WO2012176896A1 - Procédé de fabrication d'un charbon sans cendre - Google Patents

Procédé de fabrication d'un charbon sans cendre Download PDF

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Publication number
WO2012176896A1
WO2012176896A1 PCT/JP2012/066051 JP2012066051W WO2012176896A1 WO 2012176896 A1 WO2012176896 A1 WO 2012176896A1 JP 2012066051 W JP2012066051 W JP 2012066051W WO 2012176896 A1 WO2012176896 A1 WO 2012176896A1
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WIPO (PCT)
Prior art keywords
coal
solvent
oil
ashless coal
ashless
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/066051
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English (en)
Japanese (ja)
Inventor
濱口　眞基
貴洋 宍戸
康爾 堺
憲幸 奥山
聡則 井上
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Kobe Steel Ltd
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Kobe Steel Ltd
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Publication date
Application filed by Kobe Steel Ltd filed Critical Kobe Steel Ltd
Publication of WO2012176896A1 publication Critical patent/WO2012176896A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/02—Treating solid fuels to improve their combustion by chemical means

Definitions

  • the present invention relates to a method for producing ashless coal used as a raw material for various carbon materials, a binder for iron-making coke and forming coal, and the like.
  • Ashless charcoal (hyper coal) is also called modified coal, and is produced by extracting coal with a solvent and separating only the components that are soluble in this solvent, so that it does not substantially contain ash. Therefore, it has the feature that the characteristics of the carbon material are not easily deteriorated, and may exhibit caking properties, so that it is suitably used as a raw material for various carbon materials, a binder for iron-making coke, and formed coal.
  • a method for producing ashless coal by treating coal with a solvent is well known.
  • a method for producing ashless coal that can produce ashless coal in a high yield by treating coal using a hydrogen-donating solvent has been proposed (see, for example, Patent Document 1).
  • This invention is made
  • the present invention mixes coal and a solvent capable of dissolving coal, ashless coal soluble in the solvent, and residual coal that is insoluble in the solvent and contains ash, And a ashless coal recovery process for recovering the separated ashless coal, wherein the residual coal separated in the separation step is heat treated at a temperature of 400 ° C. or higher. And an oil content recovery step for recovering the generated oil content, and an addition step for adding a part or all of the oil content recovered in the oil content recovery step to the solvent.
  • the residual coal when the residual coal is heat-treated at a temperature of 400 ° C. or higher in the oil recovery step, the residual coal is thermally decomposed to produce oil.
  • the produced oil contains an aromatic compound having a function equivalent to that of a solvent used when producing ashless coal. Therefore, the solvent cost can be reduced by adding the recovered oil to the solvent in the separation step in the subsequent addition step.
  • the residual charcoal in the oil recovery step is continuously heat-treated. In this way, since the oil can be continuously generated, the solvent cost can be reduced over a long period of time.
  • an ashless coal production method capable of producing ashless coal at a low cost even when producing ashless coal by solvent extraction.
  • the ashless coal production apparatus 1 includes a solvent supply tank 2 for supplying a solvent, a coal supply tank 3 for supplying coal, a supply from a solvent supply tank 2 and a coal supply tank 3.
  • the slurry is prepared, and then the extraction tank 4 for extracting the solvent-soluble component (solvent-soluble component) from the slurry, the solvent (solution part) containing the solvent-soluble component, and the solvent-insoluble component (
  • an ashless coal collection tank 6 for removing the solvent from the solution portion separated in the separation tank 5 and collecting the ashless coal that is the modified coal, and heat-treating the residue coal.
  • the solvent removed from the solution part in the ashless coal recovery tank 6 may be returned to the solvent supply tank 2 and reused.
  • the ashless coal recovered in the ashless coal recovery tank 6 does not substantially contain ash because the ash is not dissolved in the solvent, and is used as a raw material for various carbon materials, a binder for iron-making coke and forming coal, etc. be able to.
  • ashless coal is (substantially) free of ash.
  • the ash content is preferably 0% by mass, but ash is inevitably contained because ashless coal is recovered through solvent extraction. Accordingly, the ashless coal referred to in the present invention is allowed to contain a small amount of ash that is inevitably contained.
  • the upper limit of the ash content allowed for ashless coal is 3% by mass, preferably 1.5% by mass, and more preferably 1% by mass.
  • the solid matter from which the oil has been collected in the oil collecting tank 8 is collected as residual charcoal and used as fuel or the like.
