CN106278367A - Under normal pressure, the device and method of coal-based carbon foam prepared by microwave heating - Google Patents

Under normal pressure, the device and method of coal-based carbon foam prepared by microwave heating Download PDF

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CN106278367A
CN106278367A CN201610634092.8A CN201610634092A CN106278367A CN 106278367 A CN106278367 A CN 106278367A CN 201610634092 A CN201610634092 A CN 201610634092A CN 106278367 A CN106278367 A CN 106278367A
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coal
based carbon
carbon foam
microwave
temperature
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CN106278367B (en
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徐国忠
王绍艳
钟祥云
徐桂英
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University of Science and Technology Liaoning USTL
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Abstract

Under normal pressure, the apparatus and method of coal-based carbon foam prepared by microwave heating, this device specifically includes that microwave protection case, it is placed in the support in microwave chemical defence case, quartz molds, is placed in the microwave generator below support and is placed in the intelligent temperature control instrument outside microwave chemical defence case and microwave power actuator.The preparation method is that the method that under normal pressure, coal-based carbon foam prepared by microwave heating, key step includes: the preparation of coal-based carbon foam precursor, microwave heating are prepared coal-based carbon foam and come into being body and body of coming into being coal-based carbon foam carries out carbonization process, prepare coal-based carbon foam.The invention has the beneficial effects as follows: be greatly shortened the time preparing coal-based carbon foam, reduce energy consumption, solving when dependence conduction of heat prepares coal-based carbon foam and the problem that macroscopic cracking even ftractures occur, this invention simultaneously has simple, it is easy to the feature of popularization.

Description

Under normal pressure, the device and method of coal-based carbon foam prepared by microwave heating
Technical field
The invention belongs to prepare coal-based carbon foam technology field, particularly relate to microwave heating under a kind of normal pressure and prepare coal base The device and method of carbon foams.
Background technology
Carbon foams is a kind of brand-new material having structure and functional characteristic concurrently, and it is that one has three-dimensional cross-linked hole, hole wall And the lightweight Carbon Materials of different holes crosslink part composition.The pore structure of carbon foams include bulk density, the porosity, true density, Hole pattern, average pore diameter, the density (the hole number that i.e. unit volume carbon foams has) in hole), pore-size distribution etc..By changing Raw material type and character and preparation parameter, it is possible to achieve the cutting of carbon foams pore structure, and then carbon foams performance can be realized Regulation and control.Therefore, carbon foams possesses as thermal management materials, absorbing material, electromagnetic shielding material, catalyst carrier, adsorption material The character of material；Owing to carbon foams has biocompatibility, also there is the potential quality of application at life science；Carbon foams can also be with Other metals or nonmetal being combined prepare structural material；Due to carbon foams light weight, dimensionally stable, easily process, Ke Yiyong Mould prepared by fibrous woven and composite and space microscope base etc..In a word, the preparation of carbon foams, application, modification etc. are ground Study carefully at home for receiving significant attention.And the preparation of carbon foams is the most important link in carbon foams research and application.
Up to the present, the preparation method of carbon foams includes following several:
(1) foaming agent foam method
Foaming agent foam method is to prepare the common method of resin base carbon foams.The method is with resin as raw material, with foaming agent Mixing, under high pressure, uses reactor external heat, and heat conducts heat by the outer wall of reactor to material, when temperature liter To resin softening point temperatures above, then decompression step by step, make foaming agent decompose or volatilization, stay room to form bubble in resin Foam, last carbonization, graphitization (high-temperature process) obtain carbon foams.If presoma resin is thermoplastic resin, also need before carbonization Through peroxidating, solidification process.And in actual applications, sometimes for the intensity of raising resin base carbon foams, even with thermosetting Property resin is presoma, also to carry out oxidation processes before carbonization.
The method needs to add foaming agent, additionally needs and presoma is carried out pre-oxidation treatment, and therefore cost is the highest.
