WO2011129434A1 - Méthode de gazéification de charbon par décomposition thermique et appareil de gazéification de charbon par décomposition thermique - Google Patents

Méthode de gazéification de charbon par décomposition thermique et appareil de gazéification de charbon par décomposition thermique Download PDF

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WO2011129434A1
WO2011129434A1 PCT/JP2011/059380 JP2011059380W WO2011129434A1 WO 2011129434 A1 WO2011129434 A1 WO 2011129434A1 JP 2011059380 W JP2011059380 W JP 2011059380W WO 2011129434 A1 WO2011129434 A1 WO 2011129434A1
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coal
furnace
gasification
gas
reforming
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PCT/JP2011/059380
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English (en)
Japanese (ja)
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小水流　広行
小菅　克志
正人 景山
矢部　英昭
卓 武田
眞須美 糸永
泰樹 並木
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新日鉄エンジニアリング株式会社
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Priority to JP2012510712A priority Critical patent/JP5450800B2/ja
Priority to CN201180018845.8A priority patent/CN102939361B/zh
Priority to AU2011241502A priority patent/AU2011241502B2/en
Publication of WO2011129434A1 publication Critical patent/WO2011129434A1/fr

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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
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    • C10J3/76—Water jackets; Steam boiler-jackets
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/466—Entrained flow processes
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/485—Entrained flow gasifiers
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/485—Entrained flow gasifiers
    • C10J3/487—Swirling or cyclonic gasifiers
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
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    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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    • C10J3/723—Controlling or regulating the gasification process
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    • C10J2200/00—Details of gasification apparatus
    • C10J2200/15—Details of feeding means
    • C10J2200/152—Nozzles or lances for introducing gas, liquids or suspensions
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0909—Drying
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
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    • C10J2300/093—Coal
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
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    • C10J2300/0959—Oxygen
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    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
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    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C—CHEMISTRY; METALLURGY
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    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1678—Integration of gasification processes with another plant or parts within the plant with air separation
    • C—CHEMISTRY; METALLURGY
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    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]

Definitions

  • the present invention relates to a coal pyrolysis gasification method and a coal pyrolysis gasification apparatus for producing a product gas containing at least hydrogen gas and carbon monoxide gas by rapidly gasifying and pyrolyzing coal in an air flow layer.
  • This application claims priority based on Japanese Patent Application No. 2010-95495 filed in Japan on April 16, 2010, the contents of which are incorporated herein by reference.
  • Patent Document 2 a method for hydrocracking coal is shown.
  • This method of hydrocracking coal involves injecting coal and hydrogen into the high-temperature gas produced when gasifying coal and carbonaceous raw materials with oxygen, and conducting rapid heating and hydropyrolysis reactions of coal in the gas stream. Let it be done.
  • This coal pyrolysis method can obtain light oil and fuel gas such as methane with high yield.
  • JP-A-5-295371 JP 2004-217868 A Japanese Patent Laid-Open No. 61-246287
  • an apparatus including a reactor having two stages of upper and lower two chambers is used.
  • a coal-burning burner is installed at an angle to the gasification furnace so that the coal and char to be charged form a swirling flow in the furnace.
  • the swirl flow formed in the gasification furnace flows while maintaining the swirl flow in the upper reforming furnace of the reactor. For this reason, when coal is blown into the reforming furnace, the charged coal particles flow in the vicinity of the furnace wall in a swirling flow, which may cause adhesion of coal particles to the furnace wall of the reforming furnace, resulting in operational trouble. It was.
  • the swirl flow is also maintained in the reforming furnace in this way, the particle concentration of the coal charged into the reforming furnace varies, and the temperature rise of the particles is uneven in the portion where the particle concentration is high. It becomes. As a result, the reaction may become non-uniform.
  • Patent Document 2 it is considered that the coal is introduced so as to swirl in the same direction as the swirl flow in the gasification furnace in order to extend the residence time of the coal particles thrown into the reforming furnace.
  • the spouted bed coal gasification furnace which changed the turning diameter of a two-stage fuel supply part is shown.
  • the gasification of coal is performed using a gasification furnace instead of a reforming furnace that performs thermal decomposition.
