WO2013129607A1 - 成形配合炭およびその製造方法、ならびにコークスおよびその製造方法 - Google Patents
成形配合炭およびその製造方法、ならびにコークスおよびその製造方法 Download PDFInfo
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- WO2013129607A1 WO2013129607A1 PCT/JP2013/055519 JP2013055519W WO2013129607A1 WO 2013129607 A1 WO2013129607 A1 WO 2013129607A1 JP 2013055519 W JP2013055519 W JP 2013055519W WO 2013129607 A1 WO2013129607 A1 WO 2013129607A1
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- coal
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- ashless
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- coke
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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
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/08—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form in the form of briquettes, lumps and the like
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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
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
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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
- C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof
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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
- C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
- C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
- C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
Definitions
- the present invention relates to a blended coal using an ashless coal obtained by extracting coal with a solvent and a by-product coal as a by-product, and a method for producing the same. It relates to coke produced from charcoal.
- the coke used for blast furnace iron making has a certain mechanical strength, reactivity, apparent density, and mass size and distribution necessary to ensure air permeability, etc. Various characteristics are required.
- the coke raw materials that meet these requirements are usually called “coking coal”, compared with high-quality boiler fuel coal, which has a certain range of caking, fluidity, or degree of coalification. Strong caking coal that is expensive and expensive is used.
- ashless coal hyper coal
- Development is actively underway.
- Ashless charcoal is obtained by removing most of the ash from the coal, substantially free of ash (target: 200 ppm by mass or less), and structurally has a relatively low molecular weight with two or three condensed aromatic rings. It has a broad molecular weight distribution from components to high molecular weight components of about 5 or 6 rings. Therefore, it exhibits high fluidity under heating.
- Some coals like caking coal, exhibit thermoplasticity at a high temperature of about 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 advanced by making use of this characteristic (see, for example, Patent Document 1), and in recent years, a carbon material is produced by using this ashless coal as a raw material. It has been tried.
- Ashless coal is a solvent that has a high affinity with coal.
- ash that does not dissolve in the solvent settles as a residue and is extracted from the extract (liquid part) separated as a supernatant. It is manufactured by removing the solvent (see, for example, Patent Documents 2 to 4).
- the residue (non-liquid part) from which the extract has been separated is recovered by a distillation method or an evaporation method (see, for example, Patent Document 3), and a residue composed of components insoluble in a solvent such as ash is generated as a by-product. .
- This by-product is called by-product charcoal and contains a lot of ash. However, it is used for various fuels because it has enough calorific value after moisture is removed during the production of ashless coal. be able to. Furthermore, since the by-product coal is derived from steam coal that is not normally used as a coke raw material, if it can be used as a coke raw material, it is considered that coke can be produced at a lower cost. However, by-product coal is a coal component that remains after obtaining ashless coal, which is a caking component, from coal, so it has poor fluidity and caking properties. It was found that the decrease in coke strength was remarkable.
- the present invention has been made in view of the above problems, and its problem is to handle coal blended with by-product coal in order to more effectively use by-product coal, which is a by-product of ashless coal.
- the present invention is to provide a coke having a sufficient strength when it is dry-distilled as a coke raw material, and a method for producing the same, even if the molded product is excellent in convenience and further contains by-product coal having low fluidity and cohesiveness. .
- the present invention provides the following coal blend, coke, a method for producing the coal blend, and a method for producing the coke.
- Molding including blended coal obtained by mixing ashless coal containing a solvent-soluble component in coal and by-product coal obtained by removing the component soluble in the solvent from coal into granular coal Coal blend, The blended coal contains 3% by weight or more of the ashless coal, 8% by weight or less of the by-product coal, and the granular coal as a balance.
- 90% or more of the granular coal has a diameter of 2 mm or less, and the blended coal according to (1).
- More than 60% of the granular coal has a diameter of 1 mm or less, and the blended coal according to (2).
- the coal such as coal that is difficult to organize as a molded product becomes stronger, and coal, ashless coal, and by-product coal are strongly bound to each other by molding, Even if it contains by-product charcoal, it becomes a blended coal that becomes coke with sufficient strength.
- the granular coal has a maximum fluidity MF value (log (ddpm)) of 0.2 to 2.0 and an average maximum reflectance Ro value of 0.8 to 1.1.
- the blended coal according to any one of (1) to (3). In this way, by defining coal with predetermined characteristics, even coal that is unsuitable for coke raw material is formed into coal blend that is produced by dry distillation to produce coke with sufficient strength.
- the coal can be pulverized into granules, so that it can be suitably mixed with ashless coal and the like, and the unity at the time of molding becomes strong.
- strength can be manufactured by prescribing
- the strength of the blended coal is improved and the surface layer is difficult to peel or exfoliate, and the coal, ashless coal, and by-product coal are more strongly bound to each other. Even if it contains raw charcoal, it is a suitable raw material for coke.
- a method for producing coke comprising a step of carbonizing a coal mixture containing a formed coal blend produced by the method for producing a formed coal blend according to (6) or (7).
- blended coal according to the present invention fuel and coke raw material suitable for storage and transportation can be obtained. According to the coke which concerns on this invention, it becomes sufficient intensity
- the formed coal blend and the manufacturing method thereof according to the present invention will be described in detail.