(2) pressurization charring
The method is also known as high pressure nitriding gas method, refers to, with Colophonium, coal or thermoplastic polymer as presoma, be placed in high pressure and set In Bei, reaching certain pressure (i.e. blow pressure) to the internal inflated with nitrogen of high pressure equipment, use reactor external heat, heat passes through The outer wall of reactor conducts heat to material, reaches design temperature (i.e. blowing temperature), at this temperature, constant temperature certain time After (i.e. foamed time), pressure release is foamed, and obtains your carbon foams and comes into being that (document having claims green foam to body, refers to that presoma completes Foaming, and solidify, form the overall semicoke of loose structure).Carry out carbonization and graphitization processing the most again.The method is adjustable Parameter has blow pressure, blowing temperature, foamed time, pressure release speed and presoma character, and therefore designability is relatively strong, is mesh The front main method preparing carbon foams, its preparation flow is as shown in Figure 1.
Two kinds of new methods are produced again based on the method:
1) spontaneous foam method
So-called spontaneous platen press refers to use thermoplastic material's (Colophonium, coal or thermoplastic polymer etc.), after being heated in presoma Molecular side chain breaks to form the little molecule of gaseous state, volatilizes parent together with original small-molecule substance, relies on these gases to reach One blow pressure, constant temperature certain time under blowing temperature, the foaming of pressure release nucleation obtains carbon foams and comes into being body, then through carbonization, Obtain carbon foams.Require to carry out graphitization processing according to application scenario.
2) limit space law
The method is the invention that Wang Chengyang teaches seminar.The isostatic pressed that raw material produces in mould endogenous cause of ill volumetric expansion has It is beneficial to be formed the hole of uniform pore diameter.Concrete grammar is as follows: seals after mesophase pitch powder is put people's mould, then is added by mould Heat, to asphalt softening point temperatures above, is lowered the temperature after insulation a period of time, obtains the raw body of carbon foams, then will carry out carbonization and graphitization Process, i.e. obtain intermediate phase pitch-based carbon foams.In the case of in holding mould, gross space is certain, can be by adjusting mould Interior feeding quantity regulates pressure, it is achieved Carbon foam pore size control；Also can be foamed by adjustment in the case of feeding quantity is certain During the size in mold freedom space regulate pressure, it is achieved the pore size control of Carbon foam.
In recent years, coal-based carbon foam, owing to feed coal is cheap, wide material sources, is considered most application potential, is subject to Extensive concern.The U.S. with medium degree of metamorphism bituminous coal as raw material, use pressurization charring prepare coal-based carbon foam, formed many specially Profit, and at touchstone company industry.Consistent through analyzing these patents to the requirement of coal, i.e. require coal must low ash low The free wxpansion ordinal number of sulfur and coal is 3-5 (i.e. caking property is good).And China's coal has high ash high-sulfur, bad adhesion and mixed coal and occupies Many, such coal is not suitable for preparing coal-based carbon foam.Applicant is for this present situation, with liquor zinci chloridi that proportion is 1.35 or benzene It is flotation fluid with the combination solution of carbon tetrachloride, the vitrinite in separation and concentration medium degree of metamorphism bituminous coal, obtain vitrinite rich Collection thing, uses pressure charring (also known as high pressure nitriding gas method) to prepare carbon foams with it for raw material, and the granted China of the method invents Patent (utilizes the method that pretreatment bituminous coal prepares coal base graphitization carbon foams, Patent No. ZL 2,012 1 0364942.9).Root When preparing large scale (a diameter of 120mm, the cylinder of a length of 300) carbon foams according to patented method, during preparation, use external heat, heat Conducted to material core by the wall of high pressure equipment.Find: prepare carbon foams body opening born of the same parents' ratio of coming into being more uniform, but prepare carbon foams Nascent body for up to 10 hours, and the carbon foams obtained is come into being there is macroscopic cracking in body, even ftractures.
