WO2015037583A1 - 炭素材料の製造方法、および炭素材料 - Google Patents
炭素材料の製造方法、および炭素材料 Download PDFInfo
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- WO2015037583A1 WO2015037583A1 PCT/JP2014/073806 JP2014073806W WO2015037583A1 WO 2015037583 A1 WO2015037583 A1 WO 2015037583A1 JP 2014073806 W JP2014073806 W JP 2014073806W WO 2015037583 A1 WO2015037583 A1 WO 2015037583A1
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- ashless coal
- coal
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- carbon material
- oxidation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
Definitions
- the present invention relates to a method for producing a carbon material, and more particularly to a method for producing a carbon material having a high purity and a high density used as a structural member, an electric / electronic material, a metal reducing material, and the like, and a carbon material. .
- High-density carbon materials are widely used as structural members and electrical / electronic materials because of their excellent heat resistance and chemical stability and electrical conductivity. Further, since carbon exhibits an action of reducing many metal oxides at a high temperature, it is also used as a metal reducing agent in refining of titanium and the like.
- High-density carbon materials can be produced by combining carbon components with high carbon content such as coke and carbonizing without melting and thermoplastic materials such as coal tar pitch. And the method of mixing and shaping
- Self-sintering is a property that allows molding without adding a binder component and carbonizes it while maintaining its shape by heat treatment.
- mesocarbon microbeads are known.
- carbon materials are required to have less impurities other than carbon (so-called ash), but since conventional carbon materials have a high impurity content, high-purity carbon materials are It was difficult to provide.
- ashless coal has high heat fluidity and has the property of melting at 200 to 300 ° C. regardless of the quality of the raw coal. It also has the property of expanding when heated to around 400 ° C. For this reason, carbonizing a molded body made of ashless charcoal causes foaming and expansion due to high temperature heating, so that the carbon material is cracked or chipped, or powdered to maintain the shape of the molded body. There is a problem that the carbon material cannot be formed or the density of the carbon material is lowered due to the porous structure.
- Patent Document 2 a ashless coal reforming technique
- self-sinterability is improved by heating ashless coal to adjust the volatile content to a predetermined range, and it does not expand even when carbonized, and there is no cracking, chipping or powdering. It is possible to provide a high-purity carbon material that retains its shape during molding.
- Patent Document 2 makes it possible to use ashless coal as a carbon raw material having self-sintering properties and achieve high purity of the carbon material, but there is room for improvement in density. there were. That is, when using ashless coal with reduced volatile content, the carbon material has low deformability against carbonization shrinkage caused by evaporation of moisture and the like when carbonized (heated at high temperature), so a void is formed in the carbon material, There was a problem that the density was low.
- the present invention has been made by paying attention to the above-described circumstances, and its object is to provide a method for producing a carbon material having high purity and high density, and a carbon material having high purity and high density. Is to provide.
- the method for producing a carbon material according to the present invention that has solved the above problems comprises an oxidation step of oxidizing ashless coal, an oxidized ashless coal obtained in the oxidation step, and an ashless coal that is not oxidized.
- An oxygen increase rate of the oxidized ashless coal obtained in the oxidation step is from 2.0 to 2.0, and a carbonization step in which the molded body obtained in the molding step is carbonized.
- the mixing ratio of the oxidized ashless coal in the molding step is 60 to 95 parts by mass with respect to a total of 100 parts by mass of the oxidized ashless coal and the non-oxidized ashless coal. There is a gist to be.
- the oxidation is air oxidation, and that the oxidation is performed at a temperature of 150 ° C. or higher and lower than the ignition point of the ashless coal.
- the present invention also includes a carbon material obtained by carbonizing a molded body obtained by mixing oxidized ashless coal (oxidized ashless coal) and non-oxidized ashless coal, the oxidized ashless coal.
- the oxygen increase rate is 2.0 to 10.0%, and the ratio of the oxidized ashless coal in the molded body is 100 parts by mass in total of the oxidized ashless coal and the non-oxidized ashless coal.
- a carbon material having a gist of 60 to 95 parts by mass is also included.
- a carbon material having high purity and high density can be produced at low cost.
