WO2010150685A1 - Method for producing carbon materials - Google Patents
Method for producing carbon materials Download PDFInfo
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- WO2010150685A1 WO2010150685A1 PCT/JP2010/060147 JP2010060147W WO2010150685A1 WO 2010150685 A1 WO2010150685 A1 WO 2010150685A1 JP 2010060147 W JP2010060147 W JP 2010060147W WO 2010150685 A1 WO2010150685 A1 WO 2010150685A1
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- coal
- ashless coal
- ashless
- carbon material
- solvent
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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
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
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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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/02—Treating solid fuels to improve their combustion by chemical means
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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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
Definitions
- the present invention relates to a method for producing a carbon material constituting a non-ferrous metal reducing agent, a structural carbon material, or a carbon material for an electrical material, and in particular, a method for producing a carbon material used as an aggregate of an anode for aluminum electrolytic production. About.
- coal coke used for blast furnace ironmaking has properties similar to petroleum coke as carbon, and the amount is too large as a main raw material for anodes for aluminum electrolytic production.
- coal coke contains about 10% by mass of coal-derived ash, there is a problem in quality, so it is not used in this application.
- ashless coal hyper coal
- ashless coal is produced by extracting coal with a solvent, separating only the components soluble in the solvent, and then removing the solvent.
- the molecular weight of the ashless coal is widely distributed from a relatively low molecular weight component having a few condensed aromatic rings to a high molecular weight component having about 5 or 6.
- ashless coal does not substantially contain ash, exhibits high fluidity under heating, and is excellent in thermal fluidity.
- Some coals like caking coal, exhibit thermoplasticity at around 400 ° C, but ashless coal generally melts at 200-300 ° C regardless of the quality of the raw coal (softening and melting). Have sex). Therefore, application development as a binder for coke production is being promoted taking advantage of this characteristic, and in recent years, attempts have been made to produce carbon materials by using this ashless coal as a carbon material raw material. .
- the conventional method for producing a carbon material has the following problems.
- ashless coal does not contain ash and has the characteristic of softening and melting properties. Therefore, it has been found that ashless coal is effective as a caking additive when producing coke for iron making. Moreover, it is a property preferable as an aggregate (main raw material) of the anode for aluminum electrolysis manufacture not to contain ash.
- carbonization (carbonization) of ashless charcoal is caused by another general property. This is a problem in manufacturing (hereinafter, appropriately referred to as anode coke).
- the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a carbon material production method capable of economically obtaining a high-purity carbon material that is dense and has an extremely low ash content. Is to provide.
- the present inventors have found that as a raw material for anode coke, nonferrous metal reducing agent, structural carbon material, carbon material for electrical materials other than anode coke, etc. It has been found that it is preferable to adjust the atomic ratio of carbon to carbon (hereinafter, appropriately referred to as the H / C atomic ratio) within a predetermined range.
- the ashless coal is heated.
- chemical / physical changes such as decomposition of alkyl groups, aromatization reaction, decomposition of oxygen-containing functional groups, removal of low molecular weight components, etc. that decrease the hydrogen content progress, and the number of H / C atoms The ratio gradually decreases.
- the present inventors have found that foaming during carbonization can be suppressed as a result of suppressing the expansibility of ashless coal, and have reached the present invention.
- the method for producing a nonferrous metal reducing agent, a structural carbon material, a carbon material for electrical material, or a carbon material used as a raw material thereof according to the present invention is modified by reforming coal using a solvent.
- Ashless coal production process for producing ashless coal which is a tempered coal
- ashless coal heating process for heat-treating the ashless coal produced in the ashless coal production process and heating in the ashless coal heating process
- a carbonization step of carbonizing the treated ashless coal to obtain a carbon material, and an atomic ratio of hydrogen to carbon of the ashless coal heat-treated in the ashless coal heating step ( H / C) is 0.6 to 0.67.
- ashless coal which is a modified coal having a very low ash concentration
- the ashless coal heating step the ashless coal is heat-treated, so that the H / C atomic ratio of the ashless coal is regulated within the range of 0.6 to 0.67.
- a carbon material is obtained by carbonizing this ashless coal in a carbonization process.
- the H / C atomic ratio of the ashless coal after heat processing is 0.6 or more, the sinterability of ashless coal becomes sufficient, and the H / C atomic ratio is 0.67 or less.
- the expandability of ashless coal is suppressed, and during the carbonization treatment, foaming of ashless coal is suppressed, resulting in a dense and extremely low ash content carbon material.
- the heat treatment of the ashless coal is the same solvent as the solvent used for reforming the coal in the ashless coal production step. It is preferable to be carried out in the presence of
- a dense carbon material having an extremely low ash content can be obtained. Moreover, such a carbon material can be obtained economically.
