CN107949540A - The carbon precursor in plant material source - Google Patents
The carbon precursor in plant material source Download PDFInfo
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- CN107949540A CN107949540A CN201680045043.9A CN201680045043A CN107949540A CN 107949540 A CN107949540 A CN 107949540A CN 201680045043 A CN201680045043 A CN 201680045043A CN 107949540 A CN107949540 A CN 107949540A
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Abstract
The present invention relates to a kind of carbon precursor in plant material source, it is the carbon precursor being made of the mean cross-sectional dimension determined by sieve method for the small pieces of more than 4mm and below 35mm, wherein, more than length 5mm and the content of the fibrous material of below width 2mm is below 6 weight %.
Description
Technical field
The present invention relates to useful carbon in the manufacture for carbonaceous materials such as conductive material, catalyst carrier, activated carbon
Precursor and its manufacture method.
Background technology
Carbonaceous material is used for the various uses such as capacitor electrode, electrode for electrolysis, activated carbon, carrier, be from now on by
Expect field and the raw material further developed.In the past, these carbonaceous materials were by cocoanut shell, coal tar carbon, coal or oil
Pitch, furane resins or phenolic resin etc. are manufactured as raw material.In recent years, the use of fossil fuel resource is for the earth
Environmental effects, be additionally, since its reserve reduce caused by expensive reason, it is contemplated that be from now on use meeting
Become difficult.
Therefore, the carbonaceous material manufactured from natural material environment-friendly for the Earth attracts attention.But natural former material
Comprising the biogenic various metals for maintaining organism in material, by from the carbonaceous material of this natural material
In the case of electronic material, metal becomes impurity, produces electric fault, also, in the work as the filtering for water etc.
Property the adsorbent such as carbon in the case of, material and the metal of absorption react, and form water-soluble substances, and generation is discharged into water again
The problems such as middle.In addition, in the carbonization activation of natural material, metal can cause hole to form reaction acceleration, and porous may
Needed for proceeding to more than degree；In catalyst carrier, the catalyst metals supported and the foreign metal contained react,
Possibly using the particle diameter as target or catalyst-loaded component can not be formed.And then from the metallic element of natural material
Content is according to season, region and content is different, there is the problems such as being difficult to equalization as the raw material of industry.But and not too much
Carry out the technological development for the metal from natural material energetically to be removed.
A kind of method is provided in patent document 1, wherein the material of plant origin is carbonized at 800 DEG C~1400 DEG C
Afterwards, obtained carbide is purified using alkali as mineral acid as hydrochloric acid, sodium hydroxide.But come in plant
When the material of plant origin is carbonized with carbon chemical combination occurs for remaining metal ingredient in the material in source.Therefore, in this side
In method, the metal ingredient that chemical combination occurs in carbide with carbon can not be fully removed.In addition, in the above method, in order to remove with
Silicon after carbon compound, is excessively added hydrofluoric acid for silicon compound.But hydrofluoric acid is the high extremely toxic substance of corrosivity, and
It is insufficient for the removing effect of magnesium, calcium.Further, in the above method, there are metal in the material of each plant origin into
The problem of deviation, occurs for the content divided.
Patent document：Japanese Unexamined Patent Publication 2008-273816 publications.
The content of the invention
The technical problems to be solved by the invention
A kind of carbon precursor in the plant material source being sufficiently reduced it is an object of the invention to provide content of metallic element.
In addition, it is an object of the invention to provide a kind of carbon precursor, wherein carbon precursor is being impregnated in aqueous solutions of organic acids, is thus being reduced
In the demineralization of the content of metallic element in carbon precursor, the deviation of metallic element included in each small pieces of carbon precursor is formed
It is reduced.
Solve the means of technical problem
The inventors of the present invention, which are conceived in the fibrous material that plant material is included, contains substantial amounts of metallic element, it turns out that logical
Cross from plant material and remove fibrous material, the content of the metallic element in carbon precursor can be reduced.In addition, the inventors of the present invention send out
Existing, above-mentioned demineralization is occurred from the outside of small pieces towards inside, and the diameter of section of small pieces is bigger, then the removing speed of metallic element
Degree is slower, therefore in the case where forming the distribution width of the sectional dimension of small pieces of carbon precursor, different small of internal demineralization degree
Piece is mixed, and deviation is produced in the metal element content in carbon precursor.Based on these situations, the inventors of the present invention have found, if
It is to remove plant material to include the carbon precursor of fibrous material, mean cross-sectional dimension within the specific limits, then can solves
Problem is stated, so as to complete the present invention.
That is, the present invention includes following.
[1] carbon precursor in plant material source, it by the mean cross-sectional dimension determined by sieve method is more than 4mm that it, which is,
And the carbon precursor that the small pieces of below 35mm are formed, wherein, the content of the fibrous material of more than length 5mm and below width 2mm
For below 6 weight %.
[2] carbon precursor described in [1], wherein fibrous material derive from the surface part of plant material.
[3] carbon precursor described in [1] or [2], the wherein content of Metal Elements K relative to metallic element aluminium content it
Than for more than 150.
[4] [1]~[3] any one of them carbon precursor, wherein the sectional dimension comprising below 40 weight % for 40mm with
On small pieces.
[5] [1]~[4] any one of them carbon precursor, wherein the sectional dimension comprising below 35 weight % for 2.5mm with
Under small pieces.