- a carbon material having high purity and high density can be provided by using a carbon raw material in which oxidized ashless coal obtained by subjecting ashless coal to oxidation treatment is blended under predetermined conditions.
- FIG. 1 is a flowchart for explaining an example of a manufacturing process of ashless coal.
- FIG. 2 is a flowchart for explaining an example of the manufacturing process of the carbon material according to the present invention.
- the present inventors have intensively studied to provide a high-purity and high-density carbon material using ashless coal as a carbon raw material.
- ashless coal has high softening and melting properties and expandability, so ashless coal alone has high purity and high density. No carbon material can be produced.
- the volatile content of ashless coal is adjusted as in Patent Document 2, although softening meltability and expansibility are improved, voids are formed during the carbonization treatment, and sufficient densification cannot be achieved. Problems arise.
- the present inventors examined a carbon raw material that can achieve high densification of the carbon material while reducing the softening meltability and expansibility of ashless coal and suppressing voids during the carbonization treatment.
- oxidized ashless coal obtained by subjecting ashless coal to oxidation treatment is the main component (aggregate component), and further, ashless coal that has not been oxidized (blended ashless coal) is blended as a binder component. It has been found that it is effective to use a mixed carbon raw material. In other words, it was found that softening meltability and expansibility can be improved by oxidizing ashless coal.
- oxidized ashless coal is inferior in self-sintering properties, a molded body formed only from oxidized ashless coal is very brittle, and when it is carbonized, cracks develop and partly collapses and pulverizes. There was a problem.
- an additive serving as a binder for improving the bonding between oxidized ashless coal particles was examined.
- an additive such as pitch which has been conventionally used as a binder, is blended, the above-mentioned problems such as cracking and pulverization are improved, but the carbonization shrinkage ratio is higher than that of oxidized ashless coal, and the residual carbon ratio is high. Since it is low, voids remain in the carbon material, and there is a problem that the ash content derived from the binder component is mixed and the purity is lowered.
- unmodified ashless coal that does not oxidize, that is, as-produced ashless coal that has not been subjected to modification treatment such as oxidation treatment
- unmodified ashless coal When blended as a binder component, the unmodified ashless coal softens and melts to function as a binder that binds oxidized ashless coal particles, improving the above-mentioned problems such as cracking and pulverization, and molding It was found that the body shape can be maintained.
- the carbonization shrinkage rate of unmodified ashless coal is almost the same as that of oxidized ashless coal, formation of voids due to carbonization shrinkage is suppressed, and the density can be increased.
- a mixed carbon raw material in which oxidized ashless coal obtained by subjecting ashless coal to oxidation treatment and non-oxidized ashless coal is used as the carbon raw material.
- Ashless coal refers to coal that has a very low ash concentration of residual inorganic substances (silicic acid, alumina, iron oxide, lime, magnesia, alkali metal, etc.) when coal is ashed by heating at 815 ° C. Specifically, an ash concentration of 5000 ppm or less (based on mass), preferably 2000 ppm or less, is referred to as ashless coal.
- ashless coal has no moisture and exhibits higher thermal fluidity than raw coal.
- ashless coal having such properties can be used, and the production method is not particularly limited, and various known production methods can be adopted.
- ashless coal can be manufactured through the following steps S1 to S3 (see FIG. 1), but the following ashless coal manufacturing steps (S1 to S3) can be changed as appropriate, and various processing steps can be performed as necessary. May be added.
- a coal pulverization step for pulverizing raw coal and unnecessary items such as dust are removed before or after each step within a range that does not adversely affect each step.
- Other steps such as a removing step and a drying step of drying the obtained ashless coal may be included.
- the slurry heating step (S1) is a process in which coal and an aromatic solvent are mixed to prepare a slurry, and heat treatment is performed to extract a coal component into the aromatic solvent.
- the type of coal as a raw material (hereinafter also referred to as “raw coal”) is not particularly limited. From the economical point of view, non-thin coal with almost no softening and melting properties, or low quality coal such as brown coal, lignite, sub-bituminous coal, sub-bituminous coal, etc. Is preferably used.
- the aromatic solvent is not particularly limited as long as it has a property of dissolving coal.