- the coal blend according to the present invention is obtained by mixing ashless coal and by-product coal into coal and forming it into a lump of a predetermined three-dimensional shape as a coal blend. It is used as a blended coal for fuel and coke raw materials.
- the shape and size of the formed coal blend are not particularly defined and are designed according to the application.
- ashless coal, by-product coal, and coal, which are raw materials of the formed blended coal will be described.
- Ashless coal is a modified coal from which ashes and non-soluble coal components are removed from coal as much as possible. It is substantially free of ash, and at the same time contains many components with high fluidity and caking properties. Ashless coal is obtained by extracting coal with a solvent having a high affinity with the coal to obtain an extract from which insoluble components such as ash are separated, and removing the solvent from the extract by evaporation or the like. Manufactured. Accordingly, ashless coal contains a large amount of organic matter that is soluble and soft and soluble in the solvent among the coal components, and is dehydrated in a mixture (slurry) of coal and solvent before extraction and separation.
- ashless coal contains a large amount of volatile matter, has excellent thermal fluidity, and has high caking properties, so it may be contained together with low-grade coal and by-product coal such as weakly caking coal and non-caking coal.
- low-grade coal and by-product coal such as weakly caking coal and non-caking coal.
- the ashless coal has a content (excluding moisture) in the formed blended coal of 3% by weight or more, and further according to the fluidity of the blended coal. Prepared.
- the upper limit of the content of ashless coal is not particularly specified, but if it is too much, the strength is lowered when it is made coke, and it is preferably 10% by weight or less.
- the ashless coal is preferably as small as possible in order to increase the strength of the blended coal and coke, and specifically, the diameter (maximum length) is preferably 1 mm or less. In this invention, quality does not ask
- By-product coal is a by-product generated in the process of producing ashless coal from coal.
- ashless coal is produced by extracting a component soluble in a solvent from coal.
- the insoluble components separated as a residue are further removed from the solvent to become by-product coal. Therefore, the by-product coal has low softening meltability because the organic matter soluble in the solvent and softening and melting is removed as ashless coal with respect to the raw coal, and the ash content insoluble in the solvent is low. Is concentrated from the raw coal to a high concentration of about 10 to 20% by mass.
- the main component of by-product coal is carbon (C), as is the case with coal, and, like ashless coal, it is dehydrated in a mixture (slurry) of coal and solvent before extraction and separation. Therefore, the water content is reduced to about 0.2 to 3% by mass, and it has a sufficient calorific value.
- By-product charcoal has low fluidity and does not have caking properties. If it is contained in a large amount, strength decreases when coke is formed. Therefore, the content (excluding moisture) in the formed blended coal is 8% by weight or less, Furthermore, it is prepared according to the coalification degree and fluidity of coal to be blended, and blending of ashless coal, and is preferably 1% by weight or more.
- the by-product coal is preferably as small as possible in order to increase the strength of the blended coal and coke, and specifically, the diameter (maximum length) is preferably 1 mm or less.
- the ash content in coal refers to a residual inorganic substance when coal is incinerated by heating to 815 ° C. and includes silicic acid, alumina, iron oxide, lime, magnesium oxide, alkali metal oxide, and the like.
- the quality of the raw material coal for obtaining by-product coal does not matter as in the case of ashless coal. The details of the production method of by-product coal will be described later as part of the ashless coal production process.
- the ashless coal and the by-product coal do not need to be manufactured from the same raw material coal, and do not need to be based on the same manufacturing apparatus and method.
- coal About coal, the kind (quality, quality) is selected according to the use of forming blended coal.
- the maximum fluidity MF value log (ddpm)
- the average maximum reflectance Ro value 0.8 to 1.1.
- Coal having an MF value of less than 0.2 and an Ro value of less than 0.8 is too low in quality and unsuitable for coke, or extremely reduces the blending and does not reduce costs.
- coal having an MF value exceeding 2.0 and an Ro value exceeding 1.1 can be produced alone in coke, resulting in high raw material costs.
- the raw material cost can be reduced by applying the medium-low coalification degree medium-low fluidity coal, which is generally difficult to be used as a coke raw material.
- the coal can be contained in an amount of 80% by weight or more, further 85% by weight or more in terms of dry coal.
- coal is good also as dry coal by air drying etc., it may be mixed and shape
- the coal is preferably finely pulverized in the same manner as ashless coal and by-product coal.
- 90% or more of the coal is preferably granular with a diameter of 2 mm or less. It is more preferable that the percentage is more than 1 mm in diameter.
- the particle diameter refers to the maximum length of a particle, and 90% or more is a particle having a diameter of 2 mm or less.
- 90% or more is an eye. It means to pass through.
- the strength of the coal blend can be increased as the particle size of the coal, ashless coal, and by-product coal is smaller, and the strength when coke is further increased. .
- the molding coal according to the present invention contains a small amount of moisture.
- Water becomes a so-called binder (binder) for bonding ashless coal, by-product coal, and coal particles into a lump, and improves the strength of the blended coal.
- the water is not particularly defined, and generally used water such as tap water can be used. Therefore, although it is possible to form other than water as long as it is liquid, water is cheap and easily available, and it is attached to and impregnated with coal itself, and is contained in an amount of about 2 to 8% by mass.
