KR20140124800A

KR20140124800A - Coal blend briquette and process for producing same, and coke and process for producing same

Info

Publication number: KR20140124800A
Application number: KR1020147023876A
Authority: KR
Inventors: 마키 하마구치; 노리유키 오쿠야마; 고지 사카이; 다케하루 다나카; 다카노리 오카; 다카히로 시시도; 가즈히데 이시다; 아츠시 고타니
Original assignee: 가부시키가이샤 고베 세이코쇼
Priority date: 2012-02-29
Filing date: 2013-02-28
Publication date: 2014-10-27
Also published as: EP2821461A1; EP2821461A4; TWI485237B; CN104136578A; JP2013181062A; AU2013226908A1; EP2821461A8; AU2013226908B2; WO2013129607A1; TW201402801A

Abstract

An unburned coal containing a component soluble in a solvent in coal, and a blended coal obtained by mixing a co-produced coal obtained by removing a soluble component from the coal from the coal and by-produced coal. The blend contains 3 wt% or more of the ashless coal, 8 wt% or less of the by-product, and the granular coal as a remaining amount.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a molded composite carbon and a method for producing the same,

The present invention relates to an ashless coal obtained by extracting coal with a solvent and a shaped coal using the by-product as a by-product, and a method for producing the same. In particular, the present invention relates to a blended coal as a coke raw material, .

Coke used in the blast furnace steel requires various characteristics such as the size and distribution of the lumps necessary for securing a constant mechanical strength, reactivity, apparent density, and further air permeability, which are not easily broken in the blast furnace. Coarse coal, which is generally called " coking coal " and has a high degree of cohesion, fluidity, or degree of coagulation and is high in quality and high in cost compared to fuel coals for general boilers, is used as a raw material for coke. In recent years, attempts have been made to use lower-cost and lower-quality coal as a raw material for coke in the background of persecution of resources and price hikes. For example, there has been a variety of techniques for blending low- .

Further, in some cases, coal is used as a reformed coal modified for effective use of resources. Particularly in recent years, development of so-called non-coal (hypercall) has been actively promoted from the viewpoint of high efficiency utilization as fuel. The non-ash coal is a coal ash that has removed most of the ash from the coal. It contains substantially no ash (target 200 mass ppm or less), and from the relatively low-molecular-weight constituent, And has a broad molecular weight distribution up to high molecular weight components. Thereby exhibiting high fluidity under heating. Some coal may exhibit thermoplasticity at a high temperature of about 400 ° C, such as coking coal, but the ashless coal generally melts at 200 to 300 ° C (regardless of the quality of the raw coal) (softening and melting property). Accordingly, application of this property to develop a binder for coke making has been progressing (see, for example, Patent Document 1), and in recent years, it has been attempted to produce a carbon material by using the ashless coal as a raw material.

The ash coal is produced by extracting coal at a high temperature with a solvent having high affinity with coal and precipitating ash that is not dissolved in the solvent as a residue and removing the solvent from the separated extract (liquid portion) as a supernatant See Patent Documents 2 to 4). On the other hand, in the remaining portion (non-liquid portion) from which the extract is separated, the solvent is recovered by the distillation method or the evaporation method (see, for example, Patent Document 3), and the residue containing insoluble components such as ash Occurs.

Japanese Patent Application Laid-Open No. 2008-174592 Japanese Patent No. 3,198,305 Japanese Patent No. 4,061,351 Japanese Patent No. 4,708,463

This by-product is called a by-product and contains a lot of ash but since the water is removed during the production process of the ash-tan, it can be used for various fuels because it has sufficient calorific value. In addition, since the by-product carbon is derived from a general carbon which is not normally used for the coke raw material, it is considered that the coke can be produced at a lower cost if it can be used as the raw material for the coke.

However, since the by-produced coal is a coal component remaining after obtaining the ash-free component ash component from the coal, the fluidity and the cohesiveness are insufficient, and when it is used for the coke raw material, it has been found that the decrease in the coke strength is remarkable even if a small amount is contained .

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a molded composite excellent in handling and convenience with respect to compounded carbon mixed with by-product carbon in order to more effectively utilize the by- And a method of producing the coke which has a sufficient strength even when it contains carbon dioxide which is low in flowability and low degree of cohesion and is dried as coke raw material.