[6] [1]~[5] any one of them carbon precursor, wherein plant material are cocoanut shells.
[7] carbide obtained by [1]~[6] any one of them carbon precursor.
[8] method, it is the manufacture method of carbon precursor, including：
1) the step of crushing plant material, and cutting the top layer for taking plant material；With
2) it will be crushed in step 1) and cut the step of having taken the plant material on top layer to carry out whole grain；
3) plant material obtained from step 2) removes the step of trickle material,
Above-mentioned steps 1) it is to be carried out by using the device for applying shearing force.
[9] method described in [8], wherein above-mentioned steps 1) and 2) carried out by using same apparatus.
Invention effect
For the present invention carbon precursor, due to eliminating the fibrous material containing substantial amounts of metallic element and nonmetalloid,
Therefore the raw material of carbonaceous material can be suitable as.In addition, the carbon precursor of the present invention is by with specific mean cross-sectional dimension
Small pieces are formed, therefore in above-mentioned demineralisation procedure, the deviation of the content of the metallic element of each carbon precursor reduces, metallic element
Content is reduced.Therefore, in the case of by the carbonization of the carbon precursor of the present invention, uniform carburized carbonaceous material can be obtained.
And then the content of the metallic element in carbon precursor reduces, thus when carbon precursor is carbonized, the redox of metallic element causes
The decomposition of carbon component be lowered, carbide can be manufactured with the good rate of recovery.
Embodiment
In the present invention, the carbon precursor in plant material source refers to the raw material of the manufacture for carbonaceous material, by the small of plant material
Piece is formed.As plant material, it is not particularly limited, cocoanut shell, coffee bean and rice hulls etc. can be enumerated.
Particularly, from obtained possibility, from the viewpoint of the reducing effect of metal element content, preferred cocoanut shell.Separately
Outside, cocoanut shell is mainly made of the part for being referred to as shell of dense structure, therefore can be suitable as carbon precursor.As coconut
Shell, is not particularly limited, can use Cocoa Cortex cocois radicis, palm kernel (パ ー system coconut) etc. cocoanut shell.Use the feelings of cocoanut shell
Under condition, preferably using by be generally also used as the raw material such as fuel, activated carbon, be referred to as the cocoanut shell of cocoanut shell small pieces and crush and obtain
Material.
Can be arbitrary coffee bean no matter the place of production of coffee bean, kind as coffee bean.Coffee bean can be extraction
Coffee bean before going out the coffee as beverage or the commonly referred to as coffee grounds being withdrawn as after the coffee of beverage
Extraction residue.
Small pieces for the carbon precursor for forming plant material source of the invention, the averga cross section ruler determined by sieve method
Very little (hereinafter referred to as mean cross-sectional dimension) is more than 4mm and below 35mm.Thus, in demineralisation procedure, the outside of each small pieces
Reduce with the deviation of the reduction amount of the metallic element in inner side, metallic element and nonmetallic member can be removed effectively from carbon precursor
Element.
In the present invention, mean cross-sectional dimension refers to, forms the average value of the sectional dimension of each small pieces of carbon precursor.Section
Size refers to, in screening, when small pieces pass through sieve, small pieces parallel in the section of sieve to measurable most long-diagonal into
Size in the case of row measure.In the present invention, mean cross-sectional dimension is determined by sieve method.As sieve method, as long as
The method that the small pieces of carbon precursor can be categorized as to required size, is not particularly limited.As what is used in sieve method
Sieve, can properly select according to the species for the carbon precursor sieved, such as can be using the size of opening portion
The combination of the sieve of 0.85mm, 1.7mm, 2.8mm, 4mm, 6.7mm, 9.5mm, 15mm, 20mm, 30mm, 40mm.As this sieve
The representational commercially available product of the combination of net, such as ア ズ ワ Application Co. Ltd. system stainless steel mesh etc. can be enumerated.In addition, by carbon
Precursor input sieve after, can manual vibrating screen panel, oscillator vibrating screen panel can also be used.As long as the time shaken
The time that carbon precursor can be fully sieved by each sieve, be not particularly limited, preferably carry out 0.1 minute~
30 minutes, further preferably carry out 0.5 minute~10 minutes.
Mean cross-sectional dimension is specifically carried out as follows definite.By sieve with opening size order from small to large, most lower
The opening size of the sieve in portion is arranged on for least way and receives on ware.Carbon precursor is put on the sieve of topmost, is carried out
Concussion.Measure receives the quality of each carbon precursor obtained on ware and each sieve.By each quality divided by put into screening in carbon before
The all-mass of body, obtains mass ratio.Here, for each mean cross-sectional dimension for the carbon precursor being sized, to receiving in ware
The opening size that obtained carbon precursor is denoted as the sieve of minimum is sieved, to carbon precursor remaining on each sieve, by opening for each sieve
Mouth size is denoted as X, is the average value [=(X of X and Y in the case that the opening size of the sieve of the upper level of the sieve is denoted as Y
+ Y)/2].Each mass ratio is multiplied with corresponding mean cross-sectional dimension, the carbon using their aggregate values as the present invention
The mean cross-sectional dimension of precursor.
In addition, in the present invention, the mean cross-sectional dimension of carbon precursor is preferably more than 4mm and below 35mm, more preferably 5mm
Above and below 30mm, more preferably more than 6mm and below 20mm.
