet is sprayed to mesophase pitch, and mesophase pitch droplet cools balling-up in spray chamber, and now the temperature of spray chamber is 50 DEG C, and pressure is 1.2atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in vertical oxidized still, is freely warming up to 270 DEG C by room temperature, be warming up to 320 DEG C with 0.3 DEG C/min subsequently, and be incubated 2h, complete the spherular cure treatment of mesophase pitch; Microsphere after cure treatment is placed in charring furnace, is freely warming up to 400 DEG C by room temperature, be warming up to 500 DEG C with 2 DEG C/min subsequently, and be incubated 2h, continue to be warming up to 950 DEG C with 2 DEG C/min, and be incubated 2h, obtain the MCMB after carbonizing; MCMB after charing is placed in graphitizing furnace, freely 1200 are warming up to by room temperature, 2200 DEG C are warming up to subsequently with 30 DEG C/min, and be incubated 2h, furnace cooling obtains greying and obtains MCMB, sieve to obtain finished product carbon microspheres to the MCMB after greying, the size distribution of gained MCMB is 35-65 μm.
Embodiment 7:
Naphthalene system synthetic mesophase asphalt phase and purification coal tar mesophase pitch are placed in hot plate with 7:3 weight ratio, are heated to 390 DEG C, 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; The mixed oxidization gas containing 20% oxygen and nitrogen or argon gas that pressure is 6.0Mpa, temperature is 40 DEG C enters gas atomization head; Gas atomization head gas jet is sprayed to mesophase pitch, and mesophase pitch droplet cools balling-up in spray chamber, and now the temperature of spray chamber is 50 DEG C, and pressure is 1.6atm, and microsphere falls in powder collector; The mesophase pitch microsphere of collection is placed in vertical oxidized still, take air as oxidizing medium, is freely warming up to 230 DEG C by room temperature, is warming up to 290 DEG C subsequently, and is incubated 2h with 0.2 DEG C/min, completes the spherular cure treatment of mesophase pitch; Microsphere after cure treatment is placed in charring furnace, is freely warming up to 400 DEG C by room temperature, be warming up to 600 DEG C with 2 DEG C/min subsequently, and be incubated 3h, continue to be warming up to 800 DEG C with 1 DEG C/min, and be incubated 1h, obtain the MCMB after carbonizing; MCMB after charing is placed in graphitizing furnace, freely 1200 are warming up to by room temperature, 2400 DEG C are warming up to subsequently with 10 DEG C/min, and be incubated 1h, furnace cooling obtains greying and obtains MCMB, sieve to obtain finished product carbon microspheres to the MCMB after greying, the size distribution of gained MCMB is 15-35 μm.
Referring to shown in Fig. 5, is the grain size distribution 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 μm, and median size is 16.6 μm.
Refer to shown in Fig. 6, be the scanning electron microscope (SEM) photograph of the embodiment of the present invention 2 acquired results, 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 is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the present invention by submitted to claims determination scope of patent protection.
Claims (8)
1. prepare the gas atomization device of MCMB for one kind, it is characterized in that: comprise mesophase pitch melting electric furnace (1), Spiral extrusion conveyor (4), spray chamber (5), and gas atomization head (13), one end of described Spiral extrusion conveyor (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), powder collector (11) is set bottom described spray chamber, the inwall of described spray chamber is provided with temperature control pipeline (7), temperature control pipeline (7) is connected with temperature controlling system (12), described gas atomization head includes two gas jets, and the axial angle between two nozzles is 30-90 °, and described Spiral extrusion conveyor is with ejector nozzle, and the load of this ejector nozzle is 1.0-3.5kg/min.
2. gas atomization device as claimed in claim 1, it is characterized in that: described spray chamber is provided with strainer (9) further, 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 gas atomization head includes two gas jets, and described gas jet diameter is 1-2 times of ejector nozzle.
4. the preparation method based on the MCMB of gas atomization device according to claim 1, it is characterized in that: spray through Spiral extrusion conveyor after the presoma of MCMB is heated to molten state in mesophase pitch melting electric furnace, 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 cure treatment, after carbonizing process and graphitization processing, screening, collect, wherein, the method for cure treatment is: in oxidizing atmosphere, after room temperature is to 160-270 DEG C, is heated to 220-350 DEG C with the heat-up rate of 0.1-0.3 DEG C/min, and insulation 0.5-10 hour, MCMB surface forms stable C-O-C oxo bridge structure, the method of described charing process is: under nitrogen or argon gas condition, 1-3 DEG C/min is warming up to 350-650 DEG C, insulation 1-4 hour, continues to be warming up to 800-1200 DEG C of insulation 1-4 hour, furnace cooling with 1-5 DEG C/min, the method of described graphitization processing is: under an argon atmosphere, rises to 2000-2400 DEG C after being warming up to 1200 DEG C with 10-50 DEG C/min temperature rise rate, insulation 0.5-2 hour, furnace cooling.
5. preparation method as claimed in claim 4, it is characterized in that: in atomization treating processes, atmosphere pressures is 0.3-9MPa, high pressure gas are the mixed oxidization gas that non-oxidized gas or oxygen and non-oxidized gas are formed, 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%.
6. preparation method as claimed in claim 4, is characterized in that: the temperature of described spray chamber is 15-60 DEG C, and spray chamber pressure is 0.6-1.6atm.
7. preparation method as claimed in claim 4, it is characterized in that: in described cure treatment method, described oxidizing atmosphere is air, oxygen, ozone, nitrogen peroxide or sulphur trioxide atmosphere.
8. preparation method as claimed in claim 4, is characterized in that: the presoma of MCMB elects naphthalene system synthetic mesophase asphalt phase as, one or more grindings purified in coal tar mesophase pitch or modification coal measures mesophase pitch are rear crosses 100 mesh sieves and obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310614323.5A CN103663440B (en) | 2013-11-25 | 2013-11-25 | Gas atomization method and device for preparing mesocarbon microbeads |
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| CN201310614323.5A CN103663440B (en) | 2013-11-25 | 2013-11-25 | Gas atomization method and device for preparing mesocarbon microbeads |
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| CN103663440A CN103663440A (en) | 2014-03-26 |
| CN103663440B true CN103663440B (en) | 2015-07-22 |
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