The present invention provides the following formulated coal, coke, a method for producing molded composite coal, and a method for producing coke.

(1) An unshaped carbon containing unburnt carbon containing a soluble component in a solvent in coal, and a blended carbon obtained by mixing a coal ash by-produced by removing a soluble component from coal,

Characterized in that the blend contains 3 wt% or more of the ashless coal, 8 wt% or less of the by-product, and the granular coal as a remaining amount.

(2) The shaped mixture coal according to (1), wherein at least 90% of the granular coal has a diameter of 2 mm or less.

(3) The shaped mixture coal according to (2), wherein the granular coal has a diameter of 1 mm or less in an amount of more than 60%.

By specifying the combination of the ashless coal and the by-product carbon as described above, the cohesion of the coal or the like, which is difficult to bind as a molded product, becomes strong and the coal, the ashless coal and the by-produced coal are strongly bonded to each other by molding. Resulting in a molding compounding coke which has a sufficient strength.

(4) The coal according to any one of (1) to (3), wherein the granular coal has a maximum flow MF value (log (ddpm)) of 0.2 to 2.0 and an average maximum reflectance Ro value of 0.8 to 1.1 &Lt; / RTI >

By defining the coal with the predetermined characteristics in this way, even if the coal is unsuitable for the coke raw material, it can be formed into a shaped mixture made of coke of sufficient strength.

(5) A coke comprising a coal mixture containing the shaped mixture as described in (4).

Thus, by using a predetermined amount of briquette, it is possible to obtain a coke having a sufficient strength and a uniform coke even if the by-product is contained and having a low raw material cost.

(6) an ash-free coal manufacturing process of extracting coal with a solvent, separating the extract and the residue, removing the solvent from the extract, and producing an ashless coal containing a soluble component in the solvent of the coal ,

A byproduct carbon manufacturing process for producing by-product carbon by removing the solvent from the separated residue in the ashless carbon manufacturing process;

A coal pulverizing step of pulverizing coal into a granular form,

Mixing the granular coal and the by-product coal to the granular coal to obtain a blend containing 3 wt% or more of the ashless coal and 8 wt% or less of the by-product;

And a molding step of molding the compounded carbon.

(7) The method of producing a molded composite as recited in (6), wherein the temperature of the compounding carbon in the molding step is 80 to 200 占 폚.

By performing such a procedure, the coal can be appropriately mixed with the ashless coal or the like by pulverizing the coal into a granular form, so that the binding at the time of molding becomes strong. In addition, by specifying the combination of the ashless coal and the by-product carbon, a molded composite coal to be a raw material of coke having sufficient strength can be produced. Further, by setting the blended carbon to a predetermined temperature at the time of molding, the strength of the blended carbon is improved and the surface layer is hardly peeled off or removed, and furthermore, the coal, the ashless coal and the by- It becomes a raw material of a suitable coke.

(8) A method for producing a coke comprising a step of dry-calcining a coal mixture comprising a shaped mixture produced by the method for producing a shaped mixture according to (6) or (7).

Since the compounded coal is already molded in this manner, a coke usable for the production of pig iron can be produced.

According to the molded composite according to the present invention, fuel and coke raw material suitable for storage and transportation can be obtained. According to the coke of the present invention, by using the by-products, sufficient strength is obtained at a low raw material cost. Further, according to the method for producing a molded composite coal and the method for producing a coke according to the present invention, since the by-products can be effectively used, economical efficiency in the production of ashless coal is improved.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view schematically showing a modified carbon manufacturing apparatus for producing a by-product carbon as a raw material for a molding compound according to the present invention. Fig.

The molded composite carbon according to the present invention and its production method will be described in detail.

[Molding compounding]

The shaped mixture according to the present invention can be obtained by mixing the ashless coal and the by-produced coal into coal to form a blend of a predetermined three-dimensional shape, and as in the case of the case of each of coal and non- It is used as a blend of coke raw materials. The shape and size of the molding compounding are not specifically defined, but are designed according to the use. Hereinafter, the ashless coal, by-product coal, and coal, which are raw materials for forming blend, will be described.