Preferably, the content for the small pieces that the sectional dimension of carbon precursor of the invention is more than 40mm is below 40 weight %.
Thus, when the carbon precursor of the present invention is carried out demineralization, until the inside of carbon precursor can equably remove metallic element.
In addition, in most cases, sectional dimension is that the small pieces of below 2.5mm are crushed during plant material by dusting
Fibrous material.Therefore, from the viewpoint of metal element content is reduced, it is preferred that the section of carbon precursor of the invention
The content for the small pieces that size is below 2.5mm is below 35 weight %.
In the present invention, as long as the mean cross-sectional dimension that the shape for forming each small pieces of carbon precursor can be obtained as described above
For the shape of more than 4mm and below 35mm, it is not particularly limited, such as can is that granular, micro mist shape, threadiness etc. are various
Shape.Preferably, the full-size for forming each small pieces of the carbon precursor of the present invention is below 100mm, more preferably 50mm
Below.If full-size is below 100mm, in demineralisation procedure, aqueous solutions of organic acids can permeate well, can be effective
Ground carries out demineralization, is therefore preferred.Full-size refers to that the maximum of the size in the three-dimensional shape of small pieces, refers to from upper
In the perspective plane for just observing the small pieces for being placed in horizontal plane, the size in the case of being measured to measurable most long-diagonal.
In addition, in the carbon precursor of the present invention, the content of fibrous material is below 6 weight % with respect to 100 weight % of carbon precursor.
In the present invention, fibrous material refers to more than length 5mm and the following materials of width 2mm, its shape is not particularly limited, can be with
It is variously-shaped, such as further includes flat pattern, material that fibrous material deforms in crushing process etc..It is preferred that
, in carbon precursor of the invention, the content of the fibrous material of more than length 5mm and below width 2mm is relative to carbon precursor
100 weight % are below 5 weight %, more preferably below 4 weight %.Reduced in the state of carbon precursor above-mentioned fibrous material this
The foreign structure of sample, thus can not only reduce the metallic element of remaining, but also can improve the quality of carbon source materials.
In addition, in the fibrous material of plant material, in most cases, according to the species of each metallic element, its content is
Different, in general, the comparision contents of aluminium are few, the comparision contents of potassium are more.Therefore, the reduction of metal element content of the invention is utilized
Effect goes out effect not only for the few material exhibits of aluminium equal size, and also shows effect for the material more than potassium equal size,
It is preferable.In addition, in most cases, for carbon precursor, the content of the metallic element of each plant material used is different.From this
Kind viewpoint considers, in the present invention, no matter the content of the metallic element of each plant material, and the reduction for the metallic element of carbon precursor
Effect is shown, therefore uses the content of potassium relative to the ratio of the content of aluminium.In general, in the carbon precursor of the present invention, metal member
The content of plain potassium is relative to the content of metallic element aluminium than being preferably more than 150, being more preferably more than 200, more preferably
More than 250.If the content of Metal Elements K is more than 150 relative to the content ratio of metallic element aluminium, the metal in carbon precursor
The content of element and nonmetalloid is sufficiently reduced, therefore can be preferably used as being used for electronic unit, activated carbon, catalyst
With the raw material of the carbonaceous material of the various uses such as the porous bodies such as carrier.In the present invention, the measure of the content of metallic element can make
Carried out with fluorescent x-ray analyzer (such as Co., Ltd. リ ガ Network ZSX Primus μ).
For the carbon precursor of the present invention, in the case that the moisture content of plant material is 10% or so, bulk density is preferably
The scope of 0.4g/cc~0.63g/cc, 0.45g/cc~0.6g/cc, more preferably 0.5g/cc~0.55g/cc.If heap
Within the above range, then it is appropriate to form the mean cross-sectional dimension of the small pieces of carbon precursor to product density, therefore preferably.
The carbon precursor of the present invention can remove above-mentioned fibrous material to obtain from plant material.But above-mentioned threadiness
Material is sealed at the surface part of plant material, therefore in the case of for example being removed by handwork, can not be fully
Remove.Therefore, for the carbon precursor of the present invention, by using the device for applying shearing force, cut and take top layer, and the plant that will be crushed
Raw material carries out whole grain, it is possible thereby to manufacture.
Therefore, the invention further relates to the manufacture method of carbon precursor, it includes：
The step of 1) plant material is crushed, and cuts the top layer for taking plant material,
2) it will be crushed in step 1) and cut the step of taking the plant material on top layer to carry out whole grain, and
3) plant material obtained from step 2) removes the step of trickle material,
Above-mentioned steps 1) it is to be carried out by using the device for applying shearing force.
In the present invention, by using the device for applying shearing force, while plant material is crushed, it can cut and take plant
The top layer of raw material.
As the device of application shearing force, such as single-shaft crusher and double-shaft crusher can be enumerated.In the present invention, for
Single-shaft crusher and double-shaft crusher, the shearing force produced between rotating sword and fixed blade and between rotating sword is by plant
During raw material is crushed to required granularity (sectional dimension), the top layer for taking plant material can be cut, is therefore preferred.For example,
The form for being racked plant material using 2 jaws crushed, does not produce the jaw pressure of shearing force on the top layer of plant material
In device as broken machine, it is difficult to cut the top layer for taking plant material.
