CN110475919A - The manufacturing method of Porous carbon fiber plate and the manufacturing method of Porous carbon electrode - Google Patents
The manufacturing method of Porous carbon fiber plate and the manufacturing method of Porous carbon electrode Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Inert Electrodes (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
It is an object of the present invention to provide a kind of manufacturing method for the Porous carbon fiber plate that manufacturing cost is relatively low and manufacture efficiency is high, and used the manufacturing method of the Porous carbon electrode of the Porous carbon fiber plate.The manufacturing method of Porous carbon fiber plate of the invention, has: by the Electrospun of the solution dissolved with ashless coal, in the process of substrate surface felted accumulation microfibre；The process for heating the microfibre deposit obtained in above-mentioned accumulation process.As above-mentioned accumulation process, can have: the process of Mixture Density Networks and solvent；From the above-mentioned coal in the slurry obtained via above-mentioned mixed processes, make the process for the ingredient dissolution for dissolving in above-mentioned solvent；By the above-mentioned slurry after being dissolved out via above-mentioned dissolution process, the process for being separated into the liquid component containing solvent soluble ingredient and solvent insoluble component.The manufacturing method of Porous carbon electrode of the invention, has the Porous carbon fiber plate that will be manufactured according to the manufacturing method of the Porous carbon fiber plate, the process for being configured to electrode.
Description
Technical field
The present invention relates to the manufacturing methods of the manufacturing method of Porous carbon fiber plate and Porous carbon electrode.
Background technique
As the manufacturing method with gas and the Porous carbon fiber plate of the fluid diffusion of liquid, it is known that will
Short carbon fiber mixes the method forming felted and making with binder substance.In the manufacturer of existing Porous carbon fiber plate
In method, since it is desired that being formed by binder substance, so there are rooms for improvement for its manufacture efficiency.
As the manufacturing method for not needing molding Porous carbon fiber plate, proposition has fibrous carbon made of making Electrospun
The method of change (referring to No. 2011/070893 Japanese Unexamined Patent Publication 2011-157668 bulletin, International Publication No. bulletin).Existing
In electrical spinning method, to asphalt series substance supply preheating gas carry out spinning, or to containing can Electrospun polymer substance and
The constituent of organic compound and transition metal carries out spinning.
In the manufacturing method of the Porous carbon fiber plate carried out like this by existing Electrospun, needed in carbon raw material
Substance other than special material and carbon.Therefore, in the manufacture of the Porous carbon fiber plate carried out based on existing Electrospun
In method, there are rooms for improvement in terms of manufacturing cost.
[advanced technical literature]
[patent document]
[patent document 1] Japanese Unexamined Patent Publication 2011-157668 bulletin
No. 2011/070893 bulletin of [patent document 2] International Publication No.
Summary of the invention
The present invention is based on above-mentioned such situations to form, it is intended that it is relatively low to provide a kind of manufacturing cost, and manufactures
The manufacturing method of high-efficient Porous carbon fiber plate, and the system of the Porous carbon electrode using the Porous carbon fiber plate
Make method.
The invention done for solving the above subject is a kind of manufacturing method of Porous carbon fiber plate, has: logical
The Electrospun of the solution dissolved with ashless coal is crossed, on the surface of the substrate the process of felted accumulation microfibre；Heating is by above-mentioned accumulation
The process for the microfibre deposit that process obtains.
In the manufacturing method of the Porous carbon fiber plate, use ashless coal as carbon raw material.Ashless coal is less expensive,
And there is excellent Electrospun, do not need the substance other than carbon.In addition, in the manufacturing method of the Porous carbon fiber plate
In, it just can be with high-specific surface area by Electrospun without implementing the processing of molding etc. based on the graphitization that ashless coal is excellent
It is readily derived the Porous carbon fiber of microfibre shape.Therefore, the manufacturing method of the Porous carbon fiber plate, manufacturing cost
It is relatively low, and manufacture efficiency is high.
As above-mentioned accumulation process, wherein can have following process: the process of Mixture Density Networks and solvent；From via above-mentioned mixing
Make the process for the ingredient dissolution for dissolving in above-mentioned solvent in above-mentioned coal in the slurry that process obtains；It will be molten in above-mentioned dissolution process
Above-mentioned pulp separation after out at the liquid component containing solvent soluble ingredient and solvent insoluble component process.So by making
Coal to solvent extraction is used as ashless coal, can further increase manufacture efficiency, and can reduce manufacturing cost.
The content of the voltage of adjustable Electrospun or the ashless coal in above-mentioned solution, being averaged for the carbon fiber made are straight
Diameter is 0.5 μm or more, 5 μm or less.So by the way that the average diameter of obtained carbon fiber to be adjusted in above range, thus
Fiber moderately tangles each other when Electrospun, and fluid diffusion improves.
It is the manufacturing method of Porous carbon electrode, having will pass through for solving another invention made of the above subject
The process that the Porous carbon fiber plate that the manufacturing method of the Porous carbon fiber plate is fabricated is configured to electrode.