  • Part or all of the oil recovered in the oil recovery tank 8 flows through the introduction pipe 9 and is added to the solvent supply tank 2.
  • the introduction pipe 9 may be provided with a liquid feed pump or the like as necessary (none of which is shown).
  • the ashless coal manufacturing method includes a separation step S1 and an ashless coal recovery step S2, and further includes an oil recovery step S3, Addition process S4.
  • the above-described process is allowed while including an appropriate process that can be normally performed before the separation process S1 or after the addition process S4 or between the above-described processes.
  • an appropriate process for example, a process for removing impurities such as dust, sulfur compounds, and trace metals from the solvent containing the solvent-soluble component obtained in the separation process S1 and the oil obtained in the oil recovery process S3, solvent And a step of adjusting the oil content to an arbitrary temperature.
  • Separation process S1 is a process of mixing coal and a solvent capable of dissolving coal, and separating the coal into ashless coal that is soluble in this solvent and residual coal that is insoluble in this solvent and contains ash. . This process is performed by the solvent supply tank 2, the coal supply tank 3, the extraction tank 4, and the separation tank 5 shown in FIG.
  • the raw material coal is preferably bituminous coal, but subbituminous coal, lignite, anthracite, etc. can also be used.
  • the moisture content of coal is high, it is preferable to perform dehydration in a dehydration step (not shown) prior to the separation step S1.
  • the moisture content may be about 10% or less.
  • the particle size of coal shall be 5 mm or less. This is for efficient dissolution with a solvent and for keeping the particle size of the residual charcoal uniform.
  • the solvent preferably contains a bicyclic aromatic compound, and more preferably contains this as a main component.
  • a main component means occupying most as a component contained quantitatively.
  • the solvent that can be used in combination with the bicyclic aromatic compound may be any solvent that can dissolve the raw material coal.
  • the bicyclic aromatic compound include naphthalene, biphenyl, and alkyl-substituted products thereof.
  • methyl naphthalene is preferable.
  • the methylnaphthalene may be either 1-methylnaphthalene or 2-methylnaphthalene.
  • the bicyclic aromatic compound may be naphthalene, biphenyl or a dimethyl-substituted product thereof, or an ethyl-substituted product.
  • a bicyclic aromatic compound is preferable as a solvent used in the present invention because it has a strong extractability of soluble components to coal but has a relatively low boiling point and high thermal stability.
  • anthracene oil or creosote oil is generally used as a solvent used for dissolving coal. These have a high extraction power for coal, but are a byproduct of coal dry distillation for producing coke and are not necessarily inexpensive. Also, because the production volume is limited, it is difficult to cover the coal solvent extraction process. A further disadvantage associated with these known materials is that complete recovery from ashless coal is not easy. That is, anthracene oil and creosote oil contain a component with a high boiling point and a polar component having a very strong affinity with coal in a considerably high concentration.
  • the solvent used in the present invention preferably includes a bicyclic aromatic compound, and more preferably includes this as a main component.
  • Separation (solid-liquid separation) of ashless coal, which is a soluble component, and residual coal, which is an insoluble component can be performed by, for example, a filtration method or a gravity sedimentation method.
  • the heating temperature and pressure at the time of separation are preferably set to the same conditions as when coal is dissolved with a solvent.
  • the heating temperature is preferably set to 300 to 420 ° C., for example, at the time of dissolution, extraction and separation, but is generally set to 400 ° C. or lower.
  • the heating time in the separation step S1 is preferably shorter than the oil recovery step S3 described later. For example, it is preferably 20 to 60 minutes.
  • the pressure is preferably 0.8 to 2.5 MPa, for example.
  • the ashless coal recovery step S2 is a step of recovering the ashless coal separated in the separation step S1. That is, since the solvent part is contained in the solution part isolate
  • the ashless coal as a product from which the solvent has been removed can be suitably used as a raw material for various carbon materials, a binder for iron-making coke and forming coal, and the like.
  • the process described above is a commonly performed process.
  • the present invention is characterized in that the following steps are performed subsequent to the steps described above.
  • the oil component recovery step S3 is a step of recovering the oil component produced by heat-treating the residual coal separated in the separation step S1 at a temperature of 400 ° C. or higher. This process is performed by the heat treatment tank 7 and the oil recovery tank 8 shown in FIG.