  • the inventions described in Patent Documents 1 and 2 are different from those in the reactor.
  • the reaction is different. That is, in pyrolysis, coal is decomposed without using oxygen, so that tar is generated in addition to gases such as hydrogen, carbon monoxide, and methane.
  • An object of the present invention is to provide a coal pyrolysis gasification method and a coal pyrolysis gasification apparatus capable of suppressing operational troubles and reaction nonuniformity in a reforming furnace.
  • the coal pyrolysis gasification method comprises a cylindrical gasification furnace in the lower stage and a cylindrical reforming furnace in the upper stage, and two stages of upper and lower two chambers connected between them by a throat serving as an enlarged diameter portion.
  • a gas bed reactor at least coal and an oxygen-containing gas are introduced into the gasification furnace, and gasification gas is generated by partially oxidizing the coal, and the gasification gas is supplied to the reforming furnace.
  • gasification gas is supplied to the reforming furnace.
  • a method for pyrolyzing and gasifying coal to produce a generated gas wherein the coal to be fed into the gasification furnace is introduced by air current conveyance so as to form a swirling flow in the circumferential direction in the gasification furnace. And the coal to be charged into the reforming furnace is The swirling flow of the coal to be charged into the gasification furnace to introduce by pneumatic conveying towards a circumferential direction opposite.
  • the charging positions of the two or more coals in the reforming furnace may be positions at equal intervals in the circumferential direction on the furnace wall of the reforming furnace.
  • the reforming is further performed by airflow conveyance in a circumferential direction opposite to the swirling flow of coal to be input into the gasification furnace.
  • the coal is introduced into the reforming furnace by air flow in a circumferential direction opposite to the swirling flow of coal to be fed into the reforming furnace, and from the other two or more locations with respect to the furnace wall of the reforming furnace.
  • the input angles of coal may be the same angle, and may be different from the input angles of coal from the two or more locations.
  • the two or more coal input positions in the reforming furnace and the other two or more coal input positions may be alternately positioned in the circumferential direction.
  • the coal pyrolysis gasification apparatus is a coal pyrolysis gasification apparatus used in the coal pyrolysis gasification method, wherein the lower stage is a cylindrical gasification furnace, and the upper stage is a cylindrical reformer.
  • the nozzle that is fed into the gasification furnace by air-flowing at least the coal forms a swirl flow in the circumferential direction in the gasification furnace.
  • the reforming furnace has a nozzle for feeding coal into the reforming furnace by air flow, and a nozzle for feeding coal into the reforming furnace by carrying the air current, Of coal to be put into the gasifier It is arranged to introduce coal toward a circumferential direction opposite to the swirling flow.
  • the dispersibility of the coal charged into the reforming furnace is improved in the reforming furnace, and the operation in the reforming furnace is performed. Trouble and non-uniform reaction can be suppressed.
  • a coal pyrolysis gasifier 20 includes a gas stream reactor 21 (hereinafter referred to as a gas stream reactor) having an upstream gasification furnace 2 and a downstream reforming furnace 1. 21 or simply referred to as reactor 21).
  • a gas stream reactor having an upstream gasification furnace 2 and a downstream reforming furnace 1. 21 or simply referred to as reactor 21).
  • the gasification furnace 2 gasifies the gasified coal 9 introduced into the inside using oxygen 12 as an oxidizing agent (gasifying agent) and mainly contains carbon monoxide, carbon dioxide, hydrogen, and water vapor as components. A gas 14 is generated.
  • oxygen 12 as an oxidizing agent (gasifying agent)
  • the temperature in the gasification furnace 2 since it is necessary to melt the ash contained in the gasification coal 9 and discharge it from the gasification furnace 2, the temperature in the gasification furnace 2 must be equal to or higher than the melting point of the ash. There is. Therefore, the gasification gas 14 introduced from the gasification furnace 2 to the reforming furnace 1 is also at a high temperature.
  • the reformed coal 10 is heated to cause a thermal decomposition reaction, and contains at least hydrogen gas and carbon monoxide gas.
  • a product 16 containing product gas can be obtained.