In the manufacturing method of the Porous carbon electrode, because to the manufacturing method by the Porous carbon fiber plate
The Porous carbon fiber plate being fabricated is formed and forms electrode, thus can with relatively low manufacturing cost and efficiently
Manufacture to rate the electrode with fluid diffusion.
As described above, the manufacturing method of Porous carbon fiber plate of the invention and use the Porous carbon fiber plate
Porous carbon electrode manufacturing method, manufacturing cost is relatively low, and manufacture efficiency is high.
Detailed description of the invention
Fig. 1 is the outline process for indicating the manufacturing method of Porous carbon fiber plate of an embodiment of the invention
Figure.
Fig. 2 is the general flowchart of the accumulation process of Fig. 1.
Fig. 3 is the schematical skeleton diagram for indicating Electrospun portion.
Fig. 4 is the optical microscope photograph of the Porous carbon fiber plate of embodiment 1.
Fig. 5 is the electron scanning micrograph of the carbon fiber of the Porous carbon fiber plate of embodiment 1.
Fig. 6 is the figure for indicating the pore diameter distribution of the Porous carbon fiber plate of embodiment 1.
Specific embodiment
Hereinafter, the manufacturing method of manufacturing method and Porous carbon electrode for Porous carbon fiber plate of the invention
One embodiment is illustrated.
(manufacturing method of Porous carbon fiber plate)
The manufacturing method of the Porous carbon fiber plate, as shown in Figure 1, mainly having accumulation process S1 and heating process
S2.The manufacturing method of the Porous carbon fiber plate, for example, can by mainly have coal supply unit, solvent supply unit, mixing unit,
The manufacturing device progress in heating portion, dissolution portion, separation unit, Electrospun portion and heating part.
[accumulation process]
In accumulation process S1, by the Electrospun of the solution dissolved with ashless coal, felted accumulation is fine on the surface of the substrate
Fiber.Accumulation process S1 has the first mixed processes S11, dissolution process S12, solid-liquid separation process S13, evaporation as shown in Figure 2
Separation process S14, the second mixed processes S15 and electrospinning wire process S16.
The first mixed processes of < >
Mixture Density Networks and solvent in the first mixed processes S11.First mixed processes S11, such as pass through coal supply unit, molten
Agent supply unit and mixing unit carry out.
(coal supply unit)
Coal is supplied to mixing unit by coal supply unit.As coal supply unit, it is able to use the normal pressure used under normal pressure state
Hopper, the well known coal scuttle of pressurization hopper used under normal pressure state and pressurized state etc..
The coal supplied from coal supply unit is the coal of the raw material as ashless coal.Various qualities are able to use as above-mentioned coal
Coal.It such as can be suitable for using the high bituminous coal of the extraction yield of ashless coal and more cheap low grade coal (ub-bituminous coal and lignite).Separately
It outside, is suitable for using by the coal of tiny crushing if being classified with granularity to coal.So-called herein " by coal of tiny crushing " meaning
It is the coal that the quality of coal of the granularity lower than 1mm is 80% or more relative to the ratio of the quality of coal totality.In addition, being supplied as from coal
The coal supplied to portion is also able to use lump coal.So-called herein " lump coal " means the quality of the coal of granularity 5mm or more relative to coal
The coal that the ratio of overall quality is 50% or more.Lump coal and the coal facies ratio by tiny crushing, the grain of the coal of undissolved solid
Degree is kept as greatly, therefore can make the aftermentioned separative efficiency in separation unit.Here, so-called " granularity (partial size) " refers to foundation
The value of the sieve test rule measurement of JIS-Z8815:1994.In addition, in the differentiation that the granularity based on coal carries out, such as can
Enough use the made of metal mesh screen of JIS-Z8801-1:2006 defined.
Lower limit of the carbon containing rate as above-mentioned low grade coal is preferably 70 mass %.On the other hand, as above-mentioned low-grade
The upper limit of the carbon of coal containing rate is preferably 85 mass %, more preferably 82 mass %.If the carbon of above-mentioned low grade coal is containing rate lower than upper
Lower limit is stated, then the dissolution rate of solvent soluble ingredient is likely to decrease.Conversely, if the carbon of above-mentioned low grade coal is higher than on above-mentioned containing rate
Limit, the then cost of the coal supplied are possible to increase.
In addition, as the coal supplied from coal supply unit to mixing unit, it also can be used and mix a small amount of solvent and slurried
Coal.By supplying the coal of slurried from coal supply unit to mixing unit, coal is easy to mix with solvent in mixing unit, can make coal
Quickly dissolve.But if when slurried the amount of solvent that mixes it is more, it is molten for being warming up to slurry in aftermentioned heating portion
The heat of temperature unnecessarily becomes larger out, therefore manufacturing cost is possible to increase.
(solvent supply unit)
Solvent is supplied to mixing unit by solvent supply unit.Above-mentioned solvent supply unit has the solvent tank of storage of solvent, from this
Solvent is supplied to mixing unit by solvent tank.The solvent supplied from above-mentioned solvent supply unit is being mixed with the coal supplied from coal supply unit
Conjunction portion is mixed.