Plant material is crushed and cuts time on the top layer for taking plant material and is not particularly limited, the side dependent on implementation
The species of method, is preferably 1~120 minute, more preferably 3~100 minutes.If the time that cellulosic part is removed is in above-mentioned model
In enclosing, then it is appropriate to remove the time of cellulosic part, is preferable from the viewpoint of economy.
As atmosphere the step of carrying out removing cellulosic part, it is not particularly limited, it is different according to the method for implementation.This
In invention, remove cellulosic part the step of carried out usually in air atmosphere.
Plant material is crushed, and after cutting the top layer for taking plant material, in order to obtain defined granularity (sectional dimension)
Carbon precursor, carry out whole grain.Whole grain can be carried out by such as getting off：The plant material on top layer has been taken to put into by crushing and cutting
Unsanctioned raw material is again returned to broken plant by the sieve with regulation opening size, recycling by the raw material of the sieve
Raw material and the step of cut the top layer for taking plant material.The opening size of sieve can be fitted according to the size of required carbon precursor
Locality selection.
It is to carry out the plant material of crushing by being installed on the sieve of lower part as single-shaft crusher and double-shaft crusher
The type of discharge, preferably takes the big plant material of the opening size than sieve to top by rotating sword and repeats to receive powder
It is broken until become it is smaller than the opening size of sieve and from sieve discharge.As this single-shaft crusher, such as Ji can be used
Field makes made plastic breaker.
The manufacturing method of the present invention can usually carry out at room temperature, be not particularly limited, can be in 0 DEG C~40 DEG C of model
Enclose progress.
Plant material is crushed, remove the step of cellulosic part and/or whole grain step be preferably repeated 1 time~5 times,
More preferably it is repeated 1 time~3 times.
In general, fibrous material, the quilt that dusting occurs by crushing are further included by the plant material that whole grain step obtains
The trickle materials such as thin fine plant material.The fibrous material that dusting occurs contains substantial amounts of metallic element, therefore preferably
Remove trickle material.Therefore, the method for the present invention includes remove trickle material from the plant material obtained by whole grain step
Step.In the present invention, trickle material refers to, sectional dimension is preferably shorter than 1.3mm, is more preferably less than 2.25mm, is further preferred
Carbon precursor less than 3.4mm.
As the method for removing trickle material, it can enumerate and put into the carbon precursor after whole grain with defined open-mouth ruler
Very little sieve, after sieve is shaken, the method for remaining carbon precursor on recycling sieve.As sieve, such as can use above-mentioned
The sieve used in screening operation.After carbon precursor is put into sieve, sieve can be shaken manually, concussion can also be used
Machine shakes sieve.As long as the time that the time shaken can fully be sieved carbon precursor by sieve is i.e.
Can, it is not particularly limited, preferably carries out 0.1 minute~30 minutes, further preferably carries out 0.5 minute~10 minutes.
Obtained carbon precursor can be washed and/or dried as needed.
In addition, in the present invention, as needed, by the way that the carbon precursor obtained as described above is immersed in aqueous solutions of organic acids
In, can be into the demineralization for the content reduction for exercising metallic element.
The organic acid used in above-mentioned demineralization does not preferably include the element that phosphorus, sulphur, halogen etc. become impurity source.Organic acid is not
In the case of comprising elements such as phosphorus, sulphur, halogens, omit washing after demineralization and by remaining have the carbon precursor of organic acid into
In the case of row carbonization, it can also obtain being suitable as the carbide of carbon source materials, therefore be favourable.In addition, after use
The liquid waste processing of organic acid do not have to use special device, and can relatively easily carry out, therefore be favourable.
As the example of organic acid, saturated carboxylic acid, such as formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid, lemon can be enumerated
Acid etc.；Unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid etc.；Aromatic carboxylic acid, such as benzoic acid,
Phthalic acid, naphthoic acid etc..From the viewpoint of the corrosion caused by possibility, acidity is obtained and the influence for human body,
Preferably acetic acid, oxalic acid and citric acid.
For organic acid, the viewpoint such as the processing of solubility, discarded object from the metallic compound of dissolution, environment adaptability is examined
Consider, can be mixed with aqueous solution, used in the form of aqueous solutions of organic acids.As aqueous solution, water, Shui Heshui can be enumerated
Mixture of solubleness organic solvent etc..As water-miscible organic solvent, such as methanol, ethanol, propane diols, ethylene glycol can be enumerated
Deng alcohol.
As the sour concentration in aqueous solutions of organic acids, it is not particularly limited, can be adjusted according to the sour species used
Concentration uses.In the present invention, in general, on the basis of the total amount of aqueous solutions of organic acids, using the weight % of 0.001 weight %~20,
Organic sour water of the acid concentration of the scope of the weight % of the weight % of more preferably 0.01 weight %~18, further preferred 0.02 weight %~15
Solution.If acid concentration is in above range, the dissolution rate of appropriate metallic element and/or nonmetalloid can be obtained,
Therefore can with can be practical time carry out demineralization.In addition, the sour residual quantity in carbon precursor is reduced, therefore for system hereafter
The influence of product also reduces.
The pH of aqueous solutions of organic acids is preferably less than 3.5, more preferably less than 3.The pH of aqueous solutions of organic acids is not less than upper
In the case of stating value, dissolution velocity of the metallic element in aqueous solutions of organic acids will not reduce, and can remove effectively metal member
Element.