(Non-ash: not less than 3% by weight)

Non-ash coal is a reformed coal that removes ash and inferior coal components from coal as much as possible. It contains substantially ash and contains many components with high fluidity and high cohesion. The unburned coal is produced by extracting coal with a solvent having a high affinity for the coal to obtain an extract which is obtained by separating insoluble components such as ash, and removing the solvent from the extracted coal by evaporation or the like. Therefore, since the unburned coal contains a large amount of soft matter-soluble organic matter soluble in the solvent and dehydrated in the state of a mixture (slurry) of coal and solvent before extraction and separation, 3% by mass. Therefore, since the ashless coal contains a large amount of volatile matter, is excellent in thermal fluidity, and has a high degree of cohesion, even if it is contained together with low-grade coal and by-product coal such as weak coking coal and coking coal, It is possible to obtain a coke having a certain degree of strength, suppress the generation of dust, to be a molding compound suitable for storage, etc., and to give these low-grade coals a degree of cohesion at the time of carbonization. In order to impart a sufficient strength to coke, the ashless coal is produced in accordance with the fluidity of the coal to be incorporated and the content (excluding moisture) in the molded composite coal is 3 wt% or more. The upper limit of the content of ash carbon is not specifically defined, but if it is too large, the strength is lowered in the case of coke, so that the content is preferably 10 wt% or less. In order to increase the strength of the molded composite coal and the coke, the ashless coal is preferably as small as possible, and more specifically, it is preferable to set the diameter (maximum length) to 1 mm or less. In the present invention, the quality of raw coal for obtaining ashless coal is not required. Details about the manufacturing method of the ash-tan are described later.

(By-product carbon: 8 wt% or less)

By-product is a by-product from the process of manufacturing ash from coal. As described above, ashless coal is produced by extracting components soluble in a solvent from coal. On the other hand, the insoluble component separated as the residue is further removed sufficiently to become a by-product. Therefore, since the organic coal having the softening and melting ability soluble in the solvent is removed from the raw coal by the ashless coal, the by-product coal is low in the softening and melting property, and the ashes insoluble in the solvent are concentrated from the raw coal to 10 to 20 mass % &Lt; / RTI > However, since the main component is carbon (C) like raw coal and dehydrated in the state of a mixture (slurry) of coal and solvent before extraction and separation as in the ashless coal, the water content is 0.2 to 3 mass %, Which is sufficient to generate heat. Since the by-product is low in fluidity and does not have a high degree of cohesion, if it is contained in a large amount, the strength of the coke is lowered. Therefore, the content (excluding water content) in the molding compound coal is 8 wt% or less, It is produced according to the coalification degree, the fluidity, and the combination of the unburned coal, and is preferably 1% by weight or more. In order to increase the strength of the molded composite coal and the coke, it is preferable that the by-product be as small as possible. Specifically, it is preferable to set the diameter (maximum length) to 1 mm or less. The ash in coal refers to residual inorganic matter when coal is heated to 815 DEG C and is converted into silicic acid, alumina, iron oxide, lime, magnesium oxide, alkali metal oxide, and the like. In the present invention, the raw coal for obtaining the by-products is not required to be of the same quality as the non-coal. Details of the production method of the by-product carbon are described later as a part of the manufacturing process of the ash-free carbon. Further, the ash and coal may not be produced from the same raw coal, and may not be subjected to the same production apparatus and method.

(Coal)

Regarding coal, the kind (grade, quality) is selected according to the use of the molding compounding coal. Particularly in the case of using a blend of coke raw materials, it is preferable that the maximum flow MF value (log (ddpm)) is 0.2 to 2.0 and the average maximum reflectance Ro value is 0.8 to 1.1. If the MF value is less than 0.2 and the Ro value is less than 0.8, the quality of the coal is too low to make coke, or the mixture is extremely reduced, and the cost can not be reduced. Conversely, coal having an MF value of more than 2.0 and an Ro value of more than 1.1 can be produced by coke alone, and the raw material cost becomes high. That is, among the bituminous coal, it is possible to reduce the cost of the raw material by applying the intermediate low carbon steel which is generally difficult to make into the coke raw material. Further, two or more kinds of coal different from the range of coalification degree and fluidity may be applied. In the molding compounded coal, coal may be contained in an amount of 80% by weight or more, more preferably 85% by weight or more in terms of dry charcoal. The coal may be dry coal by air drying or the like, but it may be mixed and formed with ashless coal and by-product coal in a state containing water.