The solvent supplied from solvent supply unit, as long as being just not particularly limited for coal can be dissolved, such as can be suitable for using
From the dinuclear aromatics of coal.This dinuclear aromatics, due to the molecular structure class of basic structure and coal
Seemingly, so the compatibility with coal is high, relatively high extraction yield can be obtained.As the dinuclear aromatics from coal, example
Methylnaphthalene oil, naphtalene oil when can such as enumerate destructive distillation coal and manufacture coke as the distilled oil of by-product oil.
The boiling point of above-mentioned solvent is not particularly limited, but for example as the boiling point under the normal pressure (0.1MPa) of above-mentioned solvent
Lower limit, preferably 180 DEG C, more preferably 230 DEG C.On the other hand, the upper limit as the boiling point under the normal pressure of above-mentioned solvent, preferably
It is 300 DEG C, more preferably 280 DEG C.If the boiling point of above-mentioned solvent is lower than above-mentioned lower limit, solvent is readily volatilized, it is therefore possible to
The adjustment of the mixing ratio of coal and solvent in slurry and peace preservation association become difficult.Conversely, if the boiling point of above-mentioned solvent is higher than above-mentioned
The upper limit, then the separation of solvent soluble ingredient and solvent is difficult, it is possible to which the rate of recovery of solvent can reduce.
(mixing unit)
The coal that mixing unit mixing is supplied from coal supply unit and the solvent supplied from solvent supply unit.
Preparation vessel is able to use as above-mentioned mixing unit.Above-mentioned coal and solvent are fed into the preparation vessel via supply pipe
In.In above-mentioned preparation vessel, the coal being supplied to and solvent are mixed, and are modulated into slurry.In addition, above-mentioned preparation vessel has stirring
Machine is kept while slurry made of being stirred with blender, thus maintains the admixture of slurry.
The coal concentration in terms of anhydrous coal benchmark in slurry in preparation vessel, according to the suitable decision such as the type of solvent, but
As the lower limit of above-mentioned coal concentration, preferably 10 mass %, more preferably 13 mass %.On the other hand, as above-mentioned coal concentration
The upper limit, preferably 25 mass %, more preferably 20 mass %.If above-mentioned coal concentration is lower than above-mentioned lower limit, through dissolving out process
S12 and the amount of dissolution of solvent soluble ingredient dissolved out tail off relative to slurry treating capacity, and it is therefore possible to included in solution
The content of ashless coal is insufficient.Conversely, above-mentioned solvent soluble ingredient holds in a solvent if above-mentioned coal concentration is higher than the above-mentioned upper limit
Easily saturation, it is therefore possible to the reductions of the dissolution rate of above-mentioned solvent soluble ingredient.
< dissolves out process >
In dissolution process S12, in the coal in the slurry obtained from via above-mentioned first mixed processes S11, make solvable
It is dissolved out in the coal ingredient of solvent.Process S12 is dissolved out, such as is carried out by heating portion and dissolution portion.
(heating portion)
Heating portion makes slurry obtained in above-mentioned first mixed processes S11 heat up.
As heating portion, just it is not particularly limited as long as can heat up in the slurry that inside passes through, such as resistance can be enumerated
Heating type heating and load coil.In addition, its constituted mode of heating portion is also possible to heat up using heating agent, example
If being also configured to, there is the heating tube being arranged around the flow path for the slurry that inside passes through, supply and steam to the heating tube
The heating agent of gas, oil etc., so as to so that slurry heats up.
The temperature of slurry after the heating of heating portion, is suitable for decision according to used solvent, but as above-mentioned slurry
The lower limit of temperature, preferably 300 DEG C, more preferably 360 DEG C.On the other hand, the upper limit as the temperature of above-mentioned slurry, preferably
420 DEG C, more preferably 400 DEG C.If the temperature of above-mentioned slurry is lower than above-mentioned lower limit, it is likely that dissolution rate reduces.Conversely, on if
The temperature for stating slurry is higher than the above-mentioned upper limit, then solvent excessively gasifies, and it is therefore possible to be difficult to control the concentration of slurry.
In addition, the pressure as heating portion, is not particularly limited, can be normal pressure (0.1MPa).
(dissolution portion)
Dissolution portion makes to dissolve in molten in the coal from the slurry that above-mentioned mixing unit obtains and heats up via above-mentioned heating portion
The coal ingredient of agent dissolves out.
It is able to use extraction tank as dissolution portion, supplies the slurry after above-mentioned heating to the extraction tank.In above-mentioned extraction tank
In, the temperature and pressure of the slurry is kept on one side, dissolves out the coal ingredient for dissolving in solvent from coal.In addition, above-mentioned extraction
Take slot that there is blender.Slurry is stirred using the blender, above-mentioned dissolution can be promoted.