- the aromatic solvent having such properties include monocyclic aromatic compounds such as benzene, toluene and xylene, and bicyclic aromatic compounds such as naphthalene, methylnaphthalene, dimethylnaphthalene and trimethylnaphthalene.
- the bicyclic aromatic compound includes other naphthalenes having an aliphatic side chain, and biphenyl and alkylbenzene having a long-chain aliphatic side chain.
- a bicyclic aromatic compound which is a non-hydrogen donating solvent is preferable.
- the non-hydrogen-donating solvent is a coal derivative that is a solvent mainly composed of a bicyclic aromatic and purified mainly from a carbonization product of coal.
- the reason why the non-hydrogen-donating solvent is preferable is that the non-hydrogen-donating solvent is stable even in a heated state and has excellent affinity with coal. This is because it is a solvent that can be easily recovered by a method such as distillation, and the recovered solvent can be recycled.
- the boiling point of the aromatic solvent is too low, the required pressure in the heat extraction or in the separation step (S2) described later increases, and loss due to volatilization increases in the step of recovering the aromatic solvent.
- the recovery rate of group solvents is reduced. Furthermore, the extraction rate in heat extraction is also reduced.
- the boiling point of the aromatic solvent is preferably 180 to 330 ° C.
- the coal concentration with respect to the aromatic solvent is not particularly limited. Although depending on the type of raw material coal, if the coal concentration relative to the aromatic solvent is low, the proportion of the coal component extracted into the aromatic solvent is less than the amount of the aromatic solvent, which is not economical. On the other hand, the higher the coal concentration, the better. However, if the coal concentration is too high, the viscosity of the slurry becomes high, and it becomes difficult to move the slurry and separate the liquid component and the solid component in the separation step (S2).
- the coal concentration is preferably in the range of 10 to 50% by mass, more preferably in the range of 20 to 35% by mass on the basis of dry coal.
- the slurry heating temperature is preferably 350 ° C. or higher, more preferably 380 ° C. or higher, and preferably 420 ° C. or lower.
- the heating time is not particularly limited, but if the extraction time is long, the thermal decomposition reaction proceeds too much, the radical polymerization reaction proceeds, and the extraction rate decreases.
- it is the said heating temperature, Preferably it is 120 minutes or less, More preferably, it is 60 minutes or less, More preferably, it is 30 minutes or less, Preferably it is more than 0 minute, Preferably it is 10 minutes or more.
- the lower limit of the temperature at the time of cooling is preferably 300 ° C. or higher. If it cools to less than 300 degreeC, the dissolving power of an aromatic solvent will fall, the reprecipitation of the coal component once extracted will occur, and the yield of ashless coal will fall.
- Heat extraction is preferably performed in a non-oxidizing atmosphere. Specifically, it is preferably performed in the presence of an inert gas such as nitrogen. This is because contact with oxygen during heating extraction is dangerous because it may ignite, and the cost increases when hydrogen is used.
- an inert gas such as nitrogen
- the pressure in the heat extraction depends on the temperature at the time of heat extraction and the vapor pressure of the aromatic solvent used, but when the pressure is lower than the vapor pressure of the aromatic solvent, the aromatic solvent volatilizes and enters the liquid phase. It is not trapped and cannot be extracted. On the other hand, if the pressure is too high, the cost of the equipment and the operating cost increase, which is not economical.
- a preferable pressure is approximately 1.0 to 2.0 MPa.
- the separation step (S2) is a step of separating the slurry heat-treated in the slurry heating step (S1) into a liquid component and a solid component.
- the liquid component is a solution containing a coal component extracted into an aromatic solvent.
- the solid component is a slurry containing ash and insoluble coal insoluble in an aromatic solvent.
- the method for separating the slurry into a liquid component and a solid component in the separation step (S2) is not particularly limited, and a known separation method such as a filtration method, a centrifugal separation method, or a gravity sedimentation method can be employed.
- a gravity sedimentation method that allows continuous operation of a fluid and is suitable for a large amount of processing at a low cost.