The temperature of aqueous solutions of organic acids when impregnating carbon precursor is not particularly limited, and is preferably 20 DEG C~98 DEG C, more preferably
For 25 DEG C~60 DEG C, more preferably 30 DEG C~40 DEG C of scope.If the temperature of aqueous solutions of organic acids when impregnating carbon precursor
In above range, then can suppress used in acid decomposition, can obtain with can be practical time can implement the metal of demineralization
The dissolution rate of element, is therefore preferred.Furthermore it is possible to carry out demineralization without using the device of Te Do, it is therefore preferred.Into
One step, in the present invention, demineralization can also be carried out at room temperature.From the viewpoint of never needing to heating unit and security, this
Kind situation is preferable.
In the present invention, during demineralization the renewal of aqueous solutions of organic acids can at least carry out 1 time.As aqueous solutions of organic acids
Update method, following methods can be enumerated：When aqueous solutions of organic acids is continuously added in carbon precursor, making its stop regulation
Between, extract the method while being impregnated；It is immersed in by carbon precursor in aqueous solutions of organic acids, when making as defined in its stop
Between, after carrying out de- liquid, aqueous solutions of organic acids is newly added, method that dipping-de- liquid is repeated etc..Furthermore it is possible to be will be organic
The method that aqueous acid all updates or the method for updating a part for aqueous solutions of organic acids.
As the time being immersed in carbon precursor in aqueous solutions of organic acids, can suitably be adjusted according to the acid used
Section.In the present invention, for dip time, from the viewpoint of economy and demineralization efficiency, when being usually 0.1~100 small, preferably
For 0.2~80 when small, more preferably 0.5~50 it is small when scope.
The weight of the carbon precursor of dipping can be according to the organic acid used relative to the ratio of the weight of aqueous solutions of organic acids
Species, concentration and temperature of aqueous solution etc. are suitably adjusted, be usually the weight % of 0.1 weight %~200, be preferably 1 weight %~
The scope of 150 weight %, more preferably the weight % of 1.5 weight %~120.If within the above range, dissolution is to aqueous solutions of organic acids
Metallic element be difficult to from aqueous solutions of organic acids separate out, be suppressed, be therefore preferred for adhering to again for carbon precursor.Separately
Outside, it is preferable from the viewpoint of economy if within the above range, volumetric efficiency is appropriate.
As the atmosphere for carrying out demineralization, it is not particularly limited, can be different according to the method used in dipping, preferably big
Carried out in gas atmosphere.
These operations can preferably be repeated 1 time~5 times, more preferably be repeated 1 time~3 times.Be repeated dipping-
In the case of de- liquid, it can usually be repeated 2 times~8 times, preferably be repeated 3 times~5 times.In the present invention, after demineralization,
Washing step and/or drying steps can be carried out as needed.
In addition, for the carbon precursor after demineralization, the average content of potassium be preferably below 680ppm, more preferably 650ppm with
Under, more preferably below 600ppm.In addition, for the carbon precursor after demineralization of the invention, the average content of calcium is preferably
Below 52ppm, more preferably below 50ppm, more preferably below 48ppm.In the present invention, the average content of metallic element
Refer to, the value that the content of the metallic element in each carbon precursor or carbide is averagely obtained, such as carbide
In metallic element average content, the carbon precursor that will have carried out demineralization processing all recycles, they are carbonized obtained carbonizations
Thing crushes, for obtaining the content of substance-measuring metallic element, it is hereby achieved that.
By the way that the carbon precursor of the present invention is burnt till, the carbide available for carbonaceous material can be obtained, which can
For various uses such as the porous bodies such as electronic unit, activated carbon, carriers for catalysts.
As the heating-up temperature in burning till, it is not particularly limited, can be carried out in 250 DEG C~1000 DEG C of scope.In mistake
In the case of high temperature, crystallization causes carbon skeleton upright and outspoken, is not preferred as the carbonaceous material for various electronic materials
's.In addition, in the case of too low temperature, the possibility that accumulation of heat is caught fire becomes higher, and the oxygen in air causes oxygen easily occurs
Change, exist and preserve the problem of security is lower.Burn till scope preferably at 270 DEG C~900 DEG C, more preferably at 280 DEG C~800 DEG C
Scope, further preferably 400~750 DEG C scope carry out.Burnt till in above range, the carbonaceous material obtained from suppression
It is preferable from the viewpoint of going bad caused by oxidation of material etc., ensuring storage stability.
In addition, as firing rate, it is not particularly limited, it is different according to heating means, it is preferably 1 DEG C/min~200
DEG C/min, more preferably 1 DEG C/min~100 DEG C/min.If firing rate is within the above range, it is condensed when being carbonized,
The rate of recovery of good carbonaceous material can be obtained, is therefore preferred.In addition, the working time of the machine used is appropriate
, therefore be preferable from the viewpoint of economy.
As the temperature controlled mode in burning till, can be warming up to quickly required temperature mode or
Temperature is temporarily maintained in 250~400 DEG C of scopes, is heated up again, is warming up to the mode of required temperature.It is temporary transient within the above range
The mode of temperature is maintained to contribute to that the recycling of carbonation rate, carbon density and carbonaceous material is easily condensed, improved during carbonization sometimes
Rate.