In addition, be not particularly limited as the dissolution time in dissolution portion, but from the extraction quantity and extraction of solvent soluble ingredient
From the perspective of taking efficiency, preferably 10 minutes or more, 70 minutes or less.
< solid-liquid separation process >
In solid-liquid separation process S13, by via the above-mentioned slurry after above-mentioned dissolution process S12 dissolution, it is separated into containing molten
The liquid component and solvent insoluble component of agent soluble ingredient.Solid-liquid separation process S13 can be carried out by separation unit.In addition, molten
Agent insoluble component refers to the ash content and insoluble coal mainly contained insoluble in extraction solvent, in addition to this also contains extraction solvent
Extracted residues.
(separation unit)
As the method for aforesaid liquid ingredient and solvent insoluble component in separation separation unit, such as it is able to use gravity and sinks
Drop method, filtration method, centrifugal separation use subsider, filter, whizzer respectively.
Hereinafter, being illustrated by taking settling methods as an example for separation method.So-called settling methods are in subsider
The separation method for settling solvent insoluble component using gravity and being separated by solid-liquid separation.When being separated by settling methods,
The liquid component of the soluble ingredient containing solvent accumulates in the top of subsider.The liquid component is carried out using filter device as needed
After filtering, it is discharged to aftermentioned spraying portion.On the other hand, solvent insoluble component is discharged from the lower part of separation unit.
In addition, slurry can be continuously fed into separation unit on one side when being separated by settling methods, on one side from heavy
The liquid component and solvent insoluble component of slot discharge soluble ingredient containing solvent drop.It is possible thereby to carry out at continuous separation of solid and liquid
Reason.
In separation unit maintain slurry time be not particularly limited, such as can for 30 minutes or more, 120 minutes with
Under, the sedimentation separation in separation unit is carried out within this time.In addition, as coal and when using lump coal, because sedimentation separation obtains
Efficient activity, so the time for maintaining slurry in separation unit can be shortened.
In addition, the temperature and pressure of the slurry after capable of heating up with heating portion is same as temperature and pressure in separation unit
Sample.
< evaporates separation process >
In evaporation separation process S14, steam solvent from the liquid component separated via above-mentioned solid-liquid separation process S13
Hair.It is separated by the evaporation of the solvent, ashless coal (HPC) can be obtained.The obtained ashless coal, ash content 5 mass % with
Lower or 3 mass % are hereinafter, be practically free of ash content, and moisture is then absolutely not.
As the method that evaporation separates above-mentioned solvent, it is able to use including the general way of distillation and evaporation (spray drying
Method etc.) separation method.By carrying out the separation of solvent from aforesaid liquid ingredient, can be obtained from aforesaid liquid ingredient substantially
Ashless coal without ash content.
On the other hand, make solvent evaporation separation from above-mentioned solvent insoluble component, extract residue can be obtained.Although extract residue is not
Display softening meltbility, but be detached from containing oxygen functional group.Therefore, extract residue is as mixed coal in use, the mixed coal will not be hindered to be wrapped
The softening meltbility of the other coals contained.Therefore, which can use as a part of the mixed coal of such as coke raw material.Separately
Outside, extract residue is same as general coal, can also be used as fuel utilization.
The second mixed processes of < >
In the second mixed processes S15, the ashless coal obtained via above-mentioned evaporation separation process S14 is dissolved in solvent.
By the dissolution of the ashless coal, the solution dissolved with ashless coal can be obtained.
As the solvent for dissolving ashless coal, as long as ashless coal dissolution is just not particularly limited, with former containing oxygen atom or nitrogen
The organic compound of son is principal component.So by making the principal component of above-mentioned solvent containing the organic of oxygen atom or nitrogen-atoms
The compatibility of compound, solvent and ashless coal is high, is easy to improve the content of the ashless coal in the solution for carrying out Electrospun.Its result
It is that the yield of Porous carbon fiber increases, therefore the manufacturing cost of Porous carbon fiber plate can reduce.As such molten
Agent can enumerate pyridine (C5H5N), tetrahydrofuran (C4H8O), methylformamide ((CH3)2NCHO), N-Methyl pyrrolidone
(C5H9NO) etc..The wherein preferred high pyridine and tetrahydrofuran with ashless coal compatibility.In addition, having containing oxygen atom or nitrogen-atoms
Machine compound can be one kind, in addition can also mix two or more organic compounds.
The lower limit of the content of ashless coal as above-mentioned solution, preferably 20 mass %, more preferably 25 mass %.It is another
Aspect, the upper limit of the content of the ashless coal as above-mentioned solution, preferably 60 mass %, more preferably 50 mass %, further
Preferably 40 mass %.If the content of above-mentioned ashless coal is lower than above-mentioned lower limit, droplet treatment is easy when Electrospun, therefore aftermentioned
Electrospinning wire process S16 in be possible to be difficult to obtain microfibre.Conversely, if the content of above-mentioned ashless coal is higher than the above-mentioned upper limit,
The diameter of the microfibre then obtained by Electrospun is excessive, and it is therefore possible to the reductions of the specific surface area of Porous carbon fiber plate.