- a liquid component hereinafter also referred to as “supernatant liquid” that is a solution containing coal components extracted into an aromatic solvent
- a solvent from the lower part of the gravity sedimentation tank, a solvent. It is possible to obtain a solid component (hereinafter also referred to as “solid content concentrate”) which is a slurry containing ash and coal insoluble in water.
- the ashless coal acquisition step (S3) is a step of separating the aromatic solvent from the supernatant to acquire ashless coal having an extremely low ash concentration.
- the method for separating the aromatic solvent from the supernatant is not particularly limited, and a general distillation method, evaporation method (spray drying method, etc.), etc. can be used.
- the aromatic solvent separated and recovered can be used repeatedly. Ash liquid can be obtained from the supernatant by separating and collecting the aromatic solvent.
- by-product coal in which the ash is concentrated by separating the aromatic solvent from the solid concentrate may be produced (by-product coal acquisition step).
- the method for separating the aromatic solvent from the solid concentrate can use a general distillation method or evaporation method as in the ashless coal acquisition step (S3) for acquiring ashless coal from the liquid component. .
- An oxidation process (C1) is a process which oxidizes ashless coal, Comprising: Oxidized ashless coal is obtained.
- unmodified ashless coal and oxidized ashless coal obtained in the oxidation step are mixed to form a carbon raw material (hereinafter sometimes referred to as “mixed carbon raw material”).
- mixed carbon raw material a carbon raw material
- a part of the prepared ashless coal may be oxidized in the oxidation step (C1) to produce oxidized ashless coal, and the remaining unmodified ashless coal may be mixed with oxidized ashless coal.
- the oxygen content of the ashless coal before and after the oxidation treatment is measured based on JIS M8813 (oxygen content calculation method), and the oxygen increase rate of the oxidized ashless coal (oxidation-free). It is necessary to set the oxygen content of the ash coal—the oxygen content of the ashless coal before the oxidation) within the range of 2.0% to 10.0%.
- the oxygen increase rate of oxidized ashless coal is less than 2.0%, the ashless coal is not sufficiently modified, so melting and expansion occurs during carbonization, the shape is deformed, and the carbon material is porous It becomes a body and the density becomes low.
- the oxygen increase rate of oxidized ashless coal exceeds 10.0%, the carbonized shrinkage rate when carbonized decreases, resulting in a difference in carbonized shrinkage rate between oxidized ashless coal and unmodified ashless coal. Thus, voids are formed and the desired high density cannot be achieved.
- the oxygen increase rate of the oxidized ashless coal is preferably 4.0% or more, more preferably 6.0% or more, preferably 9.0% or less, more preferably 8.5% or less.
- the oxidation method of ashless coal is not particularly limited, and may be oxidized so that the oxygen increase rate of ashless coal falls within a predetermined range.
- Examples of the oxidation method include oxidation in an oxidizing atmosphere such as oxygen, ozone, nitrogen dioxide, and air, preferably air oxidation using oxygen in the air as an oxidizing agent. Further, from the viewpoint of cost, oxidation in an air atmosphere is more preferable.
- the oxidation temperature (temperature maintained during oxidation) may be appropriately adjusted so that a desired oxygen increase rate is obtained. If the oxidation temperature is low, the ashless coal may be insufficiently oxidized, and the above-described reforming effect may not be sufficiently exhibited. Further, when the oxidation temperature is low, the time required to achieve a desired oxygen increase rate becomes long, and the productivity deteriorates. On the other hand, if the oxidation temperature becomes too high, the oxidation rate becomes too fast, making it difficult to control the degree of oxidation of ashless coal.
- the oxidation temperature is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, preferably less than the ignition point of ashless coal, more preferably 350 ° C. or lower.
- the oxidation time (retention time at a predetermined temperature) may be adjusted as appropriate so as to obtain a desired oxygen increase rate. If the oxidation time is short, the ashless coal may become insufficiently oxidized. On the other hand, if the oxidation time is long, the ashless coal is excessively oxidized, and voids are generated as described above, which may cause a decrease in density.
- the preferred oxidation time in the above temperature range is 0.5 hours or more, more preferably 1 hour or more, preferably 6 hours or less, more preferably 3 hours or less. What is necessary is just to cool to room temperature after oxidation.