In sum, there is common ground in the method for carbon foams made above: the main equipment i.e. preparing carbon foams is high pressure Equipment；All in the external heat of high pressure equipment, heat is entered to the raw material prepared used by carbon foams by the metallic walls of high pressure equipment Row conduction of heat.The lowest, when closing on high pressure equipment owing to being used for preparing the heat conductivity of the coal of carbon foams or vitrinite's enriched substance After the material of metallic walls reaches blowing temperature, the temperature of material core is far from reaching blowing temperature, from appts wall to material core There is bigger temperature difference in portion.After the material of nearby device wall forms semicoke, the heat conductivity of semicoke is high, just can significantly improve The temperature of material adjacent with semicoke, produces from high pressure equipment wall to material core foaming process layer by layer.So will bring two to ask Topic, one is to cause the time preparing carbon foams longer because the heat conductivity of presoma is low, power consumption height；Further, since send out layer by layer Bubble, causes there is many bed boundarys inside carbon foams, and internal residual thermal stress is relatively big, causes carbon foams to produce macroscopic cracking, very To cracking.Especially latter problem becomes bottleneck prepared by large scale coal-based carbon foam.
Summary of the invention
It is an object of the invention to provide a kind of can be greatly shortened coal-based carbon foam come into being body preparation time, reduce energy Consumption；And solve coal-based carbon foam and there is macroscopic cracking and under the normal pressure of problem of Cracking, coal-based carbon foam prepared by microwave heating Device.
Another object of the present invention is to provide microwave heating under a kind of normal pressure to prepare coal-based carbon bubble for realizing said method The method of foam.
The technology of the present invention is as follows:
To achieve these goals, the technical solution adopted in the present invention is:
Under a kind of normal pressure of the present invention, the device of coal-based carbon foam prepared by microwave heating, it is characterised in that: include that microwave is prevented Protecting box, the support being arranged in microwave protection case and the quartz molds being placed on support, set in the outside of described quartz molds There is heat-insulation layer, heat-insulation layer is provided with the steam vent connected with quartz molds, be provided with row at the top of described microwave protection case Trachea and temperature thermocouple installing hole, have microwave introduction channel in the bottom of described support, and microwave generator is placed in microwave The bottom of introduction channel, is provided with temperature thermocouple on the top of described microwave protection case, the thermometric end position of this temperature thermocouple In quartz molds in presoma, described temperature thermocouple signal output part is connected with the signal input part of intelligent temperature control instrument, The signal output part of this intelligent temperature control instrument is connected with microwave power actuator, and microwave power actuator is connected with microwave generator, For the power according to temperature thermocouple measured value real-time monitoring microwave generator 13.
Further, described microwave protection case and support use 304 corrosion resistant plate plates to be made.
Further, described heat-insulation layer selects alumina silicate fiber felt as heat-insulation layer.
The method that under a kind of normal pressure of the present invention, coal-based carbon foam prepared by microwave heating, the method includes: prepare coal-based carbon Foam precursor, preparing coal-based carbon foams and come into being body and body of coming into being coal-based carbon foams carries out carbonization process, its feature exists In: include following operating procedure:
(1) presoma of coal-based carbon foam is prepared:
It is divided into the bituminous coal powder of 20.00%～45.00% to be broken to 60～200 mesh, as preparing coal dry ash free basis volatilization Base carbon foams powdery precursor, standby；
The coal-based carbon foam powdery precursor maybe will prepared, then through vitrinite's enriched substance that concentration and separation obtains, will It is as preparing coal-based carbon foam powdery precursor, standby；
Or coal-based carbon foam powdery precursor is joined in metal die, with forcing press, coal original washing powder shape presoma is carried out It is forced into 5～20MPa, makes coal-based carbon foam type shape presoma, standby；
(2) add hot preparation coal-based carbon foams to come into being body:
Described coal-based carbon foam powdery precursor or carbon foams type shape presoma are joined in quartz molds, utilizes silicon Acid aluminum fiber mat parcel quartz molds, then quartz molds is placed on support, the thermometric end of temperature thermocouple is inserted quartz mould In powdery precursor in tool or type shape carbon foams presoma, then intelligent temperature control instrument is arranged on 400 DEG C～500 DEG C, microwave The temperature signal that power governor records according to intelligent temperature control instrument, is automatically adjusted the power of microwave generator, with 5 DEG C/min～50 DEG C/min is warming up to 400 DEG C～500 DEG C, constant temperature 30～60 minutes, after constant temperature terminates, close microwave power supply, naturally cool to room temperature After, just obtain coal-based carbon foams and come into being body.