- water is added to the coal, including the amount contained in ashless coal and by-product coal, so that it is 0.5 mass% or more and 13 mass% or less. It is preferable to adjust.
- the moisture amount may be adjusted when coal or the like is mixed.
- water is not particularly defined, and generally used water such as tap water can be used.
- the water content of less than 0.5% by mass is insufficient to collect coal, ashless coal, and by-product coal during molding.
- water exceeds 13 mass%, it will become difficult to form a water film on the surface of each grain of coal, ashless coal, and byproduct coal, and to adhere to each other.
- water is preferably 4 to 9% by mass.
- the method for producing a formed coal blend according to the present invention includes an ashless coal production process for producing ashless coal from coal, a byproduct coal production process for producing byproduct coal from coal, and pulverizing the coal into granules.
- a coal pulverization step, a mixing step of mixing the ashless coal, the by-product coal and the coal to obtain a blended coal, and a molding step of forming the blended coal are performed.
- each step will be described.
- the reformed coal production apparatus 10 includes a solvent storage tank 1, a slurry preparation tank 2 provided with a stirrer, a preheater 3, an extraction tank 4 provided with a stirrer, and a gravity settling tank 5.
- the solid content concentrate receiver 6 and the supernatant receiver 7 are further provided with a pump, a distillation means (not shown), a cooling mechanism, and the like as will be described later.
- a method for producing ashless coal and byproduct coal using the modified coal production apparatus 10 will be described.
- a predetermined amount of coal (raw coal) and a solvent supplied from a solvent storage tank 1 by a pump are respectively supplied to a slurry preparation tank 2.
- coal and a solvent are mixed with the equipped stirrer to prepare a slurry.
- a predetermined amount of the slurry is heated in the preheater 3 and further stirred in the extraction tank 4 for a predetermined time, so that the bonds between the molecules constituting the coal are loosened, causing mild pyrolysis, and the extraction proceeds.
- the solvent-soluble component is separated into a solvent (extract) in which the solvent-soluble component is dissolved and a component insoluble in the solvent (solid content, residue), and is supplied to the gravity settling tank 5.
- the solvent can be removed from the extract or the solid concentrate by a method such as a distillation method or an evaporation method such as a spray drying method.
- Solute (ashless coal) and solid content (by-product charcoal) obtained by removing the solvent are powdery particles having a diameter of about 0.2 to 1.0 mm, or these particles are aggregated as primary particles. In some cases, secondary particles having a diameter of about 50 mm at the maximum are mixed.
- the solvent (recovered solvent) removed by the solid content receiver 6 and the supernatant receiver 7 is recovered and regenerated as necessary, and is added to the slurry preparation tank 2 and the solvent storage tank 1. It may be supplied and reused.
- conditions and the like in each operation will be described.
- the coal used as raw material for ashless coal and by-product coal does not need to be of the same type as the coal mixed with the formed blended coal regardless of the type (quality, quality, brand). Therefore, bituminous coal with a high extraction rate (ashless coal recovery rate) may be used, or cheaper inferior quality coal (subbituminous coal, lignite) may be used. Also, in order to facilitate the extraction and increase the yield of ashless coal, the coal should be pulverized into as small particles as possible before being introduced into the modified coal production apparatus 10 (slurry preparation tank 2).
- the particle diameter (maximum length) is preferably 1 mm or less.
- Solvent is a solvent that has high affinity with coal, that is, dissolves coal.
- solvents include monocyclic aromatic compounds such as benzene, toluene, and xylene, polar solvents such as N-methylpyrrolidone (NMP) and pyridine, and ashless coal (and by-product coal).
- NMP N-methylpyrrolidone
- ashless coal and by-product coal.
- a non-hydrogen donating solvent aromatic solvent mainly composed of a bicyclic aromatic compound. Therefore, in the byproduct charcoal manufacturing process in the present embodiment, it is assumed that an aromatic solvent is used as the solvent.
- An aromatic solvent that is a non-hydrogen-donating solvent is a coal derivative that is mainly a bicyclic aromatic solvent purified from a coal carbonization product. Since this aromatic solvent is relatively stable even under the above-described extraction conditions and has excellent affinity with coal, the proportion of the soluble component of coal extracted into the solvent (extraction rate) is sufficiently high, As a result, the yield of ashless coal is high, and at the same time, by-product coal in which soluble components remain as a by-product as much as possible is obtained.
- the aromatic solvent can be easily recovered from the extract or the like by a method such as distillation, and the recovered solvent can be circulated and reused as it is (see FIG. 1).
- the main components of the aromatic solvent include bicyclic aromatic compounds such as naphthalene, methylnaphthalene, dimethylnaphthalene, and trimethylnaphthalene.
- Other components include naphthalenes having an aliphatic side chain, anthracenes, and fluorenes.
- the hydrogen donating solvent can achieve a higher extraction rate regardless of the type of coal, the yield of ashless coal is further increased.
- the hydrogen donating solvent include partially hydrogenated aromatic compounds such as tetralin and tetrahydroquinoline, or hydrogenated liquefied oil of coal.