  • Such a gas bed reactor 21 has a two-stage upper and lower two-stage system in which the gasification furnace 2 is provided in the lower stage and the reforming furnace 1 is provided in the upper stage.
  • the gas stream reactor 21 is connected to the gasification furnace 2 and the reforming furnace 1 through a throat 3 in which the diameter of the gasification furnace 2 and the reforming furnace 1 are increased from the small-diameter gasification furnace 2 toward the reforming furnace 1. It has a so-called throat structure.
  • the reforming furnace which is the upper chamber is formed by introducing a throat 3 that gradually expands after once constricting the gas flow path to partially increase the flow velocity. 1 is prevented from dropping into the gasification furnace 2 which is a lower chamber. Thereby, independent reaction conditions can be set for each chamber.
  • the gasification furnace 2, the reforming furnace 1 and the throat 3 have a cylindrical structure with a circular horizontal cross section.
  • the gasified coal 9 in the gasification furnace 2 is partially oxidized and becomes high temperature, the ash contained in the gasified coal 9 becomes a molten slag 15. Therefore, it is preferable to provide the slag tap 6 which can discharge
  • tube 17 for the furnace wall of the gasification furnace 2 so that the molten slag 15 may adhere to this furnace wall, and a wall surface may be protected.
  • the gasification furnace 2 is provided with one or more gasification burners for introducing both the gasification coal 9 and the oxygen-containing gas 11 which is an oxidizing agent for partially oxidizing the gasification coal 9. 5 is installed.
  • the oxygen-containing gas 11 oxygen 12, or oxygen 12 and water vapor 13 can be employed.
  • the gasified coal 9 and the oxygen-containing gas 11 are blown into the gasification furnace 2 using the gasification burner 5 and rapidly mixed.
  • gasification furnace 2 the carbon and hydrogen components in the hydrocarbon contained in the gasification of coal 9 to be turned on, as much CO, it is preferable to convert into H 2 enhances the gasification conversion.
  • the injection nozzle for the oxygen-containing gas 11 is positioned at the same height as the injection nozzle for the gasified coal 9 and the oxygen-containing gas 11 and the gasified coal 9 are input at the same level. Thereby, even if it separates a coal inlet and an oxygen containing gas inlet, it can suppress that the gasification conversion rate of the gasification coal 9 falls. Further, the gasified coal 9 is fed into the gasification furnace 2 by being transported using an airflow carrier gas different from the oxygen-containing gas 11.
  • the airflow carrier gas a non-oxidizing gas such as nitrogen gas or a gas generated during the process can be used, but is not limited thereto.
  • the gasification burner 5 is installed at an angle so as to form a swirling flow of the gasified coal 9 in the circumferential direction in the gasification furnace 2. Thereby, the residence time of the gasification coal 9 in the gasification furnace 2 can be ensured, and the gasification conversion rate can be increased.
  • Two or more gasification burners 5 are preferable so as to form a stable swirl flow in the gasification furnace 2.
  • the gasification burner 5 is located below the gasification furnace 2 for stable discharge of the slag 15 generated in the gasification furnace 2.
  • the direction of the gasification burner 5 is set to a virtual circle of 1/10 to 2/3 of the diameter of the gasification furnace 2 (the central axis of the gasification furnace 2). And a direction tangential to the same axis).
  • the operating pressure and temperature of the gasification furnace 2 are maintained at 0.1 to 20 MPa and 1300 to 1700 ° C., for example.
  • the pressure is adjusted according to the pressure of the reforming furnace 1.
  • the gasification gas 14 generated in the gasification furnace 2 passes through the throat 3 and is sent to the reforming furnace 1.
  • the reformed coal 10 is input to cause a pyrolysis reaction of the coal.
  • product gas, char, tar and the like are produced from the coal as the product 16.
  • the produced gas can be used as a fuel or chemical raw material
  • the char can be used as a solid fuel
  • the tar can be used as a chemical raw material or fuel.
  • the reformed coal 10 is charged into the reforming furnace 1 while being transported by the airflow transport gas. At this time, even if the reformed coal 10 is carried into the reforming furnace 1 alone while being transported by the air current carrying gas, it is possible to produce the product 16 by causing the reformed coal 10 to undergo a thermal decomposition reaction.