- the method for producing a carbon material according to the present invention includes an ashless coal production process, an ashless coal heating process, and a carbonization process. Hereinafter, each step will be described.
- An ashless coal manufacturing process is a process of manufacturing ashless coal which is reformed coal by modifying coal using a solvent.
- the ashless coal as used in the field of this invention is what is called hyper coal, and is manufactured by solvent-extracting coal and removing ash and an insoluble coal component.
- This ashless coal has an extremely small amount of ash (ash concentration of 1.0% by mass or less) and water of approximately 0.5% by mass or less.
- a method for obtaining ashless coal known methods can be used, and the solvent type and production conditions are appropriately selected in view of the properties of coal and the design as a raw material for carbon materials.
- a typical method is to heat a mixture of a solvent having a large dissolving power to coal, often an aromatic solvent (hydrogen donating or non-hydrogen donating solvent) and coal, There is a method of extracting organic components.
- it is preferable to produce ashless coal by the following method. In the method, first, a coal component soluble in the non-hydrogen donating solvent is extracted by heating a mixture (slurry) of coal and the non-hydrogen donating solvent. Next, the slurry after extraction is separated into a liquid part and a non-liquid part, and the non-hydrogen donating solvent is separated from the liquid part to produce ashless coal.
- inferior coal As the ashless coal raw coal (hereinafter also referred to as raw coal), inferior coal is preferably used. By using inexpensive inferior coal, ashless coal can be produced at a lower cost, so that the economic efficiency can be further improved.
- the coal used is not limited to inferior coal, and bituminous coal may be used as necessary.
- the inferior coal there are coals such as non-slightly caking coal, steam coal, low-grade coal (brown coal, subbituminous coal, etc.).
- the low-grade coal include lignite, lignite, and sub-bituminous coal.
- lignite include Victoria charcoal, North Dakota charcoal, and Belga charcoal.
- sub-bituminous coal include West Banco charcoal, Vinungan charcoal, and Samarangau charcoal.
- the low-grade coal is not limited to those exemplified above. Any coal that contains a large amount of water and is desired to be dewatered is included in the low-grade coal referred to in the present invention.
- the non-hydrogen-donating solvent is a coal derivative that is a solvent mainly composed of a bicyclic aromatic and purified mainly from a dry distillation product of coal.
- This non-hydrogen donating solvent is stable even when heated, and has an excellent affinity for coal. For this reason, when a non-hydrogen-donating solvent is used, the ratio of the soluble component (herein, the coal component) extracted into the solvent increases (hereinafter also referred to as the extraction rate).
- the solvent can be easily recovered.
- the main component of the non-hydrogen donating solvent include naphthalene, methylnaphthalene, dimethylnaphthalene, and trimethylnaphthalene, which are bicyclic aromatics.
- the components of the non-hydrogen donating solvent include naphthalenes having an aliphatic side chain, anthracenes, fluorenes, and biphenyl and alkylbenzene having a long chain aliphatic side chain.
- the extraction rate of coal can be improved by heat extraction using a non-hydrogen donating solvent. Also, unlike polar solvents, non-hydrogen donating solvents can be easily recovered and thus are easily recycled. Furthermore, since it is not necessary to use expensive hydrogen, a catalyst, or the like, ashless coal can be obtained by solubilizing coal at a low cost, and economic efficiency can be improved.
- the coal concentration with respect to the solvent is preferably in the range of 10 to 50 mass%, more preferably in the range of 20 to 35 mass%, based on dry coal, although it depends on the type of raw coal.
- the coal concentration with respect to the solvent is less than 10% by mass, the proportion of the coal component extracted into the solvent decreases with respect to the amount of the solvent, which is not economical.
- the higher the coal concentration the better.
- the viscosity of the prepared slurry becomes high, so that it is difficult to move the slurry and separate the liquid part and the non-liquid part (described later).
- the heating temperature of the slurry is preferably in the range of 300 to 450 ° C.
- the heating temperature is preferably 300 to 400 ° C.
- the standard of heating time is the time to reach dissolution equilibrium, but its realization is economically disadvantageous. Therefore, the heating time is usually about 10 to 60 minutes, although it cannot be generally stated because it varies depending on conditions such as the particle size of the coal and the type of solvent. When the heating time is less than 10 minutes, extraction of the coal component tends to be insufficient. On the other hand, even if the heating time exceeds 60 minutes, the extraction does not proceed any further, which is not economical.
- Extraction of the coal component soluble in the non-hydrogen donating solvent is preferably carried out in the presence of an inert gas.
- the inert gas used is preferably inexpensive nitrogen, but is not particularly limited.