- hydrogen donating solvents are generally more expensive than aromatic solvents, and once used for extraction, most of the hydrogen donating capacity is lost. Otherwise, it cannot be reused, which further increases the cost.
- the hydrogen-donating solvent is appropriately selected in consideration of the type of coal and the design as a raw material for the intended use, such as use for coal with a low extraction rate with an aromatic solvent. Further, for example, by using an aromatic solvent and a hydrogen donating solvent in combination, the yield of ashless coal can be increased while suppressing costs (see Patent Document 4).
- the amount of coal to be mixed with the solvent depends on the type of raw coal, but is preferably in the range of 10 to 50% by mass, more preferably in the range of 20 to 35% by mass with respect to the total with the solvent on a dry coal basis.
- the amount of coal is less than 10% by mass, the amount of coal components extracted with respect to the solvent is small, and the productivity is poor.
- the coal exceeds the same amount as the solvent, that is, 50% by mass, the prepared slurry becomes highly viscous and fluidity is deteriorated, making it difficult to move between the processing systems (tanks) and to separate the extract from the residue. There is a case.
- the heating temperature of the slurry is preferably in the range of 300 to 450 ° C, more preferably in the range of 300 to 400 ° C.
- the vapor pressure of the solvent at that temperature is used so that the solvent does not volatilize at the heating temperature. High pressure.
- the pressure is excessively high, the reformed coal production apparatus 10 requires expensive equipment such as high hermeticity, and the operation cost is also increased.
- a range of 1.0 to 2.0 MPa is preferable depending on the temperature at the time of extraction and the vapor pressure of the solvent.
- solvents and coal components especially components that are soluble in the solvent, may ignite when they come into contact with oxygen. It is preferable to carry out in an inert gas atmosphere.
- the extraction time (time within the heating temperature range of the slurry) is a standard until reaching the dissolution equilibrium, but if it is to be realized, productivity is lowered. Therefore, it is preferable to complete the extraction when the increase in the extraction rate is apparently stopped or considerably slowed down.
- Such a preferable extraction time varies depending on conditions such as the particle size of coal and the type of solvent, but is usually about 10 to 60 minutes. If the extraction time is less than 10 minutes, the extraction often does not proceed sufficiently. On the other hand, if the extraction time exceeds 60 minutes, the extraction is difficult to proceed further, and therefore the productivity is poor.
- coal crushing process In the coal pulverization step, the coal mixed with the formed blended coal is pulverized into granules by a conventional method.
- ashless coal and by-product coal when coarse secondary particles as described above are mixed, the ashless coal and by-product coal are mixed in the same manner as described above. And may be pulverized together.
- the blended coal is molded into a predetermined three-dimensionally shaped lump to form a blended coal.
- the blended coal can be molded by compression molding using a molding machine or two-roll briquette molding, which is also applied in molding of carbon materials such as ashless coal.
- the pressure applied to the coal blend for molding is not particularly defined, and may be set according to the molding machine or the like.
- a blended coal with higher temperature is easier to mold due to the fluidity of ashless coal, and the strength is further improved.
- coal, ashless coal and by-product coal are strongly linked to each other.
- a suitable coal blend is obtained.
- the coal blend is preferably 80 ° C. or higher, more preferably in the range of 100 to 150 ° C.
- Such a temperature shall be at the time when the blended coal is filled in the molding die. Therefore, it may be molded by heating the blended coal or the coal before mixing with a heater or the like so that the temperature at the time of molding is 80 ° C. or higher, and filling the mold, for example, mixing blended coal Or may be heated simultaneously with the adjustment of moisture, or may be heated while forming.
- the heating temperature of the blended coal is preferably 200 ° C. or less. .
- the coke according to the present invention is obtained by dry-distilling a coal mixture obtained by mixing the above-described coal blend according to the present invention with coal for other coke raw materials under general conditions as described later.
- the content of the blended coal according to the present invention in the coal mixture is preferably 10 to 30% by mass.
- Examples of coal for coke feed include strong caking coal, semi-caking caking coal, weak caking coal, and non-caking caking coal commonly used for coke feed.
- the pulverization is performed so that, for example, 80% or more has a particle diameter of 3 mm or less.
- the blended coal according to the present invention is formed into a desired shape and has a certain strength, so that it is coke that retains the shape by being carbonized together with the coal for the coke raw material.
- the blended coal is pulverized to the same size as the coal for the coke raw material.
- coal, ashless coal, and byproduct coal are strongly bound to each other by molding, and this tie persists even when pulverized, so it does not affect the effect of mixing the coal blend according to the present invention.
- the coke obtained by dry distillation can be directly put into a blast furnace for the production of pig iron.
- the conditions for dry distillation are not particularly limited, and normal dry distillation conditions in coke production using a coke oven can be adopted.
- the volume of 10 to 50 in a chamber furnace charged with about 30 tons per gate. % Of the coal mixture is charged and subjected to dry distillation.
- it is 950 ° C. or higher, more preferably 1000 ° C. or higher, preferably 1200 ° C. or lower, more preferably 1050 ° C. or lower, preferably 8 hours or longer, more preferably 10 hours or longer, preferably 24 hours or shorter. More preferably, it is carried out by carbonization for 20 hours or less.