  • at least one of hydrogen, water vapor, and oxygen can be added at the same time to change the properties and amount of the produced gas and tar.
  • the operating pressure and temperature in the reforming furnace 1 are maintained at, for example, 0.1 to 20 MPa and 500 to 1200 ° C. Since the reforming furnace 1 and the gasification furnace 2 are connected up and down via the throat 3, both furnaces have substantially the same operating pressure.
  • the operating pressure of the reforming furnace 1 is preferably set to an operating pressure of about 1 to 3 MPa in accordance with the use of the product gas. That is, if the operating pressure of the reforming furnace 1 is too low, it is necessary to increase the furnace volume in order to ensure the gas residence time in the gasification furnace 2. As a result, since the surface area in the gasification furnace 2 increases and the amount of heat dissipated increases, it is not preferable that the operating pressure of the reforming furnace 1 is too low.
  • the equipment manufacturing cost becomes high.
  • gasification and hydrogenation can be advanced by introducing steam into the reforming furnace 1 together with the reformed coal 10.
  • the following temperature conditions are preferable. That is, of the products 16, when the recovered products to be recovered are mainly product gas and tar, a relatively low temperature condition of 500 to 800 ° C. is preferable. When the recovered product is mainly product gas, a relatively high temperature condition of 800 to 1200 ° C. is preferable. If the recovered product is mainly produced gas, reforming aids such as steam and hydrogen are added to the reforming furnace 1 and reforming aids such as steam are added to the gasification furnace 2 to modify the recovered gas. It is preferable to promote the gasification reaction in the quality furnace 1. Moreover, it is preferable that the char generated in the reforming furnace 1 is thrown in as fuel for the gasification furnace 2 together with the gasified coal 9 and recycled.
  • the swirling flow formed in the gasification furnace 2 flows and rises in the reforming furnace 1 while keeping swirling. Therefore, when the reformed coal 10 is simply put into the reforming furnace 1 perpendicularly to the furnace wall 1a, or when it is put in the same direction as this swirling flow, the particles of the reforming coal 10 ride on the swirling flow, A part with high coal concentration is created. Then, the temperature rise of the modified coal 10 becomes uneven, and a stable thermal decomposition product cannot be obtained. Moreover, since the part with high particle
  • the reformed coal injection nozzle 4 was installed at a charging angle opposite to the swirling flow (arrow F shown in FIG. 2) in the gasification furnace 2.
  • the present inventors have found that the reforming furnace 1 radial particle concentration in the reforming furnace 1, that is, the particle concentration at each position along the radial direction of the reforming furnace 1 can be made uniform. That is, in the reforming furnace 1, the reformed coal 10 flows into the reforming furnace 1 in the circumferential direction opposite to the swirling flow of the gasified gas 14 introduced from the gasification furnace 2 through the throat 3.
  • the nozzle 4 is installed at an input angle that is input by being conveyed.
  • the charging angle refers to the nozzle axis 22 of the nozzle 4 extending along the direction in which the reformed coal blowing nozzle 4 is charged from the reformed coal blowing nozzle 4 and the reforming of the nozzle installation position in the top view of the reforming furnace 1. It means a horizontal angle (angle ⁇ shown in FIG. 2) formed by a virtual line 23 from the furnace wall 1a of the furnace 1 toward the reforming furnace central axis O.
  • the number of nozzles 4 and the charging angle it is preferable to install two or more nozzles 4 at the same angle at symmetrical positions so that the flow in the reforming furnace 1 does not drift. That is, it is preferable to arrange a plurality of nozzles 4 on the furnace wall 1a of the reforming furnace 1 at equal intervals in the circumferential direction. Further, the horizontal angles of the nozzles 4 are the same, and the nozzle axis 22 of each nozzle 4 is preferably along the tangential direction of the same virtual circle 24 that is coaxial with the reformer center axis O.
  • the horizontal angle is preferably such that the diameter of the virtual circle 24 is 1/5 to 2/3 of the inner diameter of the reforming furnace 1.
  • the vertical angle which is the inclination with respect to the horizontal surface of the nozzle axis 22 of the reformed coal blowing nozzle 4 may be the same for all the nozzles 4.