- the particle size of the ashless coal to be oxidized is not particularly limited. If the particle size of the ashless coal is too large, the inside of the ashless coal is not sufficiently oxidized, and there is a risk of melting or the like when carbonized. On the other hand, if the particle size of ashless coal is too small, the handleability deteriorates.
- the average particle diameter of the ashless coal is preferably 3 mm or less, more preferably 1 mm or less, preferably 0.2 mm or more, more preferably 0.3 mm or more. Further, the maximum particle size of the ashless coal to be oxidized is preferably 3 mm or less, more preferably 1 mm or less, and still more preferably 0.5 mm or less, from the viewpoint of promoting oxidation.
- ashless coal obtained in the oxidation step and unmodified ashless coal are mixed and molded into a desired shape to obtain a molded body.
- mixing of ashless coal carbon raw material mixing step: C2
- molding molding step: C3
- the carbon raw material mixing step is a step of obtaining the carbon raw material (mixed carbon raw material) by mixing the oxidized ashless coal obtained in the oxidation step (C1) and the unmodified ashless coal.
- the carbon raw material mixing step is a step of obtaining the carbon raw material (mixed carbon raw material) by mixing the oxidized ashless coal obtained in the oxidation step (C1) and the unmodified ashless coal.
- the ratio of oxidized ashless coal in the mixed carbon raw material is 60 to 95 parts by mass with respect to 100 parts by mass of oxidized ashless coal and unmodified ashless coal in total. There is. If the mixing ratio of oxidized ashless coal becomes high and the ratio of unmodified ashless coal becomes low, the binder effect of unmodified ashless coal will not be fully exhibited, so it becomes brittle and cracks when carbonized etc. Progresses and part of it collapses and becomes pulverized, resulting in poor shape retention.
- the mixing ratio of oxidized ashless coal is preferably 80 to 90 parts by mass.
- the average particle size of the unmodified ashless coal mixed with the oxidized ashless coal is not particularly limited, but if the average particle size is too large, the mixed state in the molded body will be uneven and the effect will be sufficiently exerted. It may not be done. On the other hand, if the average particle size is too small, the handleability may deteriorate.
- the average particle size of the unmodified ashless coal is preferably 1.0 mm or less, more preferably 0.5 mm or less, and preferably 0.1 mm or more, more preferably 0.2 mm or more. Moreover, since the maximum particle size of unmodified ashless coal may be too large, non-uniformity may occur in the mixed state in the molded body, and is preferably 1.0 mm or less, more preferably 0.5 mm or less. is there.
- the average particle size of the unmodified ashless coal smaller than the average particle size of the oxidized ashless coal because the above effect of the present invention is further improved.
- the mixing method of the oxidized ashless coal and the unmodified ashless coal is not particularly limited, and a known method capable of obtaining uniform mixing may be adopted, for example, a mixer, a kneader, a single screw mixer, a twin screw Or the like can be used.
- the forming step is a step of obtaining a molded body by forming the mixed carbon raw material obtained in the carbon raw material mixing step (C2) into a desired shape.
- the method for forming the molded body is not particularly limited. For example, in addition to a method using a double roll (double roll) molding machine using a flat roll, a double roll molding machine having an almond pocket, a single axis Any method such as a press or roller type molding machine, a method using an extrusion molding machine, or press molding using a mold can be adopted.
- the mixed carbon raw material may be formed by cold forming performed at around room temperature, but hot forming performed by heating is preferable.
- the unmodified ashless coal plastically deforms and fills the voids between the oxidized ashless coal particles, A further compacted molded body can be obtained. Therefore, a carbon material with higher density can be obtained by carbonizing the compacted compact.
- the hot molding temperature is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, preferably 450 ° C. or lower, more preferably 300 ° C. or lower.
- the molding pressure is not particularly limited, and known conditions may be adopted. For example, the molding pressure is about 0.5 to 3 ton / cm 2 .
- a carbonization process is a process of carbonizing the molded object obtained at the formation process, and acquiring a carbon material.