More preferably, at least 90% of the coal is a granular material having a diameter of 2 mm or less and more than 60% is a diameter 1 Mm or less. In this specification, the particle diameter refers to the maximum length of a particle, and 90% or more of particles having a diameter of 2 mm or less means that 90% or more of the particles pass through the eye when the coal is squeezed on a sieve having a size of 2 mm It means. In the molded composite according to the present invention, the smaller the particle diameter of the coal, the unburned coal and the by-product, the higher the strength of the molded composite coal and the higher the strength when coke is produced.

The molded composite according to the present invention preferably contains a very small amount of water. The water becomes a so-called binder (binder) for forming particles of non-coal, by-product, and coal to adhere to each other to improve the strength of the molded composite. The water is not particularly defined, and generally used water such as tap water can be used. Therefore, although water can be formed in addition to water in the case of a liquid, water is inexpensive and easy to obtain, and is contained in the coal itself in an amount of about 2 to 8% by mass. In the molding compounded coal, it is preferable to add water to the coal so that the amount of water is 0.5% by mass or more and 13% by mass or less, inclusive of the substance contained in the ashless coal and the by-product. In addition, the amount of water added to the blend, that is, the amount of water before molding is substantially the same even after being molded into the molding compound, so that the water content may be adjusted when mixing coal or the like. Such water is not particularly defined, and water generally used such as tap water can be used. When the amount of water is less than 0.5% by mass in the molding compounded coal, it is insufficient to integrate coal, non-coal, and by-products at the time of molding. On the other hand, when the content of water exceeds 13 mass%, it becomes difficult to form a water film on the surfaces of the particles of coal, non-coal, and by-product, and to adhere to each other. The water content is preferably 4 to 9% by mass.

[Process for producing molding compound]

A method for producing a molded composite coal according to the present invention comprises a step of producing an ash-free coal from coal, a step of producing by-product carbon from the coal, a step of pulverizing coal into a granulated coal, 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 molding the blended coal. Hereinafter, each step will be described.

(Manufacturing process of ashless carbon, process of producing by-product carbon)

In the ashless coal manufacturing process, coal is extracted with a solvent, and the solvent is removed from the extract from which the residue is separated to produce an ashless coal. On the other hand, the by-product manufacturing process removes the solvent from the slurry of the residue to produce a by-product. In other words, the by-product is a by-product generated in the process of producing the ash-free coal from coal. Therefore, in the present embodiment, the ashless carbon manufacturing process and the by-product carbon manufacturing process will be described as one process. In addition, as far as the by-product is an equivalent component, it may not be obtained as a by-product in the production of the ashless coal, and the ash and the coal may not be produced in the same process. As the method for producing the ashless carbon, for example, the methods described in Patent Documents 2 to 4 can be used. Hereinafter, a description will be given with reference to an example of a modified carbon manufacturing apparatus that can obtain the ashless carbon and the by-produced carbon as shown in Fig.

1, the reformed coal manufacturing apparatus 10 comprises a solvent storage tank 1, a slurry production tank 2 having a stirrer, a preheater 3, an extraction tank 4 having an agitator, A solid concentration concentrate receiver 6, and an upper liquid receiver 7, and further includes a pump, a not-shown distillation unit, a cooling mechanism, and the like. Hereinafter, a method for producing ashless coal and by-products using the reforming apparatus 10 will be described as the ashless coal production process and the by-product carbon production process.

First, the coal (raw coal) and the solvent supplied from the solvent reservoir 1 by the pump are supplied to the predetermined amount slurry producing tank 2, respectively. In the slurry producing tank 2, coal and a solvent are mixed with a stirrer provided to prepare a slurry. At this time, it is preferable to remove moisture of the coal by a dehydrating means (not shown). The slurry is heated by the preheater 3 and agitated in the extraction tank 4 for a predetermined period of time so that the bond between the molecules constituting the coal is loosened so that the pyrolytic pyrolysis is generated and the extraction proceeds, (Solid content, residue) insoluble in the solvent (extraction liquid) in which the soluble component is dissolved and in the solvent, and is supplied to the gravity sedimentation accelerator 5.