  • the blowing flow rate is about several m / sec to about 20 m / sec, which is substantially equal to the flow rate when the gasified coal 9 is air-conveyed in the gasification furnace 2.
  • the concentration of particles charged into the reforming furnace 1 is higher when the operating pressure of the reforming furnace 1 is higher than when the operating pressure is low. Therefore, the swirl flow in the gasification furnace 2 is affected, and a portion having a high particle concentration in the reforming furnace 1 is more easily formed. Therefore, the effect of the present invention becomes clearer when the operation pressure is higher. Further, when the reactor 21 is scaled up, the diameter of the reforming furnace 1 is increased. Accordingly, mixing of the reformed coal 10 that has been blown with the gasified gas 14 becomes worse, and the uneven concentration of particles tends to occur. Therefore, the effect of the present invention becomes clearer in the scaled up reactor 21 having a larger throughput.
  • two or more types of charging angles ⁇ and ⁇ of the reformed coal blowing nozzles 4A and 4B may be installed in the reforming furnace 1. That is, in the reforming furnace 1 shown in FIG. 3, the charging angles ⁇ of the plurality of first nozzles 4A among the reformed coal blowing nozzles 4A and 4B are all the same. In addition, the charging angles ⁇ of the plurality of second nozzles 4B among the reformed coal blowing nozzles 4A and 4B are all the same angle, and are different from the charging angle ⁇ .
  • the diameters of the virtual circles 24A and 24B corresponding to the nozzle axes 22A and 22B of the plurality of first nozzles 4A and the plurality of second nozzles 4B are different.
  • the dispersibility of the modified coal 10 in the reforming furnace 1 can be further improved. Therefore, it is particularly preferable to install the nozzles 4A and 4B as shown in FIG. 3 when the diameter of the reforming furnace 1 is large, for example.
  • the first nozzles 4A and the second nozzles 4B are alternately installed in the circumferential direction. Thereby, it is suppressed that the flow in the reforming furnace 1 becomes an uneven flow, and the dispersibility of the reformed coal 10 in the reforming furnace 1 can be further improved.
  • the charging speed of the modified coal 10 from the first nozzle 4A and the charging speed of the modified coal 10 from the second nozzle 4B may be different from each other.
  • the reforming coal 10 in the reforming furnace 1, is directed only in the circumferential direction opposite to the swirling flow of the gasification gas 14 introduced from the gasification furnace 2 through the throat 3. Although it shall be thrown in by airflow conveyance, it is not restricted to this.
  • the reformed coal 10 may be introduced in the circumferential direction opposite to the swirl flow of the gasification gas 14, for example, in the same circumferential direction as the swirl flow. Then, the modified coal 10 may be further added.
  • Example 1 An example in the gasification pyrolysis operation using the apparatus shown in FIG. 1 is shown below.
  • the operating conditions of the gasification furnace 2 were a pressure of 2.5 MPa and a temperature of 1450 ° C.
  • the operating conditions of the reforming furnace 1 were a pressure of 2.5 MPa and a temperature of 1100 ° C.
  • the gasification coal 9 pulverized to an average particle size of 40 ⁇ m was introduced into the gasification furnace 2 by air-flow conveyance using nitrogen gas.
  • the amount of gasified coal 9 was 500 kg / h (coal ash content: 2.7%, volatile content: 45%, moisture content: 5%).
  • the input amount of the water vapor 13 to the gasification furnace 2 was set to 50 kg / h, and the input amount of the oxygen 12 was set to 310 Nm 3 / h.
  • the reformed coal 1 was charged by air-conveying the reformed coal 10 using 162 kg / h nitrogen gas. The flow rate of the air current conveyance was 10 m / sec.
  • gasified coal 9 and water vapor 13 and oxygen 12 as the oxygen-containing gas 11 are introduced from four directions toward the tangential direction of the virtual circle of 1/3 of the gasification furnace diameter, A swirling flow was generated.
  • Gasified coal 9, water vapor 13, and oxygen 12 were charged using a double-tube burner.