- 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 solid concentrate by a distillation method to obtain by-product coal. .
- the solvent was separated and recovered from the supernatant by distillation to obtain ashless coal.
- the water content of the obtained ashless coal and by-product coal was 1.5% by mass, respectively.
- Each 1 kg of these ashless coal and by-product coal was pulverized so that the particle size (maximum length) would be 1 mm or less.
- this mixture is filled in a mold having a diameter of 20 mm with 6 g per piece, and is heated to 120 ° C. and applied with a pressure of 2 ton / cm 2 to form a cylindrical tablet. did.
- Abrasion test An abrasion test was performed as an index for suppressing dust generation. First, 20 cokes were accommodated in a cylindrical container having a diameter of 250 mm and rotated at 30 RPM for 10 minutes. Next, the coke taken out from the cylindrical container was selected with a sieve having an opening of 5.66 mm, and the portion that passed through the sieve was weighed. The weight ratio (%) of the portion that passed through (powder) to the entire coke was calculated and is shown in Table 1 as the powder generation rate. The acceptance standard for suppressing dust generation was a powder generation rate of 10% or less.
- sample no. Nos. 1, 5, and 7 are examples that satisfy the scope of the present invention. Although it became lower than 8, what has sufficient intensity
- sample No. Nos. 2, 3, and 6 have low strength due to lack of ashless coal, and in particular, Sample Nos. That do not contain ashless coal. 2 was low.
- Sample No. No. 4 had low strength due to excessive by-product coal.
- blended coal according to the present invention fuel and coke raw material suitable for storage and transportation can be obtained. According to the coke which concerns on this invention, it becomes sufficient intensity
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Abstract
Description
しかしながら、副生炭は、石炭から粘結成分である無灰炭を取得した後に残る石炭成分であるから流動性や粘結性に乏しく、これをコークス原料に使用すると、少量含有させただけでもコークス強度の低下が著しいことが判明した。
(1)石炭における溶剤に可溶な成分を含む無灰炭と、石炭から前記溶剤に可溶な成分を除去して得られる副生炭と、を粒状の石炭に混合した配合炭を含む成形配合炭であって、
前記配合炭は、前記無灰炭を3重量%以上、前記副生炭を8重量%以下、前記粒状の石炭を残部として含有することを特徴とする成形配合炭。
(2)前記粒状の石炭は、90%以上が径2mm以下であることを特徴とする(1)に記載の成形配合炭。
(3)前記粒状の石炭は、60%超が径1mm以下であることを特徴とする(2)に記載の成形配合炭。
このように石炭を所定の特性に規定することで、コークス原料には不適な石炭であっても、乾留して十分な強度のコークスに製造される成形配合炭となる。
このように、所定の配合の成形炭を使用することで、副生炭を含有しても強度が十分かつ均一なコークスとなり、原料コストの低いコークスが得られる。
前記無灰炭製造工程において分離された前記残渣から前記溶剤を除去して副生炭を製造する副生炭製造工程と、
石炭を粉砕して粒状にする石炭粉砕工程と、
前記粒状にした石炭に前記無灰炭と前記副生炭とを混合して、前記無灰炭を3重量%以上、および前記副生炭を8重量%以下含有する配合炭を得る混合工程と、
前記配合炭を成形する成形工程と、を含むことを特徴とする成形配合炭の製造方法。