- the pressure is preferably 1.0 to 2.0 MPa, although it depends on the temperature during extraction and the vapor pressure of the solvent used. When the pressure is lower than the vapor pressure of the solvent, the solvent volatilizes and is not trapped in the liquid phase, and extraction is impossible. In order to confine the solvent in the liquid phase, a pressure higher than the vapor pressure of the solvent is required. On the other hand, if the pressure is too high, the cost of the equipment and the operating cost increase, which is not economical.
- the slurry is separated into a liquid part and a non-liquid part.
- the liquid part is a solution containing a coal component extracted into a solvent
- the non-liquid part is a solute containing a coal component insoluble in the solvent (coal containing ash, that is, ash coal).
- ashless coal is obtained by isolate
- a method for separating the solvent from the supernatant liquid (liquid part) a general distillation method, an evaporation method (spray drying method, etc.) or the like can be used. From the supernatant, ashless coal substantially free of ash is obtained.
- the ash content of this ashless coal is 1.0 mass% or less, and hardly contains ash.
- moisture content of this ashless coal is about 0.5 mass% or less, and shows the calorific value higher than raw material coal. Therefore, by carbonizing this ashless coal, a highly pure carbon material having a very low ash content can be obtained.
- the ashless coal heating step is a step of heat-treating the ashless coal manufactured in the ashless coal manufacturing step.
- Ashless charcoal is generally highly expansible in the as-manufactured state. Therefore, heat treatment is performed to suppress expansion.
- the heat treatment needs to be performed so that the atomic ratio (H / C) of hydrogen to carbon of the ashless coal after the heat treatment is in the range of 0.6 to 0.67.
- the H / C atomic ratio of the as-produced ashless coal that has not been treated varies depending on the raw coal type and the production conditions of the ashless coal, but is generally 0.7 to 1.0. It is in the range.
- chemical / physical changes such as alkyl group decomposition, aromatization reaction, decomposition of oxygen-containing functional groups, removal of low molecular weight components, etc. will decrease the hydrogen content.
- Advances, and the H / C atomic ratio gradually decreases. Therefore, the H / C atomic ratio is adjusted to be in the range of 0.6 to 0.67 by heat treatment.
- the H / C atomic ratio is smaller than 0.6, it means that the heat treatment is excessive. If the heat treatment is excessive, the sinterability becomes insufficient, and even if this ashless coal is carbonized, only a powdery carbon material can be obtained. Therefore, if the H / C atomic ratio is less than 0.6, a carbon material used as a raw material for anode coke cannot be obtained. On the other hand, the H / C atomic ratio being larger than 0.67 indicates that the heat treatment is insufficient, and ashless coal contains a relatively large amount of hydrogen. Therefore, if the H / C atomic ratio exceeds 0.67, ashless coal will foam during carbonization in the carbonization step. Thus, by adjusting the H / C atomic ratio in the range of 0.6 to 0.67 by heat treatment of ashless coal, while maintaining appropriate sinterability, Foaming can be suppressed.
- the method of heat treatment of ashless coal is not particularly limited, and can be performed by a known method.
- ashless coal is heated to 350 to 500 ° C., preferably 380 to 460 ° C. in a vacuum, high pressure, or inert atmosphere.
- the required treatment time varies depending on the properties of ashless coal and the treatment temperature, but is generally in the range of 10 minutes to 5 hours. In this way, the H / C atomic ratio is controlled in the range of 0.6 to 0.67 by appropriately adjusting the processing temperature and processing time in consideration of the properties of ashless coal.
- the heat treatment of ashless coal is preferably performed in the presence of the same solvent as the solvent used for coal reforming in the ashless coal production process. That is, the ashless coal is heat-treated after being mixed with a solvent so as to form a slurry.
- the amount of the solvent with respect to the ashless coal is not particularly limited, but from the viewpoint of obtaining a slurry having an appropriate viscosity, the concentration of the ashless coal with respect to the solvent is, for example, 10 to 50% by mass on the basis of dry coal, preferably 20 to It may be in the range of 35% by mass.
- the heat processing of ashless coal said here may be performed, without isolate
- a general distillation method, an evaporation method (spray drying method or the like) or the like can be used as a method for separating the solvent from the ashless coal after the heat treatment.
- the heat transfer efficiency becomes higher than when ashless coal is heated as it is, and uniform heating becomes possible. Furthermore, the manufacturing cost can be reduced by using the same solvent as the solvent used for coal reforming.
- a solvent used for the heat treatment of ashless coal alkylnaphthalene, anthracene oil, and the like are preferable.
- a carbonization process is a process of obtaining a carbon material by carbonizing the ashless coal heat-processed at the said ashless coal heating process. By this carbonization process, ashless coal is carbonized and a carbon material is obtained.
- the method and conditions for the carbonization treatment are not particularly limited, and known techniques can be used.
- ashless coal is converted into carbon by steaming and baking ashless coal at about 1000 ° C. in an inert atmosphere such as nitrogen or argon.