(3) body of coming into being coal-based carbon foams carries out carbonization process:
Body of being come into being by the coal-based carbon foam that step (2) obtains puts into retort, under the protection of noble gas, with 1 DEG C/ Min～5 DEG C/min is warming up to 950 DEG C～1050 DEG C, keeps constant temperature 30 minutes～60 minutes, naturally cools to room temperature, obtain coal Base carbon foams, the bulk density of described coal-based carbon foam and comprcssive strength are respectively at 0.10g/cm3～1.00g/cm3With 10MPa～ Between 40MPa.
Present invention additionally comprises graphitization processing: described graphitization processing is coal-based carbon bubble above-mentioned steps (3) obtained Foam puts into graphitizing furnace, under the protection of inert nitrogen gas, with 5 DEG C/min～10 DEG C/min be warming up to 2500 DEG C～ 3000 DEG C, keep constant temperature 30 minutes～180 minutes, naturally cool to room temperature, or control rate of temperature fall is by near for furnace temperature room temperature, i.e. Prepare graphitization coal-based carbon foam.
The invention have the advantage that the present invention provides heat system efficiently against the dependence conduction of heat as described in background for raw material Standby coal-based carbon foam come into being body time there is manufacturing cycle length, cost is high and carbon foams has macroscopic cracking even problem of Cracking.Main Show themselves in that
(1) it is greatly shortened and prepares coal-based carbon foam and come into being time of body, reduce energy consumption.
(2) structural integrity can be prepared and there is no the coal-based carbon foam of macroscopic cracking.
(3), for relatively relying on conduction of heat to provide heat to prepare coal-based carbon foam, microwave heating is utilized to prepare coal-based carbon bubble The porosity of coal-based carbon foam can be more effectively adjusted by foam.
Why producing above-mentioned good effect, be based primarily upon the mechanism of action of the method, it is embodied in:
It is the cardinal principle of microwave heating that one, ionic conduction and dipole rotate, and therefore adds thermal medium and has polarity and is Absorb the premise of microwave.Coal is the macromolecular mixture of a kind of complexity, has high polymer feature, and its aromatic proton periphery exists a large amount of Polarity aliphatic chain and functional group, therefore coal has the chemical basis absorbing microwave.
Two, microwave heating technique is different from traditional heating mode, and it is high by heated material internal dipole molecule Frequency moves back and forth, and produces " internal friction heat " and makes heated temperature of charge raise, is not necessary to any heat transfer process, just can make material Heating simultaneously, heat up simultaneously in inside and outside, firing rate is fast and uniform.Therefore, microwave heating is used to prepare coal-based carbon foam permissible Reach energy-conservation purpose, simultaneously because homogeneous temperature and presoma foams the most simultaneously, and then avoid the occurrence of foamed phenomenon layer by layer, Avoid overall carbon foams that macroscopic cracking or cracking occur.For preparing the cylinder coal-based carbon bubble of a diameter of 120mm, a length of 300mm Foam, prepared by the method (Patent No. ZL 2,012 1 0364942.9) utilizing pretreatment bituminous coal to prepare coal base graphitization carbon foams Coal-based carbon foam come into being body for up to 10～12 hours, and the method using this patent, prepare coal-based carbon foam and come into being The time of body only needs 1～3 hours.
The factor three, affecting coal-based carbon foam pore structure includes presoma character, blowing temperature, foamed time, intensification Speed.For relatively relying on heat exchange pattern to prepare coal-based carbon foam, microwave heating is prepared coal-based carbon foam and can more widened In the range of regulate heating rate, therefore can the bulk density of significantly more efficient regulation carbon foams.Utilize pretreatment bituminous coal system The method (Patent No. ZL 2,012 1 0364942.9) of standby coal base graphitization carbon foams prepares carbon foams, obtains carbon foams Body density can be at 0.3g/cm3～0.8g/cm3In the range of regulate, and according to the method for this patent, the bulk density of carbon foams can With at 0.1g/cm3～1.0g/cm3In the range of regulate.