(7)前記成形工程において、前記配合炭の温度が80~200℃であることを特徴とする(6)に記載の成形配合炭の製造方法。
このように、配合炭がすでに成形されているため、銑鉄の製造に使用可能なコークスを製造することができる。
〔成形配合炭〕
本発明に係る成形配合炭は、無灰炭および副生炭を石炭に混合して配合炭として、所定の立体形状の塊に成形して得られ、石炭や無灰炭等のそれぞれ単独の場合と同様に燃料やコークス原料の配合炭として利用される。成形配合炭の形状および大きさは特に規定されず、用途に応じて設計される。以下、成形配合炭の原料である無灰炭、副生炭、および石炭について説明する。
無灰炭は、石炭から灰分と非溶解性石炭成分とをできるだけ除去した改質炭で、実質的に灰分を含まないと同時に、流動性、粘結性の高い成分を多く含有する。無灰炭は、石炭を、当該石炭と親和性の高い溶剤で抽出することで、灰分等の不溶な成分を分離した抽出液を得て、この抽出液から溶剤を蒸発法等によって除去して製造される。したがって、無灰炭は、石炭成分のうち、溶剤に可溶な軟化溶融性がある有機物を多く含有し、さらに、抽出、分離前の石炭と溶剤の混合物(スラリー)の状態で脱水されているため、水分が0.2~3質量%程度に減少している。したがって、無灰炭は、揮発分を多く含有し、熱流動性に優れ、粘結性が高いため、弱粘結炭や非粘結炭等の低品位炭および副生炭と共に含有されても、特に後記するように加熱して成形されることで、ある程度の強度を有し、粉塵の発生も抑えられて、保管等に好適な成形配合炭となり、さらに、乾留時にこれらの低品位炭に粘結性を付与して、強度の高いコークスとすることができる。このようにコークスとしたときに十分な強度を付与するため、無灰炭は、成形配合炭における含有量(水分を除く)を3重量%以上とし、さらに配合される石炭の流動性に応じて調製される。無灰炭の含有量の上限は特に規定しないが、多過ぎるとコークスとしたときに却って強度を低下させるため、10重量%以下とすることが好ましい。また、無灰炭は、成形配合炭およびコークスの強度を高くするためにできるだけ小さい粒状であることが好ましく、具体的には径(最大長さ)1mm以下とすることが好ましい。本発明において、無灰炭を得るための原料石炭については、品質を問わない。無灰炭の製造方法の詳細については、後記する。
副生炭は、石炭から無灰炭を製造する過程で生じる副生物である。前記した通り、無灰炭は、石炭から溶剤に可溶な成分を抽出して製造される。一方、残渣として分離された不溶な成分が、さらに溶剤を十分に除去されて副生炭となる。したがって、副生炭は、原料石炭に対して、溶剤に可溶な軟化溶融性がある有機物が無灰炭となって除去されているため、軟化溶融性は低く、また、溶剤に不溶な灰分が原料石炭から濃縮されて10~20質量%程度の高濃度になる。ただし、副生炭は、その主成分は原料石炭と同様に炭素(C)であり、また、無灰炭と同様に、抽出、分離前の石炭と溶剤の混合物(スラリー)の状態で脱水されているので、水分が0.2~3質量%程度に減少していて、発熱量を十分に有している。副生炭は、流動性が低く、粘結性がないために、多く含有するとコークスとしたときに強度が低下するので、成形配合炭における含有量(水分を除く)を8重量%以下とし、さらに配合される石炭の石炭化度や流動性、ならびに無灰炭の配合に応じて調製され、好ましくは1重量%以上である。また、副生炭は、成形配合炭およびコークスの強度を高くするためにできるだけ小さい粒状であることが好ましく、具体的には径(最大長さ)1mm以下とすることが好ましい。なお、石炭における灰分とは、石炭を815℃に加熱して灰化したときの残留無機物を指し、ケイ酸、アルミナ、酸化鉄、石灰、酸化マグネシウム、アルカリ金属酸化物等である。本発明において、副生炭を得るための原料石炭については、無灰炭と同様に品質を問わない。副生炭の製造方法の詳細については、無灰炭の製造工程の一環として後記する。また、無灰炭と副生炭とは、同じ原料石炭から製造されたものでなくてよく、同じ製造装置および方法によらなくてよい。
石炭については、その種類(品位、品質)は成形配合炭の用途に応じて選択される。特にコークス原料の配合炭とする場合は、最大流動度MF値(log(ddpm)):0.2~2.0、平均最大反射率Ro値:0.8~1.1であることが好ましい。MF値が0.2未満、Ro値が0.8未満の石炭では質が低過ぎて、コークスとするには不適当で、あるいは配合を極度に低減することになり、コスト低減にならない。反対に、MF値が2.0超、Ro値が1.1超の石炭は、単独でコークスに製造可能であり、原料コストが高くなる。すなわち瀝青炭の中で、一般的にコークス原料とすることが困難とされる中低石炭化度中低流動性炭を適用することで、原料コストを低減することができる。また、これらの石炭化度、流動性の範囲から異なる2種類以上の石炭を適用してもよい。成形配合炭において、石炭は、乾燥炭に換算して80重量%以上、さらには85重量%以上含有することができる。なお、石炭は、風乾等により乾燥炭としてもよいが、水分を含んだ状態で無灰炭および副生炭と混合、成形されてもよい。
本発明に係る成形配合炭の製造方法は、石炭から無灰炭を製造する無灰炭製造工程と、石炭から副生炭を製造する副生炭製造工程と、石炭を粉砕して粒状にする石炭粉砕工程と、前記無灰炭と前記副生炭と前記石炭を混合して配合炭を得る混合工程と、前記配合炭を成形する成形工程と、を行う。以下、各工程について説明する。
無灰炭製造工程は、石炭を溶剤で抽出し、残渣を分離した抽出液から前記溶剤を除去して無灰炭を製造する。一方、副生炭製造工程は、前記残渣のスラリーから前記溶剤を除去して副生炭を製造する。すなわち副生炭は、石炭から無灰炭を製造する過程で生じる副生物である。そこで、本実施形態では、無灰炭製造工程と副生炭製造工程とを、一工程として説明する。なお、副生炭については同等の成分であれば、無灰炭の製造における副生物として得られたものでなくてもよく、無灰炭と副生炭とは同じ工程で製造されたものでなくてよい。無灰炭を製造する方法は、例えば、特許文献2~4に記載の方法を用いることができる。以下に、図1に示す無灰炭および副生炭を得ることができる改質炭製造装置の一例を参照して説明する。