A variety of filtration methods and centrifugal separation methods are generally known as a method for separating the extract from the extract and the residue. In the production of ashless coal, however, a gravity sedimentation method suitable for continuous processing of fluids at low cost and suitable for large- Is preferably used. That is, in the gravitational sedimentation accelerator 5, the extract liquid is taken out as the supernatant, and is supplied to the supernatant liquid receiver 7 through the filter unit if necessary. In the supernatant receiver (7), the extract is removed from the solvent and becomes ashless. On the other hand, the portion containing the residue precipitated in the lower portion of the gravity precipitate 5 (solid concentrate) is discharged to the solid concentrate receiver 6, the solvent is removed from the solid concentrate receiver 6, .

In the solid concentrate liquid receiver 6 and the supernatant liquid receiver 7, the solvent can be removed from the extract or the solid concentrate by a method such as an evaporation method such as a distillation method or a spray drying method. The solute (unburned coal) or solid matter (by-product) obtained by removing the solvent is a powder in the form of powder having a diameter of about 0.2 to 1.0 mm, or a powder having a diameter of about 0.2 to 1.0 mm In some cases, particles are mixed. On the other hand, the solvent (recovery solvent) respectively removed from the solid-liquid concentrated liquid receiver 6 and the supernatant liquid receiver 7 is recovered and supplied to the slurry production tank 2 or the solvent storage tank 1 It may be reused. Hereinafter, conditions and the like in each operation will be described.

The coal used as the raw material of the ash and coal ash is not necessarily the same type as the coal to be mixed with the molding compound, regardless of the type (grade, quality, item). Therefore, bituminous coal having a high extraction ratio (ash recovery rate) may be used, or cheaper crude zeolite (bituminous coal, lignite) may be used. The coal is preferably pulverized into particles as small as possible before being introduced into the reformed coal producing apparatus 10 (slurry producing tank 2) in order to facilitate the progress of extraction and increase the yield of ashless coal (Maximum length) of not more than 1 mm.

Solvent is a solvent which has high affinity with coal and dissolves coal. Examples of such a solvent include monocyclic aromatic compounds such as benzene, toluene and xylene, polar solvents such as N-methylpyrrolidone (NMP) and pyridine, and the like. In the production of ashless coal (and by- It is preferable to use a non-hydrogenated solvent (aromatic solvent) mainly comprising a ring aromatic compound. Therefore, it is explained that an aromatic solvent is used as a solvent in the by-product manufacturing step in the present embodiment.

An aromatic solvent which is a non-hydrogenated casting solvent is a coal derivative which is mainly a solvent of a bivalent aromatic group purified from a distillation product of coal. This aromatic solvent is relatively stable even under the above extraction conditions and has excellent affinity with coal. Therefore, the ratio (extraction ratio) of the soluble components of coal extracted in the solvent is sufficiently high, and as a result, It is possible to obtain a by-product which is high and, at the same time, is a by-product in which the soluble components are not as much as possible. In addition, the aromatic solvent can be easily recovered from an extractor or the like by a method such as distillation, and the recovered solvent can be recycled as it is (see Fig. 1). Examples of the main component of the aromatic solvent include naphthalene, methylnaphthalene, dimethylnaphthalene and trimethylnaphthalene, which are two-ring aromatic compounds, and naphthalenes, anthracene and fluorenes having aliphatic side chains, Biphenyl or alkyl benzene having a long chain aliphatic side chain.

On the other hand, since hydrogen-based solvents can realize a higher extraction ratio regardless of the kind of coal, the yield of ashless coal is further increased. Examples of the hydrogenated castor oil solvent include partially hydrogenated aromatic compounds such as tetralin and tetrahydroquinoline, hydrogenated liquefied oil of coal, and the like. However, since the hydrogen-donating solvent is generally higher in price than the aromatic solvent and most of the hydrogen-donating ability is lost once it is used for extraction, it can not be reused unless the regeneration treatment (hydrogenation treatment) The cost also becomes expensive. Therefore, the hydrogen-based solvent is appropriately selected in consideration of the design of the coal as a raw material for the purpose of use or the like, such as the use of coal with a low extraction rate by an aromatic solvent. Further, for example, by using an aromatic solvent and a hydrogen-conjugated solvent in combination, the yield of ashless coal can be increased while suppressing the cost (see Patent Document 4).

The amount of coal to be mixed with the solvent varies depending on the kind of the raw coal, but is preferably in the range of 10 to 50 mass%, more preferably in the range of 20 to 35 mass% with respect to the total of the solvent and the dried coal. When the content of coal is less than 10% by mass, the amount of the coal component to be extracted with respect to the solvent is small and the productivity is low. On the other hand, when the amount of coal is equal to that of the solvent, that is, more than 50 mass%, the produced slurry becomes high in viscosity and the fluidity is deteriorated, so that it is difficult to move the treatment system (separation) or separate the extraction solution and residue.