- the temperature raising rate may be about 0.1 to 5 ° C./min.
- This carbonization treatment may be performed under pressure using a hot isostatic pressing apparatus or the like.
- binder components such as asphalt pitch and tar, may be added as needed.
- the carbonization step may be performed after the heat-treated ashless coal is appropriately formed.
- Examples thereof include a pot furnace, a lead hammer furnace, a kiln, a rotary kiln, a shaft furnace, and a chamber furnace.
- the heat treatment furnace is not limited to these, and other heat treatment furnaces may be used.
- the carbon material obtained by the production method of the present invention can be suitably used as a main raw material coke for an anode for aluminum electrolytic production.
- the carbon material obtained in the present invention can also be used as a non-ferrous metal reducing agent, a structural carbon material, or a carbon material for electrical materials other than an anode for aluminum electrolytic production, or a non-ferrous metal reducing agent. It can also be used as a raw material for structural carbon materials or carbon materials for electrical materials.
- the nonferrous metal reducing agent is a reducing agent used for reduction of nonferrous metals such as silicon and titanium.
- the structural carbon material is, for example, a carbon material used as a raw material for a carbon heat insulating material or a carbon structural material such as a crucible.
- the carbon material for electric materials is a carbon material used as a raw material for carbon-made electric materials such as carbon electrodes in addition to the anode for aluminum electrolytic production.
- the description of being used as these raw materials is because, for example, it may be necessary to subject the carbon material to a secondary treatment such as heat treatment.
- the method for producing a carbon material of the present invention includes an ashless coal production process, an ashless coal heating process, and a carbonization process.
- Other processes such as a process and an ashless charcoal drying process for drying ashless charcoal may be included.
- ashless coal was manufactured by the following method.
- the raw coal is a raw coal for producing coke that is bituminous coal (coal A) or a thermal coal for thermal power generation that is bituminous coal (coal B).
- a slurry is prepared by mixing 4 kg (20 kg) of a solvent (1-methylnaphthalene (manufactured by Nippon Steel Chemical Co., Ltd.)) with 5 kg of the raw coal.
- This slurry was pressurized with 1.2 MPa of nitrogen and extracted in an autoclave with an internal volume of 30 L at 370 ° C. for 1 hour.
- This slurry was separated into a supernatant and a solid concentrate in a gravity sedimentation tank maintained at the same temperature and pressure, and the solvent was separated and recovered from the supernatant by a distillation method to obtain ashless coal.
- the ashless coal is heat-treated by the following method.
- the heat treatment of ashless coal is performed under the condition that 1-methylnaphthalene (manufactured by Nippon Steel Chemical Co., Ltd.) is used as a solvent three times as much as the ashless coal (three times by mass) or no solvent is used Done.
- the heat treatment is performed in a hermetic autoclave having an initial nitrogen pressure of 0.1 MPa, while raising the temperature up to a predetermined temperature shown in Table 1 at 10 ° C./min while stirring ashless coal, as shown in Table 1. It was performed by holding for a predetermined time.
- the gas in the autoclave is discharged and heated to 150 ° C. under a pressure of 0.001 MPa for 1 hour to distill off the solvent and the oil that may have been produced. It was recovered. And H / C atomic ratio is calculated
- the ashless coal is carbonized by the following method. 5 g of ashless coal that has been heat-treated and crushed to 1 mm or less is packed in a quartz test tube with an inner diameter of 20 mm so that the bulk density becomes 0.8 g / cc, and then in a nitrogen atmosphere at 3 ° C./min. The temperature was raised to 1000 ° C. and kept at this temperature for 30 minutes for carbonization, whereby a carbide (carbon material) was obtained.
- the produced carbide was cut to a length of 10 mm and then subjected to a crush test, and the strength was measured.
- the crush test is performed by placing the sample on the lower pressure plate, compressing the sample with the upper pressure indenter, and measuring the strength (collapse strength) when the sample collapses. And it is judged that the sample which has the intensity
- strength also changes depending on the conditions of carbonization treatment (packing density of raw materials, presence / absence of molding, or heat treatment temperature), this value is a value for relative comparison to the last.
- a carbon material having higher strength is denser and suitable as a coke raw material for an anode.
- Table 1 shows the test results. In Table 1, numerical values that do not satisfy the scope of the present invention are shown underlined. Further, 1-methylnaphthalene is indicated as MN in the table. Furthermore, FIG. 1 shows a graph showing the relationship between intensity and the H / C atomic ratio. The strength “0.00” indicates that the strength could not be measured because the strength was not strong enough to be measured.