石炭粉砕工程は、成形配合炭に混合される石炭を、常法で粒状に粉砕する。また、無灰炭や副生炭についても、前記したような粗大な二次粒子が混在する場合等は、同様に粉砕したり、無灰炭と副生炭とを前記で規定した配合で石炭に混合して、一緒に粉砕してもよい。
混合工程は、無灰炭、副生炭、石炭、さらに必要に応じて水を混合して混合物(配合炭)を得る。無灰炭、副生炭、石炭の配合、および水の含有量は、それぞれ前記の成形配合炭についての説明の通りであり、特に水は、前記した通り、石炭、無灰炭、および副生炭の水分量を勘案して、不足分を添加して調整する。例えば公知のミキサーに、無灰炭、副生炭、および予め粉砕した石炭をそれぞれホッパーから投入して、スプレー等で水を添加しながら攪拌することにより、無灰炭や副生炭の二次粒子が容易に粉砕される上、無灰炭および副生炭が無灰炭製造工程および副生炭製造工程で製造された直後、すなわち溶剤の除去のために200℃を超える温度に加熱された直後であっても、適度に冷却される。このような無灰炭や副生炭を高温の状態で水分調整する場合は、後続の成形工程までに蒸発する分も勘案して水を添加する。
成形工程は、前記配合炭を所定の立体形状の塊に成形して成形配合炭とする。配合炭の成形は、例えば無灰炭等の炭素材料の成形においても適用されている、成形機を使用した圧縮成形や、2ロール式ブリケット成形によってすることができる。成形のために配合炭にかける圧力は特に規定されず、成形機等に応じて設定すればよい。
〔コークス〕
本発明に係るコークスは、前記の本発明に係る成形配合炭を他のコークス原料用の石炭と混合した石炭混合物を、後記するように一般的な条件で乾留して得られる。石炭混合物における本発明に係る成形配合炭の含有量は、10~30質量%とすることが好ましい。また、コークス原料用の石炭は、コークス原料に一般的に使用される強粘結炭、準強粘結炭、あるいは弱粘結炭、非微粘結炭が挙げられ、これらの石炭のみでコークスを製造する場合と同様に、例えば80%以上が粒径3mm以下になるように粉砕される。前記した通り、本発明に係る成形配合炭は所望の形状に成形され、かつ一定の強度を有しているため、コークス原料用の石炭と共に乾留されることにより当該形状を保持したコークスとなる。なお、成形配合炭は、コークス原料用の石炭と大きさや形状を揃える必要はなく、大きさによっては成形された形状のままでコークス原料用の石炭と混合して乾留されてもよい。ただし、成形配合炭がコークス原料用の石炭(粉砕されたもの)と比較して相当に大きい場合は、コークス原料用の石炭の粒との流れ性の違いにより、コークス炉の炉壁部分に偏析する等の不具合を生じ易いため、成形配合炭はコークス原料用の石炭と同程度の大きさに粉砕されることが好ましい。前記した通り、成形配合炭は、石炭、無灰炭、副生炭が成形により互いに強く結び付き、この結び付きは粉砕されても持続するので、本発明に係る成形配合炭を混合する効果に影響しない。乾留して得られたコークスは、そのまま銑鉄の製造のために高炉に投入することができる。
本発明において、乾留の条件は特に限定されるものではなく、コークス炉を使用したコークス製造における通常の乾留条件を採用でき、例えば1門30トン程度を装入する室炉に容積の10~50%程度の前記石炭混合物を装入して乾留する。好ましくは950℃以上、より好ましくは1000℃以上であって、好ましくは1200℃以下、より好ましくは1050℃以下の温度で、好ましくは8時間以上、より好ましくは10時間以上、好ましくは24時間以下、より好ましくは20時間以下乾留して行う。
(無灰炭および副生炭の製造)
まず、以下の方法により、無灰炭と副生炭を製造した。
オーストラリア産瀝青炭を原料石炭とし、この原料石炭(乾燥炭に換算)と、4倍量(20kg)の溶剤(1-メチルナフタレン(新日鉄化学社製))を混合してスラリーを調製した。このスラリーを、窒素を導入して1.2MPaに加圧した状態で、内容積30Lのバッチ式オートクレーブ中370℃、1時間の条件で抽出処理した。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液と固形分濃縮液とに分離し、固形分濃縮液から蒸留法で溶剤を分離・回収して、副生炭を得た。一方、上澄液からも蒸留法で溶剤を分離・回収して、無灰炭を得た。得られた無灰炭および副生炭の水分はそれぞれ1.5質量%であった。これらの無灰炭および副生炭各1kgを、粒径(最大長さ)が1mm以下になるように粉砕した。
配合炭に混合する石炭として水分6.7質量%のオーストラリア産瀝青炭(最大流動度MF値(log(ddpm))0.5、平均最大反射率Ro値1.01)を粒径が1mm以下になるように粉砕し、無灰炭および副生炭を表1に示す配合比(%)で混合し、全体量に対してさらに0.5質量%となるように水を加えて、Vミキサーで10分間混合して混合物(配合炭)を調整した。なお、瀝青炭の水分は、石炭JIS(JIS M8812)に準じて測定した値である。
(圧壊試験)
強度の指標として圧壊試験を行った。コークスの円柱形状の軸に垂直の方向(径方向)に圧縮荷重をかけて、破壊に至る荷重を測定した。測定した荷重を圧壊荷重として、表1に示す。強度の合格基準は、圧壊荷重が100kg以上とした。
粉塵発生の抑制の指標としてアブレージョン試験を行った。まず、直径250mmの円筒容器にコークス20個を収容し、30RPMで10分間回転させた。次に、円筒容器から出したコークスを目開き5.66mmの篩で選別して、目を通った分を秤量した。この、目を通った分(粉体)のコークス全体に対する重量比(%)を算出し、粉体発生率として表1に示す。粉塵発生抑制の合格基準は、粉体発生率が10%以下とした。
本出願は、2012年2月29日出願の日本特許出願(特願2012-044219)に基づくものであり、その内容はここに参照として取り込まれる。
1 溶剤貯蔵槽
2 スラリー調製槽
3 予熱器
4 抽出槽
5 重力沈降槽
6 固形分濃縮液受器
7 上澄液受器
Claims (8)
- 石炭における溶剤に可溶な成分を含む無灰炭と、石炭から前記溶剤に可溶な成分を除去して得られる副生炭と、を粒状の石炭に混合した配合炭を含む成形配合炭であって、