The bulk density of the coal-based carbon foam made based on above-mentioned mechanism and comprcssive strength can respectively 0.10～ 1.00g/cm3With cutting in the range of 12MPa～40MPa.
Accompanying drawing explanation
Fig. 1 is the process chart that former pressure charring prepares carbon foams.
Fig. 2 is the structural representation of the device that coal-based carbon foam prepared by microwave heating under normal pressure of the present invention.
Fig. 3 is the stereoscan photograph that employing normal pressure microwave adds the pore structure of hot preparation coal-based carbon foam.
In figure: 1-microwave protection case, 2-heat-insulation layer, 3-quartz molds, 4-presoma, 5-microwave introduction channel, 6-support, 7-exhaustor, 8-temperature thermocouple, 9-temperature thermocouple installing hole, 10-exhaustor, 11-intelligent temperature control instrument, 12-microwave power Actuator, 13-microwave emitter.
Detailed description of the invention
The detailed description of the invention of the present invention is illustrated below in conjunction with accompanying drawing 2.
As shown in Figure 2, under a kind of normal pressure of the present invention, the device of coal-based carbon foam prepared by microwave heating, and its feature exists In: including microwave protection case 1, the support 6 being arranged in microwave protection case 1 and the quartz molds 3 being placed on support 6, described The outside of quartz molds 3 be provided with heat-insulation layer 2, heat-insulation layer 2 is provided with the steam vent 10 connected with quartz molds 3, described The top of microwave protection case 1 be provided with exhaustor 7 and temperature thermocouple installing hole 9, described temperature thermocouple installing hole 9 and row Pore 10 is correspondingly arranged, and installs temperature thermocouple for convenient, has microwave introduction channel 5 in the bottom of described support 6, micro- Wave producer 13 is placed in the bottom of microwave introduction channel 5, is provided with temperature thermocouple 8 on the top of described microwave protection case 1, should The thermometric end of temperature thermocouple 8 is positioned at the presoma in quartz molds 3, described temperature thermocouple 8 signal output part and intelligence The signal input part of energy temperature control instrument 11 is connected, and the signal output part of this intelligent temperature control instrument 11 is connected with microwave power actuator 12, Microwave power actuator 12 is connected with microwave generator 13, for according to temperature thermocouple measured value real-time monitoring microwave generator The power of 13.
The material of microwave protection case of the present invention and support is 304 corrosion resistant plates, and microwave protection case provides sky for material foaming Between, prevent microwave from leaking simultaneously, microwave protection upper box part panel sets two holes, and one is used for laying temperature thermocouple, another Hole is used for aerofluxus.
The microwave generation portion part of the present invention is microwave generator, produces microwave, heat to material after energising.
Temperature thermocouple uses E type thermoelectricity occasionally K-type thermocouple, for measuring the temperature of coal-based carbon foam precursor.
Quartz molds is used for filling foaming presoma, the shapes and sizes of quartz molds according to the shape of prepared carbon foams and Depending on size, the present invention uses cup-shaped quartz molds, its a size of internal diameter 125mm, high 400mm.