< electrospinning wire process >
In electrospinning wire process S16, Electrospun, In are carried out using the solution obtained in above-mentioned second mixed processes S15
Substrate surface felted accumulates microfibre.
Such as shown in Figure 3, Electrospun is carried out by the Electrospun portion with syringe 1 and substrate 2.Specifically,
Electrospun be by by above-mentioned solution be added syringe 1, between the nozzle 1a and substrate 2 of syringe 1 apply voltage E come into
Row.If between nozzle 1a and substrate 2 apply voltage E, accumulation the front end nozzle 1a droplet surface, it is mutually exclusive,
As coniform.If furthermore increasing voltage E, the repulsive force of charge is more than surface tension, then front end direction of the solution from nozzle 1a
Substrate 2 sprays.If the solution stream 3 sprayed is tiny, surface charge density becomes larger, therefore the repulsive force of charge increases, solution stream 3
It is further stretched.At this moment, the specific surface area of solution stream 3 sharply becomes larger, and thus solvent volatilizees, and spins out on the surface of substrate 2
Microfibre 4.Such Electrospun can make microfibre 4 with fairly simple device.In addition, nozzle 1a is 1 in Fig. 3
It is a, but can also have multiple nozzle 1a, while making more microfibres.
As aforesaid substrate 2, as long as conductive be just not particularly limited, it is able to use metal plate, metal foil, carbon base plate
Deng.
The lower limit of the internal diameter (nozzle inside diameter) of the front end of said nozzle 1a, preferably 0.2mm, more preferably 0.4mm.Separately
On the one hand, the upper limit as said nozzle internal diameter, preferably 0.7mm, more preferably 0.6mm.If said nozzle internal diameter is lower than upper
Lower limit is stated, then the microfibre 4 obtained attenuates, so becoming easily broken staple fiber.Therefore, it is possible to be difficult on 2 surface of substrate
Felted accumulates microfibre 4.Conversely, the diameter of obtained microfibre 4 becomes if said nozzle internal diameter is higher than the above-mentioned upper limit
Greatly, it is therefore possible to the reductions of the specific surface area of manufactured Porous carbon fiber plate.
As the lower limit of spinning spacing (front end of nozzle 1a is at a distance from substrate 2), preferably 10cm, more preferably
12cm.On the other hand, the upper limit as spinning spacing, preferably 20cm, more preferably 18cm.If spinning spacing is lower than under above-mentioned
Limit, then solvent is unable to fully volatilize, and Electrospun is possible to difficult.Conversely, what is obtained is micro- if spinning spacing is higher than the above-mentioned upper limit
Fine fibre 4 attenuates, so becoming easily broken staple fiber.Therefore, it is possible to be difficult to accumulate microfibre 4 in 2 surface felted of substrate.
As the lower limit of the applied voltage E between said nozzle 1a and substrate 2, preferably 10kV, more preferably 12kV.Separately
On the one hand, the upper limit as above-mentioned applied voltage E, preferably 30kV, more preferably 20kV.If above-mentioned applied voltage E is lower than upper
State lower limit, it is likely that can not stablize to form microfibre 4.Conversely, if above-mentioned applied voltage E is higher than the above-mentioned upper limit, gained
The distribution of the diameter of the microfibre 4 arrived is easy extension, therefore the Porous carbon fiber plate manufactured is possible to heterogeneity.
The lower limit of flow (output quantity of the solution from 1 nozzle 1a) as above-mentioned solution stream 3, preferably 1ml/h,
More preferably 1.5ml/h.On the other hand, the upper limit as the flow of above-mentioned solution stream 3, preferably 3ml/h, more preferably
2.5ml/h.If the flow of above-mentioned solution stream 3 is lower than above-mentioned lower limit, it is likely that can not stablize to form microfibre 4.Conversely, if
The flow of above-mentioned solution stream 3 is higher than the above-mentioned upper limit, then the diameter of obtained microfibre 4 becomes larger, and it is therefore possible to manufactured
Porous carbon fiber plate specific surface area reduce.In addition, the flow of above-mentioned solution stream 3 can be by nozzle inside diameter and additional
Voltage E is controlled.
The lower limit of average diameter as the microfibre 4 for being deposited in 2 surface of substrate, preferably 0.5 μm, more preferably
0.7μm.On the other hand, the upper limit as the average diameter of above-mentioned microfibre 4, preferably 5 μm, more preferably 3 μm.If above-mentioned
The average diameter of microfibre 4 is lower than above-mentioned lower limit, then microfibre 4 becomes easily broken staple fiber, and it is therefore possible to be difficult to
2 surface felted of substrate accumulates microfibre 4.Conversely, having can if the average diameter of above-mentioned microfibre 4 is higher than the above-mentioned upper limit
The specific surface area of Porous carbon fiber plate manufactured by energy reduces.In addition, from the viewpoint of controlling, above-mentioned microfibre
The applied voltage E that 4 average diameter mainly passes through Electrospun is controlled.In addition, the average diameter of above-mentioned microfibre 4 can
It is adjusted by nozzle inside diameter and spinning spacing.