- ⁇ Carbonization of the molded body is performed by heating in a non-oxidizing atmosphere. Specifically, the molded body is charged into an arbitrary heating apparatus such as an electric furnace, the inside is replaced with a non-oxidizing gas, and then heated while blowing the non-oxidizing gas into the apparatus. Unmodified ashless coal is softened, melted and resolidified by heating, and carbonized with oxidized ashless coal.
- the heating conditions may be appropriately set depending on the required characteristics of the product, and are not particularly limited, but are preferably performed by heating at a temperature of 500 ° C. or higher, more preferably 700 ° C. or higher for about 0.5 to 10 hours.
- the temperature raising rate up to the heating temperature is not particularly limited, and the temperature may be usually raised at a rate of about 0.01 ° C. to 1 ° C./min.
- the upper limit of the heating temperature is not particularly limited, and may be appropriately determined according to the equipment and the like, and may be, for example, preferably 3000 ° C. or less, more preferably 2600 ° C. or less.
- the carbonization atmosphere is preferably a non-oxidizing gas atmosphere in order to prevent deterioration due to coal oxidation.
- the type of non-oxidizing gas is not particularly limited as long as it contains no oxidizing gas in order to advance carbonization in a state in which the oxidation of the carbon material is suppressed, but an inert gas is preferable, and nitrogen gas is more preferable. .
- the carbon material thus obtained has a higher purity and higher density than conventionally known carbon materials.
- the high ash content is preferably 5000 ppm or less, more preferably 3000 ppm or less, and the density is preferably 1.50 g / ml or more, more preferably 1.60 g / ml or more, and even more preferably 1 .High density of 70 g / ml or more.
- the carbon material of the present invention is free from cracks and cracks, and retains the shape of the molded body before carbonization without being expanded, deformed, or pulverized.
- the carbon material of the present invention obtained by carbonizing a molded product mixed and molded with oxidized ashless coal (60 to 95 parts by mass with respect to a total of 100 parts by mass of charcoal) has higher purity than conventional carbon materials, and High density.
- a slurry was prepared by mixing 4 kg (20 kg) of aromatic solvent (1-methylnaphthalene (manufactured by Nippon Steel Chemical Co., Ltd.)) with 5 kg of raw coal (bituminous coal). This slurry was pressurized with 1.2 MPa of nitrogen and heat-treated (heat extraction) in an autoclave with an internal volume of 30 liters at 370 ° C. for 1 hour.
- the obtained supernatant was further filtered (a stainless mesh filter having an opening of 1 ⁇ m) to obtain an ashless coal solution.
- the ashless coal (carbon raw material A1) was produced by separating and recovering the aromatic solvent from the ashless coal solution by distillation.
- Carbon raw material mixing step: C2 Table 1 shows the ashless coal (carbon raw material A2) obtained by pulverizing the ashless coal (carbon raw material A1) so as to pass through a sieve having an opening of 0.5 mm, and the oxidized ashless coal (carbon raw material B).
- a mixed carbon raw material (carbon raw material C) was obtained by mixing at a predetermined ratio (“oxidized ashless coal blending ratio” in Table 1).
- Example No. 6 The apparent specific gravity (density) of the compact and the carbon material was measured. The results are shown in Table 1. In this example, if the density is higher than that of the conventional example (sample No. 6), the density is determined to be acceptable (preferable), and preferably the density of the carbon material is 1.50 g / ml or more (good). The case where it was preferably 1.60 g / ml or more was judged as excellent (().
- sample Nos. Satisfying the predetermined requirements of the present invention As shown in Table 1, sample Nos. Satisfying the predetermined requirements of the present invention. In Nos. 1, 2, 4, and 9 to 11, the appearance of the carbon material was not cracked, chipped, or pulverized, and the shape of the molded body was maintained. The obtained carbon material had a high purity with an ash concentration of 5000 ppm or less, and a higher density than the conventional example. Sample No. Sample No. 9 having a molding temperature higher than that of Sample No. 9 was used. 1, 2, 4, 10, and 11 were denser (1.60 g / ml or more).
- Sample No. 3 is an example in which the blending ratio of oxidized ashless coal was high.
- the density of the molded body was low, and cracking progressed when carbonized, and part of the molded body collapsed and pulverized, and the shape of the molded body could not be maintained.