By heating the slurry to a high temperature, the bond between the molecules constituting the coal is loosened, and the pyrolytic pyrolysis is carried out, and the extraction proceeds. When the temperature of the slurry is less than 300 캜, it is insufficient to weaken the bond between the molecules constituting the coal, and the extraction does not proceed sufficiently. On the other hand, when the temperature of the slurry is more than 450 ° C, the pyrolysis reaction of coal becomes very active, and the resulting pyrolytic radicals recombine, so that the extraction rate is rather unlikely to increase and the coal is less prone to degeneration. Therefore, the heating temperature of the slurry is preferably in the range of 300 to 450 占 폚, and more preferably in the range of 300 to 400 占 폚.

Since the solvent of the slurry can not be volatilized and can not be trapped in the liquid phase, the slurry can not be extracted. Therefore, in heating (preheating) or extracting the slurry, the vapor pressure of the solvent at the temperature do. On the other hand, if the pressure is excessively high, a high-priced equipment such as high hermeticity is required in the reforming apparatus 10, and the operation cost becomes high. Concretely, although it depends on the temperature at the time of extraction and the vapor pressure of the solvent, it is preferably in the range of 1.0 to 2.0 MPa. Further, since the extraction is carried out at a high temperature, the components soluble in the solvent and the coal component, particularly, the solvent, are liable to ignite when contacted with oxygen, so that the heating (preheating) or extraction of the slurry is performed in an inert gas atmosphere such as nitrogen desirable.

The extraction time (time within the heating temperature range of the slurry) is the standard until reaching the equilibrium of dissolution, but productivity tends to deteriorate when actualization is attempted. Therefore, it is preferable to complete the extraction at a time point when the increase in the extraction rate is apparently stopped or considerably gentle. Such a preferable extraction time varies depending on the conditions such as the particle diameter of the coal and the kind of the solvent, but is usually about 10 to 60 minutes. When the extraction time is less than 10 minutes, the extraction is not sufficiently progressed. On the other hand, if the extraction time exceeds 60 minutes, the extraction is difficult to proceed further, and the productivity is low.

(Coal pulverization process)

In the coal pulverizing step, the coal to be mixed with the molding compound is pulverized into granular particles by the usual method. In the case of the ashless coal and the by-produced carbon as well as the coarse secondary particles as described above, it is also possible to crush the same, or to mix the ashless coal and the by-produced coal with the coal as described above, good.

(Mixing process)

In the mixing process, an ashless coal, by-product coal, coal, and, if necessary, water are mixed to obtain a mixture (blend). The blend of the ashless coal, the by-product coal, and the coal and the water content are the same as the description of the above-mentioned molding blend, and in particular, as mentioned above, the water content of the coal, the unburned coal and the by- Is added. For example, non-stratified coal, by-product coal and pre-pulverized coal are respectively introduced into a known mixer through a hopper and stirred while adding water by spraying or the like so that the secondary particles of the ashless coal or the by-product are easily pulverized , The ashless coal and the by-product are appropriately cooled immediately after they are produced in the ashless coal manufacturing process and the by-product manufacturing process, that is, immediately after being heated to a temperature exceeding 200 DEG C for removing the solvent. In the case of adjusting the moisture content of the ashless coal or by-product coal at a high temperature, water is added in consideration of the amount of evaporation before the subsequent molding step.

(Molding step)

In the molding step, the compounded carbon is molded into a predetermined three-dimensional mass to obtain molded composite carbon. The compounding carbon may be molded by compression molding using a molding machine or two-roll briquetting, which is also applied to the molding of a carbon material such as ash carbon. The pressure to be applied to the blend for molding is not specifically defined and may be set in accordance with a molding machine or the like.