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Abstract
Description
前記のとおり、無灰炭は、灰分を含まず、軟化溶融性を有するという特長を有するため、製鉄用コークスを製造するときの粘結性補填材として有効なことがわかっている。また、灰分を含まないことは、アルミニウム電解製造用アノードの骨材(主原料)として好ましい性質である。しかし、無灰炭を加熱処理して炭素材料とする炭素化(炭化)時に、無灰炭は別の一般的性質により発泡するが、これはアルミニウム電解製造用アノードの主原料コークス(炭素材料)(以下、適宜、アノード用コークスという)製造上、問題になる。すなわち、製造したままの無灰炭を炭素化すると、炭素化時に生成する低分子化合物ガス(水蒸気、CO、CO2、炭化水素等)による気孔がそのまま残るため、アノード用コークスとして適当な緻密なコークスが生成しないという問題がある。なお、無灰炭を、非鉄金属還元剤や構造用炭素材、アノード用コークス以外の電気材料用炭素材等に使用する場合も、同様の問題が生ずる。 However, the conventional method for producing a carbon material has the following problems.
As described above, ashless coal does not contain ash and has the characteristic of softening and melting properties. Therefore, it has been found that ashless coal is effective as a caking additive when producing coke for iron making. Moreover, it is a property preferable as an aggregate (main raw material) of the anode for aluminum electrolysis manufacture not to contain ash. However, when carbonizing (carbonizing) ashless charcoal to heat it, carbonization (carbonization) of ashless charcoal is caused by another general property. This is a problem in manufacturing (hereinafter, appropriately referred to as anode coke). That is, when carbonized as-produced ashless coal, pores due to low-molecular compound gases (water vapor, CO, CO 2 , hydrocarbons, etc.) generated during carbonization remain as they are, so that the dense ash suitable for anode coke is suitable. There is a problem that coke is not generated. The same problem occurs when ashless coal is used for nonferrous metal reducing agents, structural carbon materials, carbon materials for electrical materials other than anode coke, and the like.
本発明に係る炭素材料の製造方法は、無灰炭製造工程と、無灰炭加熱工程と、炭素化工程と、を含む。以下、各工程について説明する。 Next, the method for producing the carbon material according to the present invention will be described in detail.
The method for producing a carbon material according to the present invention includes an ashless coal production process, an ashless coal heating process, and a carbonization process. Hereinafter, each step will be described.
無灰炭製造工程は、溶剤を用いて石炭を改質することにより、改質炭である無灰炭を製造する工程である。
なお、本発明でいう無灰炭は、いわゆるハイパーコールであり、石炭を溶剤抽出して灰分と非溶解性の石炭成分とを除去することにより製造される。この無灰炭は、極めて少ない灰分(灰分濃度1.0質量%以下)と、概ね0.5質量%以下の水分を有する。 <Ashless coal manufacturing process>
An ashless coal manufacturing process is a process of manufacturing ashless coal which is reformed coal by modifying coal using a solvent.
In addition, the ashless coal as used in the field of this invention is what is called hyper coal, and is manufactured by solvent-extracting coal and removing ash and an insoluble coal component. This ashless coal has an extremely small amount of ash (ash concentration of 1.0% by mass or less) and water of approximately 0.5% by mass or less.
用いられる不活性ガスとしては、安価な窒素が好ましいが、特に限定されない。また、圧力は、抽出の際の温度や用いる溶剤の蒸気圧にもよるが、好ましくは1.0~2.0MPaである。溶剤の蒸気圧より圧力が低い場合には、溶剤が揮発して液相に閉じ込められず、抽出が不可能となる。溶剤を液相に閉じ込めるには、溶剤の蒸気圧より高い圧力が必要となる。一方、圧力が高すぎると、機器のコスト、運転コストが高くなり、経済的ではない。 Extraction of the coal component soluble in the non-hydrogen donating solvent is preferably carried out in the presence of an inert gas. This is because contact with oxygen is dangerous because it may ignite, and using hydrogen increases costs.
The inert gas used is preferably inexpensive nitrogen, but is not particularly limited. The pressure is preferably 1.0 to 2.0 MPa, although it depends on the temperature during extraction and the vapor pressure of the solvent used. When the pressure is lower than the vapor pressure of the solvent, the solvent volatilizes and is not trapped in the liquid phase, and extraction is impossible. In order to confine the solvent in the liquid phase, a pressure higher than the vapor pressure of the solvent is required. On the other hand, if the pressure is too high, the cost of the equipment and the operating cost increase, which is not economical.
ここで、液部は、溶剤に抽出された石炭成分を含む溶液であり、非液部は、溶剤に不溶な石炭成分(灰分を含む石炭すなわち灰炭)を含む溶質である。 After extracting the coal component in this way, the slurry is separated into a liquid part and a non-liquid part.
Here, the liquid part is a solution containing a coal component extracted into a solvent, and the non-liquid part is a solute containing a coal component insoluble in the solvent (coal containing ash, that is, ash coal).