Retention time under the maximum temperature burnt till is not particularly limited, in general, can keep 10 minutes~300 minutes
Left and right, is kept for preferably 30 minutes~240 minutes or so.
As the atmosphere burnt till, it is not particularly limited, is carried out preferably in inert gas atmosphere, more preferably in nitrogen
Carried out in atmosphere.During being burnt till, the structure change and oxygenolysis of carbonaceous material caused by being aoxidized for the ease of avoidance
The reduction of the rate of recovery of carbonaceous material caused by growth encourage, the presence of oxidizing gas, i.e. oxygen are preferably below 1 volume %, are more excellent
Elect as below 0.5 volume %.
Inert gas flow when being burnt till is not particularly limited, and is usually the scope of the meter per second of 0.001 meter per second~1.
As the taking-out temperature after burning till, as long as do not caused the temperature aoxidized by oxygen in air, without spy
Do not limit, it is preferred that usually below 200 DEG C, be more preferably fetched into below 100 DEG C in air.
As process for calcining, it is not particularly limited, can is intermittent with the any-mode of continous way or hot outside
The any-mode of formula and internal heat type.
After manufacturing carbonaceous material, as needed, it is possible to implement burn till except metal step, pulverising step and/or further
Step.But by the method for the present invention, can be fully in the case of manufacturing carbide using the plant material of purifying
The metal ingredient of high local concentrations in purification step is removed, therefore can be omitted and further remove metal step.
The carbonaceous material obtained from the carbon precursor of the present invention can be preferred for electronic unit, activated carbon, catalyst and carry
The various uses such as the porous bodies such as body.
Hereinafter, the present invention is further illustrated by embodiment, but the present invention is not limited to the examples.
Embodiment
[mean cross-sectional dimension]
By the sieve of opening size 0.85mm, 1.7mm, 2.8mm, 4mm, 6.7mm, 9.5mm, 15mm, 20mm, 30mm, 40mm with
Opening size order from small to large, the opening size of sieve of foot are arranged on for least way and receive on ware.Most
Carbon precursor is put on the sieve on top, manually concussion 3 minutes.Hereafter, measure receives carbon precursor remaining on ware and each sieve
Quality, for each quality, obtains the ratio relative to the all-mass for putting into the carbon precursor in screening.Here, for being sieved
Each mean cross-sectional dimension for the carbon precursor divided, is 0.85mm to receiving the carbon precursor obtained in ware, for remaining on each sieve
Carbon precursor, is respectively 1.3mm [=(0.85+1.7)/2], 2.25mm [=(1.7+ according to the order of opening size from small to large
2.8)/2], 3.4mm [=(2.8+4)/2], 5.4mm [=(4+6.7)/2], 8.1mm [=(6.7+9.5)/2], 12.25mm [=
(9.5+15)/2], 17.5mm [=(15+20)/2], 25mm [=(20+30)/2], 35mm [=(30+40)/2], 60mm.With
On in the ratio relative to all-mass obtained, corresponding to the carbon precursor that will each be used in following embodiments and comparative example
Obtained value, is multiplied by corresponding mean cross-sectional dimension, using aggregate value as mean cross-sectional dimension by quality divided by its aggregate values.
[content of fibrous material]
Carbon precursor is added to rice polisher (Star イ ン バ ー De polished rice food for the emperor NR-E700), rotates carbon precursor, while mutually
Friction, thus removes cellulosic part.The weight of the carbon precursor recycled by this operation is reduced into part and is denoted as fibrous material
Content.
[content of metallic element]
The content of metallic element is evaluated using fluorescent x-ray analyzer (Co., Ltd. リ ガ Network ZSX Primus μ).
It should illustrate that for plant material, according to taking season etc., according to position in the content of metallic element there are deviation, according to
The intensity of metal existing forms (crystallinity) X-ray is different, therefore for the content of metallic element, with the metal shape in carbide
Into equal crystallinity mode be carbonized under following Carbonization Conditions after, for the metallic element in obtained carbide
With the content of nonmetalloid, x-ray fluorescence analysis is carried out, is thus determined.In addition, for the metallic element in carbon precursor
Content, for the content of the metallic element in the carbide obtained by the carbon precursor in following embodiment and comparative example, is denoted as
The content of metallic element in the carbide that the rate of recovery of the carbide calculates when being 100%.
In addition, the deviation of the metallic element in carbon precursor and carbide after demineralization is calculated by following formula：
The deviation of the content of metallic element=(maximum level-minimum content)/average content
In above-mentioned formula, average content is all to recycle the carbon precursor after demineralization, be carbonized in following Carbonization Conditions
Afterwards, carbide is crushed, be measured.For the average content of the metallic element in the carbon precursor after demineralization, carbide is denoted as
Metallic element of rate of recovery when being 100% in the carbide that calculates average content.In addition, maximum level and minimum content are,
Each 10g at 5 arbitrarily taken the carbon precursor after demineralization, after being carbonized under the Carbonization Conditions below each leisure, by each carbide
It is broken, it is measured, determines the maximum and minimum value of measured value at 5.For the metallic element in the carbon precursor after demineralization
Maximum level and minimum content, be denoted as the carbide rate of recovery for 100% when the carbide that calculates in metallic element maximum level
And minimum content.