前記配合炭は、前記無灰炭を3重量%以上、前記副生炭を8重量%以下、前記粒状の石炭を残部として含有することを特徴とする成形配合炭。 - 前記粒状の石炭は、90%以上が径2mm以下であることを特徴とする請求項1に記載の成形配合炭。
- 前記粒状の石炭は、60%超が径1mm以下であることを特徴とする請求項2に記載の成形配合炭。
- 前記粒状の石炭は、最大流動度MF値(log(ddpm))が0.2~2.0、平均最大反射率Ro値が0.8~1.1であることを特徴とする請求項1に記載の成形配合炭。
- 請求項4に記載の成形配合炭を含む石炭混合物を乾留してなることを特徴とするコークス。
- 石炭を溶剤で抽出して、抽出液と残渣とを分離し、前記抽出液から前記溶剤を除去して、前記石炭における前記溶剤に可溶な成分を含む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において分離された前記残渣から前記溶剤を除去して副生炭を製造する副生炭製造工程と、
石炭を粉砕して粒状にする石炭粉砕工程と、
前記粒状にした石炭に前記無灰炭と前記副生炭とを混合して、前記無灰炭を3重量%以上、および前記副生炭を8重量%以下含有する配合炭を得る混合工程と、
前記配合炭を成形する成形工程と、を含むことを特徴とする成形配合炭の製造方法。 - 前記成形工程において、前記配合炭の温度が80~200℃であることを特徴とする請求項6に記載の成形配合炭の製造方法。
- 請求項6に記載の成形配合炭の製造方法により製造された成形配合炭を含む石炭混合物を乾留する工程を含むコークスの製造方法。
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Cited By (13)
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WO2015037583A1 (ja) * | 2013-09-11 | 2015-03-19 | 株式会社神戸製鋼所 | 炭素材料の製造方法、および炭素材料 |
JP2015054792A (ja) * | 2013-09-11 | 2015-03-23 | 株式会社神戸製鋼所 | 炭素材料の製造方法、および炭素材料 |
US9751764B2 (en) | 2013-09-11 | 2017-09-05 | Kobe Steel, Ltd | Carbon material production method and carbon material |
RU2628606C1 (ru) * | 2013-09-11 | 2017-08-21 | Кабусики Кайся Кобе Сейко Се (Кобе Стил, Лтд.) | Способ производства углеродного материала и углеродный материал |
AU2014332906B2 (en) * | 2013-10-09 | 2017-02-02 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Ashless coal production method |
CN105612245A (zh) * | 2013-10-09 | 2016-05-25 | 株式会社神户制钢所 | 无灰煤的制造方法 |
JP2015074723A (ja) * | 2013-10-09 | 2015-04-20 | 株式会社神戸製鋼所 | 無灰炭の製造方法 |
WO2015053332A1 (ja) * | 2013-10-09 | 2015-04-16 | 株式会社神戸製鋼所 | 無灰炭の製造方法 |
US9752088B2 (en) | 2013-10-09 | 2017-09-05 | Kobe Steel, Ltd. | Ashless coal production method |
CN105612245B (zh) * | 2013-10-09 | 2018-09-11 | 株式会社神户制钢所 | 无灰煤的制造方法 |
EP3150687A4 (en) * | 2014-05-28 | 2018-01-03 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method for manufacturing blast furnace coke, and blast furnace coke |
JP2017008247A (ja) * | 2015-06-24 | 2017-01-12 | 株式会社神戸製鋼所 | 副生炭発塵抑制方法、及び低発塵性副生炭製造方法 |
CN115093869A (zh) * | 2022-03-22 | 2022-09-23 | 中冶焦耐(大连)工程技术公司 | 一种富氢高炉用高反应性高强度非均质焦炭及制备方法 |
Also Published As
Publication number | Publication date |
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TWI485237B (zh) | 2015-05-21 |
TW201402801A (zh) | 2014-01-16 |
KR20140124800A (ko) | 2014-10-27 |
EP2821461A1 (en) | 2015-01-07 |
EP2821461A8 (en) | 2015-03-11 |
CN104136578A (zh) | 2014-11-05 |
AU2013226908B2 (en) | 2015-07-23 |
JP2013181062A (ja) | 2013-09-12 |
AU2013226908A1 (en) | 2014-08-21 |
EP2821461A4 (en) | 2015-11-11 |
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