- Sample No. 5 is an example in which the proportion of unmodified ashless coal was high.
- the molded body when the molded body was carbonized, the molded body foamed and expanded, and the shape was deformed.
- the carbon material was porous and had a low density.
- Sample No. 6 is an example in which oxidized ashless coal was not blended (example of only unmodified ashless coal).
- the molded body when the molded body was carbonized, the molded body foamed vigorously and expanded, and the shape was deformed.
- the carbon material was porous and had a low density.
- Sample No. 7 is an example in which the oxygen increase rate was low because the oxidation time was short with respect to the oxidation temperature.
- the molded body when the molded body was carbonized, the molded body foamed and expanded, and the shape was deformed.
- the carbon material was porous and had a low density.
- Sample No. 8 is an example in which the oxygen increase rate was high.
- voids were generated by carbonization shrinkage during carbonization, and the carbon material became porous and the density was low.
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Abstract
Description
スラリー加熱工程(S1)は、石炭と芳香族溶剤とを混合してスラリーを調製し、加熱処理して石炭成分を芳香族溶剤に抽出する処理である。
原料となる石炭(以下、「原料石炭」ともいう)の種類は特に限定されない。経済性の観点からは、瀝青炭等の高品位炭を使用するよりも、軟化溶融性をほとんど持たない非微粘炭や、一般炭、低品位炭である褐炭、亜炭、亜瀝青炭等の劣質炭を使用することが好ましい。
分離工程(S2)は、スラリー加熱工程(S1)で加熱処理されたスラリーを、液体成分と固体成分とに分離する工程である。液体成分とは、芳香族溶剤に抽出された石炭成分を含む溶液である。固体成分とは、芳香族溶剤に不溶な灰分と不溶石炭を含むスラリーである。
無灰炭取得工程(S3)は、上澄み液から芳香族溶剤を分離して灰分濃度の極めて低い無灰炭を取得する工程である。
必要に応じて、固形分濃縮液から芳香族溶剤を分離して灰分が濃縮された副生炭を製造してもよい(副生炭取得工程)。固形分濃縮液から芳香族溶剤を分離する方法は、前記した液体成分から無灰炭を取得する無灰炭取得工程(S3)と同様に、一般的な蒸留法や蒸発法を用いることができる。
酸化工程(C1)は、無灰炭を酸化する工程であって、酸化無灰炭が得られる。なお、後記するように、本発明では無改質無灰炭と、酸化工程で得られた酸化無灰炭とを混合して炭素原料(以下、「混合炭素原料」ということがある)としている。そのため、準備した無灰炭の一部を酸化工程(C1)で酸化して酸化無灰炭を製造し、残りの無改質無灰炭を使用して酸化無灰炭と混合してもよい。
炭素原料混合工程は、酸化工程(C1)で得られた酸化無灰炭と、無改質無灰炭とを混合して炭素原料(混合炭素原料)を取得する工程である。上記したように、酸化無灰炭と無改質無灰炭とを配合することで、炭素化時の溶融や膨張が抑制されると共に炭素材料に空隙が形成されることを抑制できるため、炭素材料の高密度化に寄与する。