[Carbonization Conditions]
Regenerant is added into crucible, using silver dollar サ ー モ KTF1100 stoves (internal diameter 70mm Φ), in the nitrogen of oxygen content 15ppm
Under the flow of gas air-flow 3L/ points (0.012 meter per second), 500 DEG C are warming up to 10 DEG C/minute, keep after sixty minutes, with 6 it is small when it is cold
But, taken out below 50 DEG C.
[bulk density]
Carbon precursor is put into until the 1000cc scales of 1000cc graduated cylinders, then from the matter of the gross mass and graduated cylinder of graduated cylinder and carbon precursor
The difference of amount, obtains the quality of carbon precursor, calculates the ratio relative to the 1000cc quality measured.5 this operations are carried out, will
Its average value is as bulk density.
Embodiment 1
Cocoanut shell (Philippine, Mindanao production) 3kg is put into single-shaft crusher, and (Jitian makes made plastic breaker
1005) in, crushed, while cut and take superficial layer.Then, it is passed to be installed on the diameter of the outlet of single-shaft crusher
The sieve of 8mm, thus recycles the complete cocoanut shell of whole grain (following, referred to as broken cocoanut shell).Then, for crushing cocoanut shell 3kg,
Method is determined according to above-mentioned mean cross-sectional dimension, is sieved, and determines mean cross-sectional dimension, while by mean cross-sectional dimension 3.4mm
The cocoanut shell 120g recycling of (on 2.8mm sieves) above, is impregnated in 0.04M aqueous citric acid solution 280g, while stirring at 95 DEG C
Mix while carry out 4 it is small when demineralization.It is then cooled to room temperature, carries out de- liquid by filtering, thus recycles cocoanut shell.After demineralization
Cocoanut shell (following, be known as demineralization cocoanut shell) under vacuum 1Torr at 80 DEG C it is dry 24 it is small when.By thus obtained demineralization
Cocoanut shell is carbonized according to above-mentioned Carbonization Conditions.
Embodiment 2
In embodiment 1, instead of the sieve of diameter 8mm, using the sieve of diameter 11.5mm, in addition, similarly to Example 1
Ground manufactures carbide.
Embodiment 3
In embodiment 1, instead of the sieve of diameter 8mm, using the sieve of diameter 14.5mm, in addition, similarly to Example 1
Ground manufactures carbide.
Embodiment 4
In embodiment 1, instead of the sieve of diameter 8mm, using the sieve of diameter 20mm, in addition, similarly to Example 1
Manufacture carbide.
Comparative example 1
In embodiment 1, instead of single-shaft crusher, double-shaft crusher (the remote rattan industry small Twin-shaft without sieve is used
Crusher) and broken cocoanut shell is not sieved and all used, in addition, carbon is manufactured similarly to Example 1
Compound.
Comparative example 2
In embodiment 1, instead of single-shaft crusher, double-shaft crusher (the remote rattan industry small Twin-shaft without sieve is used
Crusher) and using stainless steel mesh and peeler will remain attached to from double-shaft crusher recycle cocoanut shell fiber
Shape material separates and broken cocoanut shell is not sieved and all used, and in addition, makes similarly to Example 1
Make carbide.
Comparative example 3
In embodiment 1, instead of single-shaft crusher, double-shaft crusher (the remote rattan industry small Twin-shaft without sieve is used
Crusher) and 4 times the cocoanut shell of recycling input double-shaft crusher is crushed repeatedly, cut take superficial layer after, recycling
Operation and broken cocoanut shell is not sieved and is all used, in addition, manufacture carbon similarly to Example 1
Compound.
Comparative example 4
In embodiment 1, instead of single-shaft crusher, using jaw crusher (レ ッ チ ェ BB50), the broken of cocoanut shell is carried out
It is broken, but adhere to fibrous material on the top layer of broken cocoanut shell, have no that the appearance taken is cut in top layer face.Utilize jaw crusher
It is broken in, cocoanut shell is put into the pulverizing chamber that 2 jaws form V-shape, in fixed jaw and the driving jaw of elliptic motion
Between crushed in the form of racking.When carrying out this broken, for the top layer of cocoanut shell, can not produce single-shaft crusher this
The shearing force of sample, therefore the top layer of cocoanut shell can not be taken by cutting.
It is mass ratio for each mean cross-sectional dimension of broken cocoanut shell for being obtained in each embodiment and comparative example, average
Sectional dimension, granularity (sectional dimension) with more than 40mm broken cocoanut shell mass ratio, the grain with below 2.5mm
The mass ratio of broken cocoanut shell, the content of fibrous material and the bulk density of degree (sectional dimension) are shown in table 1.It is in addition, each
The broken cocoanut shell and the content of the metallic element of demineralization cocoanut shell obtained in embodiment and comparative example is shown in table 2 below.
From table 1 to table 3, for the carbon precursor of the present invention, the content of fibrous material is few, and with prescribed limit
Mean cross-sectional dimension, therefore compared with being not belonging to the carbon precursor of the present invention, the content of metallic element is low, in the case of demineralization, gold
The deviation for belonging to the content of element is small.
Claims (9)
1. the carbon precursor in plant material source, it by the mean cross-sectional dimension determined by sieve method is more than 4mm and 35mm that it, which is,
The carbon precursor that following small pieces are formed, wherein, the content of the fibrous material of more than length 5mm and below width 2mm is 6 weights
Measure below %.
2. carbon precursor according to claim 1, wherein, fibrous material derives from the surface part of plant material.