上澄み液(液部)から溶剤を分離する方法としては、一般的な蒸留法や蒸発法(スプレードライ法等)等が使用可能である。上澄み液からは、実質的に灰分を含まない無灰炭が得られる。この無灰炭の灰分含有量は1.0質量%以下であり、灰分をほとんど含まない。また、この無灰炭の水分は概ね0.5質量%以下であり、また原料石炭よりも高い発熱量を示す。従って、この無灰炭を炭素化することによって、極めて灰分濃度の低い高純度の炭素材料を得ることができる。 And ashless coal is obtained by isolate | separating a non-hydrogen donating solvent from this liquid part.
As a method for separating the solvent from the supernatant liquid (liquid part), a general distillation method, an evaporation method (spray drying method, etc.) or the like can be used. From the supernatant, ashless coal substantially free of ash is obtained. The ash content of this ashless coal is 1.0 mass% or less, and hardly contains ash. Moreover, the water | moisture content of this ashless coal is about 0.5 mass% or less, and shows the calorific value higher than raw material coal. Therefore, by carbonizing this ashless coal, a highly pure carbon material having a very low ash content can be obtained.
無灰炭加熱工程は、前記無灰炭製造工程で製造された無灰炭を加熱処理する工程である。
無灰炭は、製造されたままの状態では、一般に膨張性が激しい。従って、膨張を抑制するために、加熱処理が行われる。加熱処理は、加熱処理後の無灰炭の水素と炭素の原子数比(H/C)が0.6~0.67の範囲となるように行われることが必要である。 <Ashless charcoal heating process>
The ashless coal heating step is a step of heat-treating the ashless coal manufactured in the ashless coal manufacturing step.
Ashless charcoal is generally highly expansible in the as-manufactured state. Therefore, heat treatment is performed to suppress expansion. The heat treatment needs to be performed so that the atomic ratio (H / C) of hydrogen to carbon of the ashless coal after the heat treatment is in the range of 0.6 to 0.67.
すなわち、無灰炭は、スラリー状となるように溶剤と混合されてから、加熱処理される。無灰炭に対する溶剤の量は特に限定されないが、適度な粘度のスラリーを得るという観点からは、溶剤に対する無灰炭濃度が、例えば、乾燥炭基準で10~50質量%、好ましくは、20~35質量%の範囲であればよい。また、前記溶剤に抽出された石炭成分である液部をそのまま加熱することによって、溶剤を分離することなく、ここで言う無灰炭の加熱処理が行われてもよい。なお、加熱処理後の無灰炭から溶剤を分離する方法としては、一般的な蒸留法や蒸発法(スプレードライ法等)等が使用可能である。 Moreover, the heat treatment of ashless coal is preferably performed in the presence of the same solvent as the solvent used for coal reforming in the ashless coal production process.
That is, the ashless coal is heat-treated after being mixed with a solvent so as to form a slurry. The amount of the solvent with respect to the ashless coal is not particularly limited, but from the viewpoint of obtaining a slurry having an appropriate viscosity, the concentration of the ashless coal with respect to the solvent is, for example, 10 to 50% by mass on the basis of dry coal, preferably 20 to It may be in the range of 35% by mass. Moreover, the heat processing of ashless coal said here may be performed, without isolate | separating a solvent by heating the liquid part which is the coal component extracted by the said solvent as it is. In addition, as a method for separating the solvent from the ashless coal after the heat treatment, a general distillation method, an evaporation method (spray drying method or the like) or the like can be used.
炭素化工程は、前記無灰炭加熱工程で加熱処理された無灰炭を炭素化処理することにより、炭素材料を得る工程である。この炭素化工程により無灰炭が炭素化され、炭素材料が得られる。 <Carbonization process>
A carbonization process is a process of obtaining a carbon material by carbonizing the ashless coal heat-processed at the said ashless coal heating process. By this carbonization process, ashless coal is carbonized and a carbon material is obtained.
[無灰炭の製造]
まず、無灰炭は、以下の方法により製造された。
原料石炭は、瀝青炭であるコークス製造用原料炭(石炭A)か、または、瀝青炭である火力発電用一般炭(石炭B)である。この原料石炭5kgに対し、4倍量(20kg)の溶剤(1-メチルナフタレン(新日鉄化学社製))を混合することにより、スラリーが調製される。このスラリーを1.2MPaの窒素で加圧して、内容積30Lのオートクレーブ中370℃、1時間の条件で抽出した。この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、上澄み液から蒸留法で溶剤を分離・回収して、無灰炭を得た。 Next, the manufacturing method of the carbon material according to the present invention will be specifically described with reference to examples and comparative examples.
[Manufacture of ashless coal]
First, ashless coal was manufactured by the following method.