  • Gasified coal 9 and carrier gas flow inside the double pipe, that is, inside the double pipe, and water vapor 13 flows outside the double pipe, that is, between the inner pipe and the outer pipe of the double pipe.
  • oxygen 12 are mixed and flow.
  • the reforming coal 10 is introduced from four directions toward the tangential direction of the virtual circle 24 1 ⁇ 2 of the reforming furnace diameter using the reforming coal blowing nozzle 4 as shown in FIG. A swirling flow was generated.
  • the amount of the gasification gas 14 at the throat 3 at the outlet of the gasification furnace 2 was 1134 Nm 3 / h, and the heat generation amount of the gasification gas 14 was 1879 kcal / h.
  • the amount of the product gas at the reforming furnace outlet 7 was 1279 Nm 3 / h, and the heat generation amount of the product gas was 2239 kcal / h.
  • the amount of tar produced was negligible. Further, when the inside of the reforming furnace 1 was opened and inspected after 200 hours of operation, no deposits were found on the inner surface of the furnace wall 1a of the reforming furnace 1, and the furnace wall 1a of the reforming furnace 1 was in a clean state. .
  • Example 2 has almost the same apparatus and reaction conditions as Example 1.
  • two first nozzles 4A among the reformed coal blowing nozzles 4A and 4B as shown in FIG. 3 are directed in the tangential direction of a virtual circle 24A that is 1/3 of the diameter of the reforming furnace 1.
  • the other two second nozzles 4B out of the reformed coal blowing nozzles 4A and 4B were directed in the tangential direction of a virtual circle 24B having a diameter 2/3 of the reforming furnace 1.
  • the gasification coal 9 pulverized to an average particle size of 40 ⁇ m as in Example 1 was introduced into the gasification furnace 2 by air-flow conveyance using nitrogen gas.
  • the amount of gasified coal 9 was 500 kg / h (coal ash content: 2.7%, volatile content: 45%, moisture content: 5%).
  • the input amount of the water vapor 13 to the gasification furnace 2 was 50 kg / h, and the input amount of oxygen 12 was 310 Nm 3 / h.
  • the reformed coal 10 is transported in a stream of air using a total of 160 kg / h of the reformed coal 10 from four directions using two first nozzles 4A and two second nozzles 4B. It was input by.
  • the flow rate of the air current conveyance was 10 m / sec.
  • gasified coal 9 was blown from four directions toward the tangential direction of the virtual circle of 1/3 of the gasification furnace diameter to generate a swirling flow.
  • gasified coal 9, water vapor 13, and oxygen 12 were charged using a double-tube burner. Gasified coal 9 and carrier gas flow inside the double pipe. Steam 13 and oxygen 12 are mixed and flow outside the double tube.
  • the amount of the gasification gas 14 at the throat 3 at the outlet of the gasification furnace 2 was 1134 Nm 3 / h
  • the heat generation amount of the gasification gas 14 was 1879 kcal / h
  • the temperature of the reforming furnace 1 was 1100 ° C.
  • the amount of the product gas at the reforming furnace outlet 7 was 1280 Nm 3 / h
  • the heat generation amount of the product gas was 2249 kcal / h.
  • the calorific value was increased as compared with Example 1. Further, when the inside of the reforming furnace 1 was opened and inspected after 200 hours of operation, no deposits were found on the inner surface of the furnace wall 1a of the reforming furnace 1, and the furnace wall 1a of the reforming furnace 1 was in a clean state. .
  • Comparative Example 1 has almost the same apparatus and reaction conditions as Example 1.
  • Comparative Example 1 as shown in FIG. 4, the reformed coal blowing nozzle 4 was opposed from four directions.
  • gasified coal 9 pulverized to an average particle size of 40 ⁇ m was fed into the gasification furnace 2 by airflow conveyance.
  • the amount of gasified coal 9 was 500 kg / h (coal ash content: 2.7%, volatile content: 45%, moisture content: 5%).
  • the input amount of the water vapor 13 to the gasification furnace 2 was set to 50 kg / h, and the input amount of the oxygen 12 was set to 310 Nm 3 / h.