  • the main physicochemical changes that occur in the residual coal during the heat treatment in the oil recovery step S3 are as follows. (1) Generation of gases such as hydrogen, CO, CO 2 , methane, ethane, and ethylene. (2) Generation of a carbon precursor by dehydroaromatization. (3) Decomposition of aromatic side chains by dealkylation, decarboxylation, etc. (causes generation of gas of (1) above). (4) Generation of oil containing naphthalenes and biphenyls by thermal decomposition. Of these, (4) is important in the present invention.
  • the production of oil by pyrolysis can proceed even during the solvent extraction in the separation step S1.
  • the heating temperature in the separation step S1 is set to, for example, 300 to 420 ° C., generally 400 ° C. or lower, so that the thermal decomposition rate is low and the oil content is not sufficiently generated. If the heat treatment time is lengthened, it is possible to increase the amount of oil produced even at a low temperature, but the solvent-soluble component that becomes ashless coal is polycondensed and insolubilized, and shifts to residual coal. That is, the yield of ashless coal decreases.
  • the heat treatment temperature needs to be 400 ° C. or higher in order to efficiently generate the oil from the residual coal.
  • the heat treatment temperature is less than 400 ° C., the temperature is too low, the thermal decomposition rate is slow, and a sufficient oil content cannot be generated.
  • about the upper limit of heat processing temperature it can be set to about 800 degreeC. Even if the heat treatment temperature is set too high, the amount of naphthalenes and biphenyls in the produced oil does not increase, and the heating cost increases, which is not preferable in terms of cost. Therefore, the preferable range of the heat treatment temperature is 400 ° C. to 600 ° C.
  • the heat treatment time may be about 5 to 30 minutes, but is preferably about 15 to 30 minutes, more preferably about 20 to 30 minutes.
  • An inert gas atmosphere is used during heat treatment to prevent oxidation of residual charcoal.
  • the pressure during the heat treatment may be normal pressure.
  • a kiln type, a fluidized bed type, a batch type, or the like can be used as an apparatus for performing the heat treatment. According to these, the heat treatment of the residual coal in the oil recovery step S3 can be performed continuously.
  • the oil component generated from the residual charcoal is gasified, so that it can be recovered by condensing it with a condenser and liquefying it.
  • the residual coal from which the oil has been collected in the oil collecting step S3 has a calorific value equivalent to that of the residual coal before the oil is collected on a mass basis, and therefore can be used as fuel. Of course, it can also be used for the heat treatment of the oil recovery step S3.
  • the addition step S4 is a step of adding a part or all of the oil recovered in the oil recovery step S3 to the solvent used in the separation step S1.
  • Such a process is performed by the oil recovery tank 8 and the introduction pipe 9 shown in FIG.
  • the part of the oil component is further refined by fractionating the recovered oil component, for example, by selectively increasing the concentration of the bicyclic aromatic compound, and qualitatively selecting a part of the recovered oil component. It means that only a part of the sample is taken out quantitatively, even if such purification is not performed. If a part is taken out qualitatively and added to the solvent as in the former, the concentration of the bicyclic aromatic compound in the solvent used in the separation step S1 increases.
  • the solvent to which this is added can be made more preferable because the extractability of soluble components to coal is stronger, the boiling point is relatively low, and the thermal stability is also higher. Further, in the latter case, since an amount as required can be added, it is possible to easily manage the amount of the solvent used in the separation step S1.
  • the other oil not added to the solvent can be used as a raw material for fuel or a chemical product, for example.
  • the boiling point range under normal pressure can be set.
  • the temperature may be 150 to 400 ° C.
  • the whole oil component literally means all the oil components recovered in the oil recovery step S3.
  • Coal was dissolved using methylnaphthalene under the following [conditions] to extract a solvent-soluble component. ⁇ conditions ⁇ ⁇ Solvent (methylnaphthalene) / coal ratio: 1/5 (mass basis) ⁇ Temperature: 370 °C Extraction time: 15 minutes Initial pressure: 1 MPa (nitrogen atmosphere)
  • the produced residual charcoal was heated at 350 ° C. in a nitrogen atmosphere to evaporate the solvent.
  • 10 g of the heated residual charcoal was heated for 20 minutes in a nitrogen stream at 50 mL / min at the heating temperatures shown in Comparative Example 1 and Examples 1 to 5 in Table 1 below.
  • the component analysis of the oil was performed. Component analysis was performed with a gas chromatography mass spectrometer. As a result of component analysis, it was found that naphthalenes and biphenyls, which are bicyclic aromatic compounds, are the main components.
  • the present invention is useful as a method for producing ashless coal used as a raw material for various carbon materials, iron-making coke, and a binder for forming coal.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