成形工程は、炭素原料混合工程(C2)で得られた混合炭素原料を所望の形状に成形して成形体を得る工程である。成形体とするための方法は特に限定されるものではなく、例えば、平ロールによるダブルロール(双ロール)型成形機や、アーモンド型ポケットを有するダブルロール型成形機を用いる方法の他、単軸プレスやローラータイプの成形機、押し出し成形機を用いる方法、金型によるプレス成形等、いずれの方法も採用できる。
炭素化工程は、成形工程で得られた成形体を炭素化して炭素材料を取得する工程である。
(スラリー加熱工程:S1)
原料石炭(瀝青炭)5kgに対し、4倍量(20kg)の芳香族溶剤(1-メチルナフタレン(新日鉄化学社製))を混合してスラリーを調製した。このスラリーを1.2MPaの窒素で加圧して、内容積30リットルのオートクレーブ中370℃、1時間の条件で加熱処理(加熱抽出)した。
得られたスラリーを同一温度、圧力を維持した重力沈降槽内で上澄み液と固形分濃縮液とに分離した。
得られた上澄み液を更に濾過(目開き1μmのステンレスメッシュフィルター)して無灰炭溶液を得た。無灰炭溶液から蒸留法で芳香族溶剤を分離・回収して、無灰炭(炭素原料A1)を製造した。
この無灰炭(炭素原料A1)について、JIS M 8812に定められた方法で灰分濃度を測定した。その結果、無灰炭の灰分濃度は0.07質量%(700ppm)であった。
無灰炭(炭素原料A1)を用いて試料No.1~11の炭素材料を製造した。
上記製造した無灰炭(炭素原料A1)の一部を目開き0.5mmの篩を通過するように粉砕した。粉砕した無灰炭を大気雰囲気下、表1に記載の所定の温度まで加熱し、同温度で所定の時間保持して無灰炭の酸化処理(表1中、「酸化条件」)を行った。酸化処理後、室温まで放冷して酸化無灰炭(炭素原料B)を製造した。なお、酸化処理の前後で無灰炭(室温)の酸素濃度をJIS M 8813に基づいて測定し、酸化無灰炭の酸素増加率を算出した。結果を表1に示す(表1中、「酸素増加率」)。
上記無灰炭(炭素原料A1)を目開き0.5mmの篩を通過するように粉砕した無灰炭(炭素原料A2)と、上記酸化無灰炭(炭素原料B)とを表1に示す所定の割合(表1中、「酸化無灰炭配合割合」)で混合して混合炭素原料(炭素原料C)を得た。なお、試料No.6は粉砕した無灰炭(炭素原料A2)のみを用いて他の試料と同様にして成形体を製造し、炭素化して炭素材料を製造した。
上記混合炭素原料を表1に記載の温度(表1中、「成形温度」)に保持した金型(直径30mmの円筒形キャビティ)に5gを充填し、3トン/cm2の圧力でプレス成形(保持時間1分)し、厚さ7.1mmの成形体を製造した。
得られた成形体を、窒素雰囲気中0.5℃/分の速度で1000℃まで加熱し、該温度で5時間保持して炭素化し、炭素材料(試料No.1~11)を製造した。
(炭素材料の外観観察)
上記製造した各炭素材料について、その外観を目視観察し、評価した。具体的には、炭素材料に膨張、ヒビ割れや欠け、粉化が生じていないか観察した。また炭素材料の形状が、成形体の形状を保っているかを確認した。
成形体、および炭素材料の見掛け比重(密度)を測定した。その結果を表1に示す。本実施例では高密度化について従来例(試料No.6)よりも高ければ合格(可)と判断し、好ましくは炭素材料の密度が1.50g/ml以上の場合を良好(○)、更に好ましくは1.60g/ml以上である場合を優良(◎)と判断した。
なお、本出願は、2013年9月11日付けで出願された日本特許出願(特願2013-188208)に基づいており、その全体が引用により援用される。
Claims (4)
- 無灰炭を酸化する酸化工程と、
前記酸化工程で得られた酸化無灰炭と、酸化しない無灰炭とを混合して成形する成形工程と、
前記成形工程で得られた成形体を炭素化する炭素化工程と、を含み、
前記酸化工程で得られた前記酸化無灰炭の酸素増加率は、2.0~10.0%であり、且つ
前記成形工程での前記酸化無灰炭の混合割合は、前記酸化無灰炭と前記酸化しない無灰炭の合計100質量部に対して、60~95質量部であることを特徴とする炭素材料の製造方法。 - 前記酸化が空気酸化である請求項1に記載の炭素材料の製造方法。
- 前記酸化が150℃以上、かつ前記無灰炭の発火点未満の温度でおこなわれるものである請求項1または2に記載の炭素材料の製造方法。
- 酸化された無灰炭と、酸化しない無灰炭とを混合して成形した成形体を炭素化した炭素材料であって、
前記酸化された無灰炭の酸素増加率は、2.0~10.0%であり、且つ
前記成形体での前記酸化された無灰炭の割合は、前記酸化された無灰炭と、前記酸化しない無灰炭の合計100質量部に対して、60~95質量部であることを特徴とする炭素材料。
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