In addition, felted is piled up in the microfibre 4 on 2 surface of substrate, it is stripped from substrate 2.In the Porous carbon fiber sheet
In the manufacturing method of material, using the Electrospun that ashless coal is excellent, microfibre 4 is not cut off, but continuously and randomly
Accumulation is on a substrate 2.Therefore, microfibre 4 moderately tangles, so even if such as without using binder substance, after removing
Also it is able to maintain that felted.In addition, in the manufacturing method of the Porous carbon fiber plate, it can be in the state for maintaining the felted
Under, the carbonization of microfibre 4 is carried out by aftermentioned heating process S2.
[heating process]
In heating process S2, the microfibre deposit obtained by above-mentioned accumulation process S1 is heated.This heating process S2
It can be carried out by heating part.
(heating part)
Heating part makes above-mentioned microfibre deposit by heating substantially to keep the appearance of its Set Status to carry out carbon
Change.By this carbonization, Porous carbon fiber plate can be obtained.
As above-mentioned heating part, such as be able to use well known electric furnace etc., microfibre deposit is inserted into heating part,
After being replaced to inside with inert gas, heated while being blown into inert gas into heating part, so as into
The carbonization of row microfibre deposit.As above-mentioned inert gas, be not particularly limited, such as nitrogen and argon can be enumerated etc..Its
In preferred cheap nitrogen.
As the lower limit of above-mentioned heating temperature, preferably 500 DEG C, more preferably 700 DEG C.On the other hand, add as above-mentioned
The upper limit of hot temperature, preferably 3000 DEG C, more preferably 2800 DEG C.If above-mentioned heating temperature is lower than above-mentioned lower limit, carbonization has
It may be insufficient.Conversely, improving the viewpoint with fuel consumption from the heat resistance of equipment if heating temperature is higher than the above-mentioned upper limit
It sets out, manufacturing cost is possible to rise.In addition, as heating rate, for example, can for 0.01 DEG C/min or more, 10 DEG C/min with
Under.
In addition, the lower limit as heating time, preferably 10 minutes, more preferably 20 minutes.On the other hand, as heating
The upper limit of time, preferably 10 hours, more preferably 8 hours.If heating temperature is lower than above-mentioned lower limit, carbonization is possible to not fill
Point.Conversely, the manufacture efficiency of Porous carbon fiber plate is likely to decrease if heating time is higher than the above-mentioned upper limit.
The present inventors recognize, the carbon fiber of the obtained Porous carbon fiber plate are constituted, mainly by aperture
10nm micropore below is constituted, and specific surface area is high.The mechanism for being formed with such micropore is not yet clear, but ashless coal is for example
Compared with coal tar pitch, oxygen is higher containing rate, and carbon is low containing rate.Therefore, ashless coal is considered the mixing as polycyclc aromatic compound
The flatness of object, molecule is low, and ring size is small, it is difficult to carry out molecularly oriented.That is, passing through Electrospun, solution in accumulation process S1
It is ejected from nozzle 1a, when solvent rapidly volatilizees, ashless coal condensation, but molecule is mutually laminated at random.In heating process S2, no
Such molecularly oriented occurs, but to maintain the state of random structure to be carbonized, therefore generate the carbon of Porous.In contrast,
In the high coal tar pitch of armaticity because its on one side formed molecule be parallel to each other stacking molecularly oriented while condense, recognize
For the relatively high carbon of crystallinity, the i.e. underdeveloped carbon fiber of micropore can be generated.
The upper limit of the oxygen containing rate of carbon fiber as composition Porous carbon fiber plate, preferably 0.6 mass %, more preferably
For 0.55 mass %.If the oxygen of above-mentioned carbon fiber is higher than the above-mentioned upper limit containing rate, it is likely that the intensity of carbon fiber is insufficient.
The lower limit of specific surface area as manufactured Porous carbon fiber plate, preferably 300m2/ g, more preferably
400m2/ g, further preferably 450m2/g.If above-mentioned specific surface area is lower than above-mentioned lower limit, it is likely that be difficult to as Porous
Materials'use.On the other hand, the upper limit as above-mentioned specific surface area, is not particularly limited, but usually 3000m2/ g or so.
The lower limit of the average diameter of carbon fiber as the resulting, preferably 0.5 μm, more preferably 0.7 μm.Another party
Face, the upper limit of the average diameter as above-mentioned carbon fiber, preferably 5 μm, more preferably 3 μm.If above-mentioned carbon fiber is average straight
Diameter is lower than above-mentioned lower limit, then carbon fiber becomes easily broken staple fiber, and it is therefore possible to be difficult to obtain the carbon fiber plate of felted.Instead
It, if the average diameter of above-mentioned carbon fiber is higher than the above-mentioned upper limit, it is likely that the ratio table of manufactured Porous carbon fiber plate
Area reduces.In addition, the average diameter of above-mentioned carbon fiber, is determined by the average diameter of microfibre 4, microfibre 4 is averaged
Diameter is mainly controlled by the content of the ashless coal in the applied voltage E or solution of Electrospun from the viewpoint of controlling
System.In addition, the average diameter of above-mentioned microfibre 4, can be also adjusted by nozzle inside diameter and spinning spacing.