The material of heat-insulation layer is the insulation material of microwave, preferably alumina silicate fiber felt, before it act as coal-based carbon foam Drive body insulation, after preventing the heating of coal-based carbon foam precursor, cause the external temperature of coal-based carbon foam precursor due to heat radiation Reduce, set an aperture on the top of heat-insulation layer, for aerofluxus and insertion temperature thermocouple；
The method that under a kind of normal pressure of the present invention, coal-based carbon foam prepared by microwave heating, the method includes: prepare coal-based carbon Foam precursor, preparing coal-based carbon foams and come into being body and body of coming into being coal-based carbon foams carries out carbonization process, its feature exists In: include following operating procedure:
(1) presoma of coal-based carbon foam is prepared:
It is divided into the bituminous coal powder of 20.00%～45.00% to be broken to 60～200 mesh, as preparing coal dry ash free basis volatilization Base carbon foams powdery precursor, standby；
The coal-based carbon foam powdery precursor maybe will prepared, then through vitrinite's enriched substance that concentration and separation obtains, will It is as preparing coal-based carbon foam powdery precursor, standby；
Or coal-based carbon foam powdery precursor is joined in metal die, with forcing press, powdery precursor is pressurizeed To 5～20MPa, make the type shape presoma of coal-based carbon foam, standby；Can be regulated by the consistency of pressurization regulation presoma Prepare the bulk density of coal-based carbon foam；
(2) add hot preparation coal-based carbon foams to come into being body:
Described coal-based carbon foam powdery precursor or coal-based carbon foam type shape presoma are joined in quartz molds 3, Utilize alumina silicate fiber felt to wrap up quartz molds, as heat-insulation layer 2, then quartz molds 3 is put on the frame 6, by thermometric thermoelectricity Before even thermometric end inserts the coal-based carbon foam powdery precursor in quartz molds or coal-based carbon foam, type shape drives in body 4, then Intelligent temperature control instrument being arranged on 400 DEG C～500 DEG C, opens intelligent temperature control instrument 11, microwave power actuator is according to intelligent temperature control instrument The temperature signal recorded, is automatically adjusted the power of microwave emitter, is warming up to 400 DEG C～500 with 5 DEG C/min～50 DEG C/min DEG C, constant temperature 30～60 minutes, after constant temperature terminates, close microwave power supply, after naturally cooling to room temperature, just obtain coal-based carbon foams Nascent body.
(3) body of coming into being coal-based carbon foams carries out carbonization process:
Body of being come into being by the coal-based carbon foam that step (2) obtains puts into retort, under the protection of noble gas, with 1 DEG C/ Min～5 DEG C/min is warming up to 950 DEG C～1050 DEG C, keeps constant temperature 30 minutes～60 minutes, naturally cools to room temperature, obtain coal Base carbon foams, the bulk density of described coal-based carbon foam and comprcssive strength are respectively at 0.10g/cm3～1.00g/cm3And 10MPa ～between 40MPa.
In order to improve some physical properties of coal-based carbon foam, present invention additionally comprises graphitization processing: described graphitization Process is that the coal-based carbon foam that above-mentioned steps (3) obtains is put into graphitization, under the protection of inert nitrogen gas, with 5 DEG C/min～10 DEG C/min is warming up to 2500 DEG C～3000 DEG C, keep constant temperature 30 minutes～180 minutes, naturally cool to room temperature, Or control rate of temperature fall is by near for furnace temperature room temperature, i.e. prepares graphitization coal-based carbon foam.Through graphitization processing, coal-based carbon foam Being converted into graphitization coal-based carbon foam, corresponding thermal conductivity is brought up to 60～70W/m K by 1～2W/m K.
Embodiment 1:
(1) presoma of coal-based carbon foam is prepared:
It is divided into the bituminous coal powder of 20.45% to be broken to 60～200 mesh, as preparing coal-based carbon foam powder dry ash free basis volatilization Shape presoma, standby；
The coal-based carbon foam powdery precursor maybe will prepared, then through vitrinite's enriched substance that concentration and separation obtains, will It is as preparing coal-based carbon foam powdery precursor, standby；
Or coal-based carbon foam powdery precursor is joined in metal die, with forcing press, powdery precursor is pressurizeed To 5～20MPa, make the type shape presoma of coal-based carbon foam, standby；
It is divided into the coking coal of 20.45% to be crushed to 60～200 mesh dry ash free basis volatilization, the coal dress after pulverizing 1500 grams Enter in metal die, use forcing press to be forced into 10MPa, obtain coal-based carbon foam type shape presoma；
(2) add hot preparation coal-based carbon foam to come into being body:
The type shape presoma of coal-based carbon foam step (1) obtained moves on to, in quartz molds, utilize alumina silicate fiber felt After quartz molds parcel heat-insulation layer, then the quartz molds of band heat-insulation layer is put on the support in microwave protection case, the row of opening The valve of trachea, arranges intelligent temperature control instrument, is added to 487 DEG C with the speed of 25 DEG C/min, constant temperature 30 minutes, after constant temperature terminates, closes Close microwave, be naturally cooling to room temperature, obtain carbon foams and come into being body；
(3) body of coming into being coal-based carbon foams carries out carbonization process:
Body of being come into being by the coal-based carbon foam that step (2) obtains is transferred in retort, adds with the heating rate of 2.5 DEG C/min Heat is to 1000 DEG C, and constant temperature 45 minutes, constant temperature terminates to automatically shut power off, and naturally cools to room temperature, obtains coal-based carbon foam；
(4) coal-based carbon foam is carried out graphitization processing
The coal-based carbon foam that step (3) obtains is transferred in graphitizing furnace, then with the ramp of 7.5 DEG C/min extremely 2800 DEG C, constant temperature 120 minutes, stop heating, naturally cool to room temperature, obtain graphitization coal-based carbon foam, its bulk density and Comprcssive strength is respectively 0.95g/cm3And 39.5MPa, thermal conductivity is 68m K.Normal pressure microwave adds hot preparation coal-based carbon foam The stereoscan photograph of pore structure is shown in Fig. 3.