The raw coal is a raw coal for producing coke that is bituminous coal (coal A) or a thermal coal for thermal power generation that is bituminous coal (coal B). A slurry is prepared by mixing 4 kg (20 kg) of a solvent (1-methylnaphthalene (manufactured by Nippon Steel Chemical Co., Ltd.)) with 5 kg of the raw coal. This slurry was pressurized with 1.2 MPa of nitrogen and extracted in an autoclave with an internal volume of 30 L at 370 ° C. for 1 hour. This slurry was separated into a supernatant and a solid concentrate in a gravity sedimentation tank maintained at the same temperature and pressure, and the solvent was separated and recovered from the supernatant by a distillation method to obtain ashless coal.
次に、無灰炭は、以下の方法により加熱処理される。
無灰炭の加熱処理は、溶剤として1-メチルナフタレン(新日鉄化学社製)を、無灰炭に対して3倍量(質量で3倍)用いる条件か、または溶剤を全く用いない条件下で行われる。加熱処理は、窒素初気圧0.1MPaの気密式のオートクレーブ中で、無灰炭を攪拌しながら、10℃/分で表1に示される所定の温度まで昇温すると共に、表1に示される所定の時間保持することにより行った。処理後、オートクレーブ内のガスを排出し、0.001MPaの圧力下で150℃に1時間加熱することによって、溶剤や生成したかもしれない油分を蒸留除去した後、加熱処理された無灰炭が回収された。そして、これらを元素分析することにより、H/C原子数比が求められる。 [Heat treatment]
Next, the ashless coal is heat-treated by the following method.
The heat treatment of ashless coal is performed under the condition that 1-methylnaphthalene (manufactured by Nippon Steel Chemical Co., Ltd.) is used as a solvent three times as much as the ashless coal (three times by mass) or no solvent is used Done. The heat treatment is performed in a hermetic autoclave having an initial nitrogen pressure of 0.1 MPa, while raising the temperature up to a predetermined temperature shown in Table 1 at 10 ° C./min while stirring ashless coal, as shown in Table 1. It was performed by holding for a predetermined time. After the treatment, the gas in the autoclave is discharged and heated to 150 ° C. under a pressure of 0.001 MPa for 1 hour to distill off the solvent and the oil that may have been produced. It was recovered. And H / C atomic ratio is calculated | required by carrying out elemental analysis of these.
次に、無灰炭は、以下の方法により炭素化処理される。
加熱処理されて1mm以下に粉砕された無灰炭のうち5gを、内径20mmの石英試験管に、かさ密度0.8g/ccとなるように詰めた後、窒素雰囲気中、3℃/分で1000℃まで昇温し、この温度に30分保持して炭素化することによって、炭化物(炭素材料)が得られた。 [Carbonization treatment]
Next, the ashless coal is carbonized by the following method.
5 g of ashless coal that has been heat-treated and crushed to 1 mm or less is packed in a quartz test tube with an inner diameter of 20 mm so that the bulk density becomes 0.8 g / cc, and then in a nitrogen atmosphere at 3 ° C./min. The temperature was raised to 1000 ° C. and kept at this temperature for 30 minutes for carbonization, whereby a carbide (carbon material) was obtained.
また、No.7~13、23~25は、H/C原子数比が上限値を超える。そのため、炭素化工程において無灰炭が発泡してしまい、緻密な炭素材料が得られず、強度は測定できなかった。 On the other hand, no. 4 to 6, 21, and 22 have an H / C atomic ratio that is less than the lower limit. For this reason, the carbon material became powdery and did not become a dense carbon material, and the strength was low. In addition, No. The intensity of 6 could not be measured.
No. In 7 to 13 and 23 to 25, the H / C atomic ratio exceeds the upper limit. Therefore, ashless coal foamed in the carbonization step, a dense carbon material could not be obtained, and the strength could not be measured.
Claims (2)
- 非鉄金属還元剤、構造用炭素材、電気材料用炭素材、または、これらの原料として用いられる炭素材料の製造方法であって、
溶剤を用いて石炭を改質することにより、改質炭である無灰炭を製造する無灰炭製造工程と、
前記無灰炭製造工程で製造された前記無灰炭を加熱処理する無灰炭加熱工程と、
前記無灰炭加熱工程で加熱処理された前記無灰炭を炭素化処理することにより炭素材料を得る炭素化工程と、を含み、
前記無灰炭加熱工程で加熱処理された前記無灰炭の水素と炭素の原子数比(H/C)が、0.6~0.67である炭素材料の製造方法。 A non-ferrous metal reducing agent, a structural carbon material, a carbon material for electrical materials, or a method for producing a carbon material used as a raw material thereof,
An ashless coal production process for producing ashless coal, which is a modified coal, by reforming coal using a solvent;
Ashless coal heating step of heat-treating the ashless coal produced in the ashless coal production step;
A carbonization step of obtaining a carbon material by carbonizing the ashless coal heat-treated in the ashless coal heating step,
A method for producing a carbon material, wherein the ashless coal heat-treated in the ashless coal heating step has an atomic ratio (H / C) of hydrogen to carbon of 0.6 to 0.67. - 前記無灰炭加熱工程において、前記無灰炭の加熱処理が、前記無灰炭製造工程において前記石炭の改質に使用された溶剤と同じ溶剤の存在下で行われる請求項1に記載の炭素材料の製造方法。 The carbon according to claim 1, wherein in the ashless coal heating step, the heat treatment of the ashless coal is performed in the presence of the same solvent as the solvent used for reforming the coal in the ashless coal production step. Material manufacturing method.