[advantage]
In the manufacturing method of the Porous carbon fiber plate, used by carbon raw material of ashless coal.Ashless coal is less expensive
And there is excellent Electrospun, do not need the substance other than carbon.In addition, in the manufacturing method of the Porous carbon fiber plate
In, it can be easily with high ratio by Electrospun without implementing the processing of molding etc. based on the graphitization that ashless coal is excellent
Surface area obtains the Porous carbon fiber of microfibre shape.Therefore, the manufacturing method of the Porous carbon fiber plate, manufacturing cost
It is relatively low, and manufacture efficiency is high.
In addition, the coal of solvent extraction is used as ashless coal in the manufacturing method of the Porous carbon fiber plate, from
And manufacture efficiency can be further increased, and reduce manufacturing cost.
(manufacturing method of Porous carbon electrode)
The manufacturing method of the Porous carbon electrode has forming process.In above-mentioned forming process, shape porous via this
Matter carbon fiber plate manufacturing method manufacture Porous carbon fiber plate and as electrode.Thereby, it is possible to relatively low system
This is caused, expeditiously manufacture has the electrode of fluid diffusion.It as manufacturing process, is not particularly limited, such as can enumerate
The method being punched out for the Porous carbon fiber plate.
[other embodiments]
In addition, the present invention is not limited to above embodiment.
In the above-described embodiment, the manufacturing method as Porous carbon fiber plate manufactures nothing to by solvent extraction
The method of culm is illustrated, but the manufacturing method of ashless coal is not limited to this, such as is also able to use through coal and hydrogen supply
The Hybrid Heating of property solvent and the ashless coal manufactured.
In addition, in the above-described embodiment, as the manufacturing method of Porous carbon fiber plate, in evaporation separation process
After carrying out solvent extraction to ashless coal, the solution for dissolving ashless coal and carrying out Electrospun is modulated in the second mixed processes, but can also
So that the solvent of extraction ashless coal and the solvent for carrying out the solution of Electrospun are congener solvent, to omit evaporation separation work
Sequence and the second mixed processes.In this case, the liquid component obtained by solid-liquid separation process is able to use as Electrospun
Solution.
In the above-described embodiment, the manufacturing method as Porous carbon fiber plate, for the mixed of the first mixed processes
There is the composition of preparation vessel to be illustrated in conjunction portion, but not limited to this it constitutes, if it is possible to carry out the mixing of solvent and coal, then
It can be omitted preparation vessel.Such as above-mentioned mixing is completed in this case by pipeline blender, it also can be omitted preparation vessel,
As the composition for having pipeline blender between supply pipe and separation unit.Device used in such each process is constituted, not by upper
State embodiment restriction.
In addition, the purposes of the Porous carbon fiber plate manufactured by the manufacturing method of Porous carbon fiber plate, does not limit
In electrode, but the sheet material that the requirement such as adsorption material, catalyst base has Porous can be suitable for.
[embodiment]
Hereinafter, the present invention is described in more detail by embodiment, but the present invention is not limited by these embodiments.
[embodiment 1]
The ashless coal that preparation bituminous coal is manufactured through solvent extraction is as carbon raw material.The elemental analysis value of the ashless coal is in table 1
In be expressed as " ashless coal A ".In addition, preparing pyridine as solvent.
By the mixing of the ashless coal and solvent, the solution that ashless coal dissolution retains in solvent is modulated, is made in solution
The content of ashless coal is 39 mass %.
Using the solution, Electrospun is carried out with condition shown in table 2, microfibre is accumulated on aluminum foil substrate.From aluminium foil
After upper removing microfibre deposit, 900 DEG C are warming up to 3.3 DEG C/minute of heating rate, is carried out at heating in 30 minutes
It manages (carbonization), manufactures the Porous carbon fiber plate of embodiment 1.The optical microscopy of obtained Porous carbon fiber plate shines
Piece is shown in Fig. 4.
[embodiment 2]
Be ready to pass through obtained from the solvent extraction of bituminous coal from example 1 group at different ashless coals as carbon raw material.It should
The elemental analysis value of ashless coal is expressed as " ashless coal B " in table 1.Other than using the ashless coal, similarly to Example 1
The Porous carbon fiber plate of ground manufacture embodiment 2.
[comparative example 1]
Prepare the carbobitumen as manufactured by the tar incidentally generated during the high-temperature retorting of coal.The carbobitumen
Elemental analysis value is shown in table 1.Other than using the carbobitumen as carbon raw material, ratio is manufactured similarly to Example 1
Compared with the Porous carbon fiber plate of example 1.