  • the reforming furnace 1 was charged with a total of 160 kg / h of the reformed coal 10 from four directions from the reforming coal blowing nozzle 4 toward the reforming furnace central axis O by airflow conveyance.
  • the flow rate of the air current conveyance was 10 m / sec.
  • gasified coal 9 was blown from four directions toward the tangential direction of the imaginary circle of 1/3 of the gasification furnace diameter to generate a swirling flow.
  • gasified coal 9, water vapor 13 and oxygen 12 were charged using a double-tube burner. Gasified coal 9 and carrier gas flow inside the double pipe. Steam 13 and oxygen 12 are mixed and flow outside the double tube.
  • the amount of the gasification gas 14 in the throat 3 which is the gasification furnace 2 outlet was 1134 Nm 3 / h
  • the heat generation amount of the gasification gas 14 was 1879 kcal / h
  • the temperature of the reforming furnace 1 was 1100 ° C.
  • the amount of product gas at the reforming furnace outlet 7 was 1274 Nm 3 / h
  • the heat generation amount of the product gas was 2168 kcal / h.
  • the amount of heat generation was significantly reduced as compared with Examples 1 and 2.
  • carbonaceous deposits considered to be derived from coal were found on the inner surface of the furnace wall 1a of the reforming furnace 1.
  • Comparative Example 2 has almost the same apparatus and reaction conditions as Example 1.
  • the reformed coal 10 charged into the reforming furnace 1 is the same as the swirling flow of the gasified coal 9 in the gasification furnace 2 in the tangential direction of the virtual circle 1 ⁇ 2 of the reforming furnace diameter. It was thrown in by air flow in the direction.
  • gasified coal 9 pulverized to an average particle size of 40 ⁇ m was fed into the gasification furnace 2 by airflow conveyance.
  • the amount of gasified coal 9 was 500 kg / h (coal ash content: 2.7%, volatile content: 45%, moisture content: 5%).
  • the input amount of the water vapor 13 to the gasification furnace 2 was set to 50 kg / h
  • the input amount of the oxygen 12 was set to 310 Nm 3 / h.
  • the reforming furnace 1 was charged with a total of 160 kg / h of reformed coal 10 from four directions using four reformed coal blowing nozzles 4 and fed into the reformer 1.
  • the flow rate of the air current conveyance was 10 m / sec.
  • gasified coal 9 was blown from four directions toward the tangential direction of the imaginary circle of 1/3 of the gasification furnace diameter to generate a swirling flow.
  • gasified coal 9, water vapor 13 and oxygen 12 were charged using a double tube burner. Gasified coal 9 and carrier gas flow inside the double pipe. Steam 13 and oxygen 12 are mixed and flow outside the double tube.
  • the amount of the gasification gas 14 in the throat 3 which is the gasification furnace 2 outlet was 1134 Nm 3 / h
  • the heat generation amount of the gasification gas 14 was 1879 kcal / h
  • the temperature of the reforming furnace 1 was 1100 ° C.
  • the amount of the product gas at the reforming furnace outlet 7 was 1274 Nm 3 / h
  • the heat generation amount of the product gas was 2151 kcal / h.
  • the amount of heat generation was significantly reduced as compared with Examples 1 and 2 and Comparative Example 1.
  • carbonaceous deposits considered to be derived from coal were found on the inner surface of the furnace wall 1a of the reforming furnace 1.