The operating procedure of other embodiments is same as in Example 1, and design parameter change see table 1.
Table 1 embodiment list
Note: B represents bituminous coal；V represents vitrinite's enriched substance；60 mesh-200 mesh refer to 60 mesh sieve minus mesh and The combination grain material of the oversize of 200 mesh sieve；Blowing temperature: choose the maximum Ji Shi stream of coal used or vitrinite's enriched substance The temperature that dynamic degree is corresponding；
Embodiment 1-4, the kind embodying coal changes and the change of blowing temperature, to carbon foams bulk density and comprcssive strength Impact；Embodiment 5-8 embodies change and the change of blowing temperature of vitrinite enriched substance kind, to carbon foams bulk density and The impact of comprcssive strength；When embodiment 9-13 embodies with vitrinite's enriched substance for presoma, the change of mechanical mass pressurization is to charcoal Foam volume density and the impact of comprcssive strength；When embodiment 14-18 embodies with vitrinite's enriched substance for presoma, microwave heating The change of heating rate, on carbon foams bulk density and the impact of comprcssive strength；Embodiment 19-22 embodies and is enriched with vitrinite When thing is presoma, after microwave heating to blowing temperature, the change of constant temperature time (i.e. foamed time), to carbon foams bulk density Impact with comprcssive strength.
Present disclosure additionally applies for: after the regulation of blowing temperature, be also applied for the thermoplastic material such as Colophonium and resin Carbon foams is prepared for presoma.

Claims (5)

1. under a normal pressure, the device of coal-based carbon foam prepared by microwave heating, it is characterised in that: include microwave protection case, be arranged on Support in microwave protection case and the quartz molds being placed on support, be provided with heat-insulation layer in the outside of described quartz molds, Heat-insulation layer is provided with the steam vent connected with quartz molds, is provided with exhaustor and thermometric heat at the top of described microwave protection case Galvanic couple installing hole, has microwave introduction channel in the bottom of described support, and microwave generator is placed under microwave introduction channel Portion, is provided with temperature thermocouple on the top of described microwave protection case, and the thermometric end of this temperature thermocouple is positioned in quartz molds Presoma in, described temperature thermocouple signal output part is connected with the signal input part of intelligent temperature control instrument, this intelligent temperature control The signal output part of instrument is connected with microwave power actuator, and microwave power actuator is connected with microwave generator, for according to survey The power of warm galvanic couple measured value real-time monitoring microwave generator.
Under normal pressure the most according to claim 1, the device of coal-based carbon foam prepared by microwave heating, it is characterised in that: described Microwave protection case and support use 304 corrosion resistant plate plates to be made.
Normal pressure microwave the most according to claim 1 adds the device of hot preparation coal-based carbon foam, it is characterised in that: described guarantor Temperature layer selects alumina silicate fiber felt as heat-insulation layer.