3. the carbon precursor according to claim 1 or 2, wherein the content of Metal Elements K is relative to metallic element aluminium
The ratio between content be more than 150.
4. according to claim 1 ~ 3 any one of them carbon precursor, wherein the sectional dimension comprising below 40 weight % for 40mm with
On small pieces.
5. according to claim 1 ~ 4 any one of them carbon precursor, wherein the sectional dimension comprising below 35 weight % is 2.5mm
Following small pieces.
6. according to claim 1 ~ 5 any one of them carbon precursor, wherein plant material is cocoanut shell.
7. the carbide obtained by claim 1 ~ 6 any one of them carbon precursor.
8. method, it is the manufacture method of carbon precursor, including：
1) the step of crushing plant material, and cutting the top layer for taking plant material；
2) it will be crushed in step 1) and cut the step of having taken the plant material on top layer to carry out whole grain；With
3) plant material obtained from step 2) removes the step of trickle material,
Above-mentioned steps 1) it is to be carried out by using the device for applying shearing force.
9. according to the method described in claim 8, wherein above-mentioned steps 1) and 2) carried out by using same apparatus.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2015154254 | 2015-08-04 | ||
| JP2015-154254 | 2015-08-04 | ||
| PCT/JP2016/070893 WO2017022449A1 (en) | 2015-08-04 | 2016-07-14 | Carbon precursor derived from plant material |
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| CN107949540A true CN107949540A (en) | 2018-04-20 |
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| JP (1) | JP6698658B2 (en) |
| CN (1) | CN107949540A (en) |
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| EP3650409A4 (en) * | 2017-07-06 | 2021-03-17 | Kuraray Co., Ltd. | Carbon material for negative electrode active material for non-aqueous electrolyte secondary batteries, non-aqueous electrolyte secondary battery negative electrode, non-aqueous electrolyte secondary battery, and carbon material production method |
| WO2019009333A1 (en) * | 2017-07-06 | 2019-01-10 | 株式会社クラレ | Carbon material for negative electrode active material for non-aqueous electrolyte secondary batteries, non-aqueous electrolyte secondary battery negative electrode, non-aqueous electrolyte secondary battery, and carbon material production method |
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| JPH0789707A (en) * | 1993-06-29 | 1995-04-04 | Yamahiro Toryo Kk | Continuous production of activated carbon or carbon ceramic |
| US20040192534A1 (en) * | 2000-09-29 | 2004-09-30 | Nixon Thomas Dwayne | Boron carbide based ceramic matrix composites |
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| CN104412425A (en) * | 2012-09-06 | 2015-03-11 | 株式会社吴羽 | Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same |
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| JPS531194A (en) * | 1976-06-25 | 1978-01-07 | Kyowa Hakko Kogyo Co Ltd | Granular activated carbon |
| JP3609953B2 (en) * | 1999-03-04 | 2005-01-12 | 株式会社栗本鐵工所 | Equipment for producing carbonized objects from combustible waste |
| JP3696535B2 (en) * | 2001-08-30 | 2005-09-21 | 環境工学株式会社 | Bamboo powder manufacturing method and manufacturing apparatus, dry distillation bamboo powder and dry distillation component manufacturing method and manufacturing apparatus |
| JP2007015907A (en) * | 2005-06-06 | 2007-01-25 | Ueda Holdings:Kk | Adsorbent charcoal, water-purifying agent, water-purifying sachet, water-purifying substrate and method for removing oil film |
| JP2011177656A (en) * | 2010-03-01 | 2011-09-15 | Aomori Prefectural Industrial Technology Research Center | Adsorptive material originated from tree branch and method for manufacturing the same |
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2016
- 2016-07-14 CN CN201680045043.9A patent/CN107949540A/en active Pending
- 2016-07-14 WO PCT/JP2016/070893 patent/WO2017022449A1/en active Application Filing
- 2016-07-14 JP JP2017532462A patent/JP6698658B2/en active Active
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2018
- 2018-02-01 PH PH12018500248A patent/PH12018500248A1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0789707A (en) * | 1993-06-29 | 1995-04-04 | Yamahiro Toryo Kk | Continuous production of activated carbon or carbon ceramic |
| US20040192534A1 (en) * | 2000-09-29 | 2004-09-30 | Nixon Thomas Dwayne | Boron carbide based ceramic matrix composites |
| JP5168585B2 (en) * | 2006-11-02 | 2013-03-21 | クラレケミカル株式会社 | Activated carbon and method for producing the same, non-aqueous polarizable electrode and electric double layer capacitor |
| CN101314925A (en) * | 2008-04-18 | 2008-12-03 | 中国科学院武汉岩土力学研究所 | Method of producing stalk composite fiber material for road |
| CN103311519A (en) * | 2012-03-07 | 2013-09-18 | 上海杉杉科技有限公司 | Composite hard carbon negative electrode material, and preparation method and application thereof |
| CN104412425A (en) * | 2012-09-06 | 2015-03-11 | 株式会社吴羽 | Carbonaceous material for negative electrodes of nonaqueous electrolyte secondary batteries, and method for producing same |
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| WO2017022449A1 (en) | 2017-02-09 |
| PH12018500248A1 (en) | 2018-08-13 |
| JP6698658B2 (en) | 2020-05-27 |
| JPWO2017022449A1 (en) | 2018-05-31 |
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