The blended carbon has a higher temperature, which facilitates the molding due to the fluidity of the ashless coal and further improves the strength and further improves the molding performance of the coke raw material in which coal, Combination shot can be obtained. Concretely, the blended coal preferably has a temperature of 80 ° C or higher, more preferably a range of 100 to 150 ° C. This temperature is assumed to be at the time when the compounding coal is charged into the molding die. Therefore, it is also possible to heat the coal or the like before mixing with a heater or the like in advance so that the temperature at the time of molding becomes 80 DEG C or higher, and then fill the mold or the like. For example, Or may be heated at the same time. On the other hand, when the heating temperature rises, it becomes expensive and the heating temperature of the compounding carbon is preferably 200 占 폚 or lower because there is no remarkable improvement effect on the formability and strength even when heated above 200 占 폚.

Next, the coke according to the present invention and the production method thereof will be described in detail.

〔cokes〕

The cokes according to the present invention can be obtained by carbonizing a coal mixture obtained by mixing the above-described shaped composite coal according to the present invention with other coal for coke raw material under the general conditions as described later. The content of the molding compounded coal according to the present invention in the coal mixture is preferably 10 to 30% by mass. The coal for coke raw material includes tough coal, semi-tough coal, semi-coking coal and non-coking coking coal which are generally used for coke raw materials. In the same manner as in the case of producing coke using only these coking coal, for example, 3 mm or less. As described above, since the molded composite according to the present invention is molded into a desired shape and has a constant strength, the coke is retained in the shape by being carried along with coal for coke raw material. It is not always necessary to align the size and shape with coal for coke raw material. Depending on the size, the shaped mixture carbon may be mixed with coal for coke raw material and dried in a molded form. However, when the molded composite coal is significantly larger than the coal for coke raw material (crushed), there arises a problem such as segregation in the furnace wall portion of the coke furnace due to the difference in flowability with coal particles for coke raw material It is preferable that the molded composite coal is pulverized to the same size as that of the coal for coke raw material. As described above, the molded composite carbons do not affect the effect of mixing the molded composite carbons according to the present invention, because the molded composite carbons are strongly bonded to each other by molding by coal, non-cyclic carbon, and by-product carbon, . The coke obtained by the dry distillation can be poured into the blast furnace for the production of the pig iron.

[Production method of coke]

In the present invention, the condition of the dry distillation is not particularly limited, and it is possible to adopt a normal dry condition in the production of coke using a coke furnace. For example, To about 50% of the above-mentioned coal mixture. Preferably at least 950 ° C, more preferably at least 1000 ° C, preferably at most 1200 ° C, more preferably at most 1050 ° C, preferably at least 8 hours, more preferably at least 10 hours , Preferably 24 hours or less, more preferably 20 hours or less.

Example

Next, molding compound coals and cokes according to the present invention, and a method of producing them, will be specifically described with reference to examples and comparative examples.

[Production of coke]

(Production of non-coated carbon and by-product)

First, by-produced carbon and by-produced carbon were produced by the following method.

The raw coal (raw dry coal) and the quarts (20 kg) of solvent [1-methylnaphthalene (manufactured by Shin-Etsu Chemical Co., Ltd.)] were mixed with Australian bituminous coal as a raw material coal to prepare a slurry Respectively. The slurry was subjected to extraction treatment in a 30 L batch autoclave at 370 占 폚 for 1 hour while nitrogen was introduced and pressurized to 1.2 MPa. The slurry was separated into a supernatant and a solid concentrate in the gravity sedimentation medium maintained at the same temperature and pressure, and the solvent was separated and recovered from the solid concentrate by distillation to obtain by-products. On the other hand, the solvent was separated and recovered from the supernatant by the distillation method to obtain an ashless coal. The moisture content of the obtained ashless coal and by-product was 1.5% by mass. 1 kg of each of these ashless coal and by-product carbon was crushed to have a particle diameter (maximum length) of 1 mm or less.

(Mixing, molding)

(Maximum flow MF value (log (ddpm) 0.5, average maximum reflectance Ro value 1.01) of 6.7 mass% moisture was pulverized so as to have a grain size of 1 mm or less, and ash coal and by- The coals were mixed at the blending ratio (%) shown in Table 1, water was further added so as to be 0.5% by mass with respect to the total amount, and the blend was mixed with a V mixer for 10 minutes to prepare a mixture Is a value measured based on Coal JIS (JIS M8812).

Subsequently, this mixture was charged into a metal mold having a diameter of 20 mm in an amount of 6 g per one piece, heated at 120 캜 under a pressure of 2 ton / cm 2, and molded into a columnar tablet.