Ce procédé de fabrication de charbon sans cendre comprend une étape de séparation (S1) consistant à mélanger du charbon et un solvant apte à dissoudre le charbon et à séparer celui-ci en charbon sans cendre qui est soluble dans le solvant et en charbon résiduel qui est insoluble dans le solvant contient de la cendre, et une étape de récupération de charbon sans cendre (S2) consistant à récupérer le charbon sans cendre séparé. Ce procédé est caractérisé par le fait qu'il comprend une étape de récupération de teneur en huile (S3) consistant à traiter thermiquement le charbon résiduel séparé dans l'étape de séparation (S1) à une température de 400°C ou plus ou à récupérer la teneur en huile générée, et une étape d'addition (S4) consistant à ajouter au solvant la totalité ou une partie de la teneur en huile récupérée dans l'étape de récupération de teneur en huile (S3).
PCT/JP2012/066051 2011-06-22 2012-06-22 Procédé de fabrication d'un charbon sans cendre Ceased WO2012176896A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-138623 2011-06-22
JP2011138623A JP2013006907A (ja) 2011-06-22 2011-06-22 無灰炭製造方法

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WO2012176896A1 true WO2012176896A1 (fr) 2012-12-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015224278A (ja) * 2014-05-27 2015-12-14 株式会社神戸製鋼所 無灰炭の製造装置及び無灰炭の製造方法
AU2014245203B2 (en) * 2013-03-28 2016-05-19 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Ashless-coal production device, and ashless-coal production method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4974201A (fr) * 1972-10-12 1974-07-17
JP2005120185A (ja) * 2003-10-15 2005-05-12 Kobe Steel Ltd 無灰炭の製造方法
JP2009215505A (ja) * 2008-03-12 2009-09-24 Kobe Steel Ltd 無灰炭の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4974201A (fr) * 1972-10-12 1974-07-17
JP2005120185A (ja) * 2003-10-15 2005-05-12 Kobe Steel Ltd 無灰炭の製造方法
JP2009215505A (ja) * 2008-03-12 2009-09-24 Kobe Steel Ltd 無灰炭の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2014245203B2 (en) * 2013-03-28 2016-05-19 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Ashless-coal production device, and ashless-coal production method
CN105051169B (zh) * 2013-03-28 2017-06-30 株式会社神户制钢所 无灰煤的制造装置和无灰煤的制造方法
US9938477B2 (en) 2013-03-28 2018-04-10 Kobe Steel, Ltd. Ashless-coal production device, and ashless-coal production method
JP2015224278A (ja) * 2014-05-27 2015-12-14 株式会社神戸製鋼所 無灰炭の製造装置及び無灰炭の製造方法

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