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WO2014175121A1 (en) * | 2013-04-26 | 2014-10-30 | 株式会社神戸製鋼所 | Method for manufacturing ashless coal, and method for manufacturing carbon material |
US20160272910A1 (en) * | 2013-12-25 | 2016-09-22 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method for producing ashless coal |
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JP2012184125A (en) * | 2011-03-03 | 2012-09-27 | Kobe Steel Ltd | Method for producing carbon material |
JP2014065823A (en) * | 2012-09-26 | 2014-04-17 | Kobe Steel Ltd | Production method of ashless coal |
KR101747564B1 (en) * | 2012-09-26 | 2017-06-14 | 가부시키가이샤 고베 세이코쇼 | Method for manufacturing ashless coal |
JP6199020B2 (en) * | 2012-10-12 | 2017-09-20 | 株式会社神戸製鋼所 | Production method of ashless coal |
JP6017366B2 (en) * | 2013-04-16 | 2016-10-26 | 株式会社神戸製鋼所 | Production method of ashless coal |
JP5990501B2 (en) * | 2013-10-09 | 2016-09-14 | 株式会社神戸製鋼所 | Production method of ashless coal |
JP6014012B2 (en) * | 2013-12-04 | 2016-10-25 | 株式会社神戸製鋼所 | Coke production method and coke |
JP6189811B2 (en) * | 2014-10-07 | 2017-08-30 | 株式会社神戸製鋼所 | Ashless coal blending amount determination method and blast furnace coke manufacturing method |
JP6174004B2 (en) * | 2014-12-08 | 2017-08-02 | 株式会社神戸製鋼所 | Carbon material manufacturing method |
JP7134755B2 (en) * | 2018-07-10 | 2022-09-12 | 株式会社神戸製鋼所 | coke production method |
CN113583730A (en) * | 2021-06-29 | 2021-11-02 | 山西沁新能源集团股份有限公司 | High-carbon coke and preparation method of ultrapure coal for producing high-carbon coke |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5857498A (en) * | 1981-09-30 | 1983-04-05 | Mitsubishi Heavy Ind Ltd | Preparation of reformed coal |
JP2007142204A (en) * | 2005-11-18 | 2007-06-07 | Gunma Univ | Carbon material for electric double layer capacitor and manufacturing method |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3892654A (en) * | 1974-03-04 | 1975-07-01 | Us Interior | Dual temperature coal solvation process |
US4176041A (en) * | 1977-02-24 | 1979-11-27 | Kobe Steel, Ltd. | Method for reforming low grade coals |
JPS5582789A (en) * | 1978-12-16 | 1980-06-21 | Kawasaki Steel Corp | Preparation of binder pitch for electrode |
US4522628A (en) * | 1981-12-16 | 1985-06-11 | Mobil Oil Corporation | Method for removing ash mineral matter of coal with liquid carbon dioxide and water |
US5248413A (en) * | 1992-02-28 | 1993-09-28 | University Of Kentucky Research Foundation | Process for removing sulfur and producing enhanced quality and environmentally acceptable products for energy production from coal |
JP4061351B1 (en) * | 2006-10-12 | 2008-03-19 | 株式会社神戸製鋼所 | Production method of ashless coal |
JP5128351B2 (en) * | 2007-10-23 | 2013-01-23 | 株式会社神戸製鋼所 | Carbon material manufacturing method |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5857498A (en) * | 1981-09-30 | 1983-04-05 | Mitsubishi Heavy Ind Ltd | Preparation of reformed coal |
JP2007142204A (en) * | 2005-11-18 | 2007-06-07 | Gunma Univ | Carbon material for electric double layer capacitor and manufacturing method |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014175121A1 (en) * | 2013-04-26 | 2014-10-30 | 株式会社神戸製鋼所 | Method for manufacturing ashless coal, and method for manufacturing carbon material |
JP2014214267A (en) * | 2013-04-26 | 2014-11-17 | 株式会社神戸製鋼所 | Method for manufacturing ashless coal, and method for manufacturing carbon material |
US20160272910A1 (en) * | 2013-12-25 | 2016-09-22 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method for producing ashless coal |
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