The molding compounded coal was arranged in a forced retort, and the retort was placed in a double-side heating type electric furnace, and the molding compounded coal was dried in a nitrogen stream. The temperature was raised at 3 캜 / minute and heated at 1000 캜 for 20 minutes. Thereafter, the retort was removed from the electric furnace and naturally cooled. In addition, as the evaluation standard, a sample (No. 8) of coke was produced from the molding compounded coal containing no by-product carbon. The obtained coke was evaluated in the following manner.

〔evaluation〕

(Compression test)

An impact test was conducted as an index of strength. A compressive load was applied in a direction perpendicular to the cylindrical axis of the coke (radial direction), and the load resulting from the fracture was measured. The measured load is shown in Table 1 as the collapse load. The criterion for acceptance of the strength was that the collapse load was 100 kg or more.

(Abre test)

Abrelation test was performed as an index of suppression of dust generation. First, 20 coke containers were placed in a cylindrical container having a diameter of 250 mm and rotated at 30 RPM for 10 minutes. Subsequently, the coke taken out from the cylindrical container was screened with a sieve having a graduation of 5.66 mm, and the amount of the coke passed through the eyes was weighed. The weight ratio (%) of the amount of the powder (powder) that passed through the eye with respect to the entire coke was calculated, and the powder generation rate is shown in Table 1. As a criterion for acceptance of suppression of dust generation, the powder incidence rate was 10% or less.

As shown in Table 1, the samples Nos. 1, 5 and 7 satisfy the range of the present invention and are lower than the sample No. 8 which does not contain the by-products. However, &Lt; / RTI > On the other hand, the samples Nos. 2, 3 and 6 were low in strength because of the lack of ashless carbon, and specimen No. 2 which did not contain ash carbon was particularly low. In addition, the sample No. 4 had a low strength because the by-product was excessive.

Although the present invention has been described in detail with reference to the embodiments and the examples, the spirit of the present invention is not limited to the above description, and the scope of the right should be broadly interpreted based on the description of the claims. It is needless to say that the content of the present invention can be widely modified or changed based on the above description.

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2012-044219) filed on February 29, 2012, the contents of which are incorporated herein by reference.

According to the molded composite according to the present invention, a fuel or a coke raw material suitable for storage and transportation can be obtained. According to the coke of the present invention, by using the by-products, sufficient strength is obtained at a low raw material cost. Further, according to the process for producing a molded composite coal and the process for producing a coke according to the present invention, since the by-products can be effectively used, economical efficiency in production of ashless coal is improved.

10: Reformer manufacturing equipment
1: Solvent storage tank
2: Slurry producing tank
3: Preheater
4: Extraction tank
5: gravity sedimentation emphasis
6: Solid concentrate receptacle
7: supernatant receptor

Claims

A combination blend comprising an ashless coal containing a component soluble in a solvent in a coal and a blended coal obtained by mixing a coal obtained by removing a soluble component from the coal and a by-
Characterized in that the blend contains 3 wt% or more of the ashless coal, 8 wt% or less of the by-product, and the granular coal as a remaining amount.

The method according to claim 1,
Characterized in that at least 90% of the granular coal has a diameter of 2 mm or less.

3. The method of claim 2,
Characterized in that more than 60% of the granular coal has a diameter of 1 mm or less.

The method according to claim 1,
Wherein the granular coal has a maximum flow MF value (log (ddpm)) of 0.2 to 2.0 and an average maximum reflectance Ro value of 0.8 to 1.1.

A coke obtained by drying a coal mixture comprising the shaped mixture according to claim 4.

An ash tundish manufacturing process of extracting coal with a solvent, separating the extract and residue, removing the solvent from the extract, and producing an ashless coal containing a soluble component in the solvent in the coal,
A byproduct carbon manufacturing process for producing by-product carbon by removing the solvent from the separated residue in the ashless carbon manufacturing process;
A coal pulverizing step of pulverizing coal into a granular form,
Mixing the granular coal and the by-product coal to the granular coal to obtain a blend containing 3 wt% or more of the ash and 8 wt% or less of the by-product;
And a molding step of molding the compounded carbon.

The method according to claim 6,
Wherein the temperature of the compounding carbon in the molding step is 80 to 200 占 폚.

A method for producing coke comprising a step of dry-distilling a coal mixture containing a shaped mixture produced by the method for producing a shaped mixture according to claim 6.