4. the method that under normal pressure, coal-based carbon foam prepared by microwave heating, the method includes: prepare the forerunner of coal-based carbon foam Body, prepare coal-based carbon foams and come into being body and body of coming into being coal-based carbon foams carries out carbonization process, it is characterised in that: include with Lower operating procedure:
(1) presoma of coal-based carbon foam is prepared:
It is divided into the bituminous coal powder of 20.00%～45.00% to be broken to 60～200 mesh, as preparing coal-based carbon dry ash free basis volatilization Foam powdery precursor, standby；
The coal-based carbon foam powdery precursor maybe will prepared, then through vitrinite's enriched substance that concentration and separation obtains, made For preparing the shape presoma of coal-based carbon foam powder, standby；
Or coal-based carbon foam powdery precursor is joined in metal die, with forcing press, coal-based carbon foam powdery precursor is entered Row is forced into 5～20MPa, makes coal-based carbon foam type shape presoma, standby；
(2) add hot preparation coal-based carbon foams to come into being body:
Described coal-based carbon foam powdery precursor or coal-based carbon foam type shape presoma are joined in quartz molds, utilizes silicon Acid aluminum fiber mat parcel quartz molds, then quartz molds is placed on support, the thermometric end of temperature thermocouple is inserted quartz mould In coal-based carbon foam powdery precursor in tool or coal-based carbon foam type shape presoma, then intelligent temperature control instrument is arranged on 400 DEG C～500 DEG C, the temperature signal that microwave power actuator records according to intelligent temperature control instrument, be automatically adjusted the merit of microwave generator Rate, is warming up to 400 DEG C～500 DEG C with 5 DEG C/min～50 DEG C/min, constant temperature 30～60 minutes, after constant temperature terminates, closes microwave electricity Source, after naturally cooling to room temperature, just obtains coal-based carbon foams and comes into being body.
(3) body of coming into being coal-based carbon foams carries out carbonization process:
Body of being come into being by the carbon foams that step (2) obtains puts into retort, under the protection of noble gas, with 1 DEG C/min～5 DEG C/min is warming up to 950 DEG C～1050 DEG C, keeps constant temperature 30 minutes～60 minutes, naturally cools to room temperature, obtains coal-based carbon bubble Foam, the bulk density of described coal-based carbon foam and comprcssive strength are respectively at 0.10g/cm3～1.00g/cm3With 10MPa～40MPa Between.
The method that under normal pressure the most according to claim 4, coal-based carbon foam prepared by microwave heating, it is characterised in that: also include Graphitization processing: described graphitization processing is that the coal-based carbon foam that step (3) obtains is put into graphitizing furnace, at indifferent gas Under the protection of body nitrogen, it is warming up to 2500 DEG C～3000 DEG C with 5 DEG C/min～10 DEG C/min, keeps constant temperature 30 minutes～180 Minute, naturally cool to room temperature, or control rate of temperature fall is by near for furnace temperature room temperature, obtains graphitization coal-based carbon foam.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111547703A (en) * 2020-05-22 2020-08-18 太原理工大学 Method for preparing coal-based foam carbon based on normal-pressure self-foaming

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344130A (en) * 2010-08-05 2012-02-08 常州碳元科技发展有限公司 High heat dispersion graphite material and manufacturing method thereof
CN102502575A (en) * 2011-10-24 2012-06-20 上海理工大学 Method for preparing carbon foam by using foaming agent
CN102530916A (en) * 2011-12-31 2012-07-04 上海大学 Preparation method of coal-based carbon foam
CN102849723A (en) * 2012-09-27 2013-01-02 辽宁科技大学 Preparation method of coal-based carbon foam from pre-treated bituminous coal

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344130A (en) * 2010-08-05 2012-02-08 常州碳元科技发展有限公司 High heat dispersion graphite material and manufacturing method thereof
CN102502575A (en) * 2011-10-24 2012-06-20 上海理工大学 Method for preparing carbon foam by using foaming agent
CN102530916A (en) * 2011-12-31 2012-07-04 上海大学 Preparation method of coal-based carbon foam
CN102849723A (en) * 2012-09-27 2013-01-02 辽宁科技大学 Preparation method of coal-based carbon foam from pre-treated bituminous coal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111547703A (en) * 2020-05-22 2020-08-18 太原理工大学 Method for preparing coal-based foam carbon based on normal-pressure self-foaming

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