[table 1]
In addition, oxygen amount means the component amount other than carbon, hydrogen, nitrogen and sulphur in table 1, it is to be subtracted from 100 mass %
The amount of the component amount of carbon, hydrogen, nitrogen and sulphur.
[table 2]
| Voltage | 14~18 | kV |
| Flow | 2 | ml/h |
| Spinning spacing | 15 | cm |
| Nozzle inside diameter | 0.48 | mm |
[evaluation method]
Measurement below is carried out for above-described embodiment 1,2 and comparative example 1.
<average fiber footpath>
By the average diameter (average fiber footpath) of scanning electron microscopy measurement carbon fiber.In measurement, scanning electron is measured
It is average to acquire it for arbitrary 10 fibre diameters in the microscopical visual field.The Porous carbon fiber of embodiment 1 is shown in Fig. 5
The electron scanning micrograph of the carbon fiber of sheet material.In addition, measurement result is shown in table 3.
< specific surface area >
Porous carbon fiber plate is measured using " BELSOR-max " of マ イ Network ロ ト ラ ッ Network ベ Le Co., Ltd.
Specific surface area.Measurement result is shown in table 3.
< broad pore distribution >
For the Porous carbon fiber plate of embodiment 1, the broad pore distribution of HK method measurement carbon fiber is used.Measurement result is aobvious
Show in Fig. 6.
[table 3]
As shown in Table 3, carbon material using the embodiment 1 and embodiment 2 of ashless coal compared with comparative example 1, large specific surface area.
In addition, it will be appreciated from fig. 6 that the carbon fiber of the Porous carbon fiber plate of embodiment 1 is mainly by aperture 10nm micropore structure below
At the Porous of each carbon fiber is high.In addition, as shown in Figure 5, carbon fiber is not switched off, but continuously and randomly gather,
The Porous carbon fiber plate of embodiment 1, even if being also able to maintain that this felted, and gas and liquid without using adhesive etc.
Fluid diffusion it is excellent.
In contrast, carbon material uses the comparative example 1 of coal tar pitch, it is considered that specific surface area is small, and pore is undeveloped.It therefore can
Know, according to using ashless coal as the manufacturing method of the Porous carbon fiber plate of carbon raw material, without the place for implementing molding etc.
Reason, just easily can obtain the Porous carbon fiber of microfibre shape by Electrospun with high-specific surface area.
[available in industry]
As described above, the manufacturing method of Porous carbon fiber plate of the invention and the Porous carbon fiber sheet has been used
The manufacturing method of the Porous carbon electrode of material, the manufacturing cost compared is low, and manufacture efficiency is high.
[symbol description]
S1 accumulation process
S2 heating process
The first mixed processes of S11
S12 dissolves out process
S13 solid-liquid separation process
S14 evaporates separation process
The second mixed processes of S15
S16 electrospinning wire process
1 syringe
1a nozzle
2 substrates
3 solution streams
4 microfibres
E voltage
Claims (4)
1. a kind of manufacturing method of Porous carbon fiber plate, has:
The process of microfibre is accumulated in substrate surface felted by the Electrospun of the solution dissolved with ashless coal；
The process for heating microfibre deposit obtained in above-mentioned accumulation process.
2. the manufacturing method of Porous carbon fiber plate according to claim 1, wherein as above-mentioned accumulation process, tool
It is standby:
The process of Mixture Density Networks and solvent；
From the above-mentioned coal in slurry obtained in above-mentioned mixed processes, make the process for the ingredient dissolution for dissolving in above-mentioned solvent；
By via the above-mentioned slurry after the dissolution of above-mentioned dissolution process, it is separated into liquid component and solvent containing solvent soluble ingredient
The process of insoluble component.
3. the manufacturing method of Porous carbon fiber plate according to claim 1, wherein so that obtained carbon fiber
Average diameter is 0.5 μm or more, 5 μm of modes below adjust the voltage of Electrospun or the content of the ashless coal in above-mentioned solution.
4. a kind of manufacturing method of Porous carbon electrode, wherein have by according to claim 1, claim 2 or claim
The process that the Porous carbon fiber plate that the manufacturing method of Porous carbon fiber plate described in 3 is fabricated is configured to electrode.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017076391A JP2018178284A (en) | 2017-04-07 | 2017-04-07 | Manufacturing method of porous carbon fiber sheet and manufacturing method of porous caron electrode |
| JP2017-076391 | 2017-04-07 | ||
| PCT/JP2018/004452 WO2018186018A1 (en) | 2017-04-07 | 2018-02-08 | Method of manufacturing porous carbon fiber sheet and method of manufacturing porous carbon electrode |
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| CN110475919A true CN110475919A (en) | 2019-11-19 |
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| JP (1) | JP2018178284A (en) |
| KR (1) | KR20190128737A (en) |
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| JP6767918B2 (en) * | 2017-04-19 | 2020-10-14 | 株式会社神戸製鋼所 | Method for producing composition for electric field spinning and porous carbon fiber |
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| KR20190128737A (en) | 2019-11-18 |
| JP2018178284A (en) | 2018-11-15 |
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