  • Reforming furnace 1a Reforming furnace furnace wall (furnace wall) 2 Gasification furnace 3 Throat 4, 4A, 4B Reformed coal injection nozzle 5 Gasification burner 6 Slag tap 7 Reforming furnace outlet 8 Water tank 9 Gasification coal 10 Reformed coal 11 Oxygen-containing gas 12 Oxygen 13 Water vapor 14 Gasification gas 15 Slag 16 Product 17 Boiler tube 20 Pyrolysis gasifier for coal 21 Gas stream reactors 22, 22A, 22B Nozzle axis 23 Virtual lines 24, 24A, 24B Virtual circles ⁇ , ⁇ Input angle O Reforming furnace central axis

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Abstract

L'invention concerne une méthode de gazéification de charbon par décomposition thermique utilisant un réacteur en lit à flux de gaz et chambre à deux niveaux supérieur/inférieur (20) comprenant un niveau supérieur avec une chaudière cylindrique de gazéification et un niveau inférieur avec une chaudière cylindrique de réformage (1) connectés par un gueulard à diamètre élargi (3) entre les deux, dans lequel au moins le charbon et un gaz contenant de l'oxygène sont introduits dans la chaudière de gazéification, le gaz de gazéification est généré par l'oxydation partielle du charbon, le gaz de gazéification est introduit dans la chaudière de réformage (1), au moins le charbon est introduit dans la chaudière de réformage (1), le charbon versé dans la chaudière de réformage est décomposé thermiquement par la chaleur sensible du gaz de gazéification et ainsi est généré un gaz généré contenant au moins de l'hydrogène et du monoxyde de carbone. Le charbon introduit dans la chaudière de gazéification est introduit en étant convoyé par des courants d'air dans une direction circonférentielle de façon à créer un écoulement rotationnel à l'intérieur de la chaudière de gazéification, et le charbon introduit dans la chaudière de réformage (1) est introduit en étant convoyé par des courants d'air dans une direction circonférentielle opposée à la direction de l'écoulement rotationnel dans la chaudière de gazéification.
PCT/JP2011/059380 2010-04-16 2011-04-15 Méthode de gazéification de charbon par décomposition thermique et appareil de gazéification de charbon par décomposition thermique WO2011129434A1 (fr)

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JP2012510712A JP5450800B2 (ja) 2010-04-16 2011-04-15 石炭の熱分解ガス化方法および石炭の熱分解ガス化装置
CN201180018845.8A CN102939361B (zh) 2010-04-16 2011-04-15 煤的热解气化方法及煤的热解气化装置
AU2011241502A AU2011241502B2 (en) 2010-04-16 2011-04-15 Method for thermally decomposing and gasifying coal and apparatus for thermally decomposing and gasifying coal

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140083916A (ko) * 2012-12-26 2014-07-04 에스케이이노베이션 주식회사 탄소연료 기류건조기

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105038860A (zh) * 2015-07-10 2015-11-11 北京柯林斯达科技发展有限公司 一种旋流式气化炉以及旋流式气化工艺
ITUB20153666A1 (it) * 2015-09-16 2017-03-16 Clausius Key S R L Processo ed impianto di cogenerazione tramite gassificazione di materia organica
GB2551314B (en) * 2016-06-06 2021-03-17 Kew Tech Limited Equilibium approach reactor
CN106495513B (zh) * 2016-12-26 2019-09-13 北京建筑材料科学研究总院有限公司 一种水泥窑替代燃料气化分级燃烧方法及装置
CN109401798A (zh) * 2018-12-13 2019-03-01 中国华能集团清洁能源技术研究院有限公司 一种双切圆两段式干煤粉加压气化炉及其气化方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59176391A (ja) * 1983-03-28 1984-10-05 Hitachi Ltd 石炭ガス化炉
JPS61246287A (ja) * 1985-04-24 1986-11-01 Mitsubishi Heavy Ind Ltd 噴流床石炭ガス化炉
JPS6426353U (fr) * 1987-08-05 1989-02-14
JPH08295890A (ja) * 1995-04-25 1996-11-12 Mitsubishi Heavy Ind Ltd 噴流床石炭ガス化炉
JPH11269471A (ja) * 1998-03-23 1999-10-05 Nippon Steel Corp 石炭急速熱分解炉およびチャー付着の防止方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004217868A (ja) * 2003-01-17 2004-08-05 Nippon Steel Corp 石炭の水素化熱分解方法
CN1935951B (zh) * 2006-09-21 2010-12-08 武汉凯迪工程技术研究总院有限公司 一种固体含碳原料的高温气化装置
CN101392191B (zh) * 2008-10-15 2011-11-23 合肥工业大学 两段式干煤粉气流床气化炉

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59176391A (ja) * 1983-03-28 1984-10-05 Hitachi Ltd 石炭ガス化炉
JPS61246287A (ja) * 1985-04-24 1986-11-01 Mitsubishi Heavy Ind Ltd 噴流床石炭ガス化炉
JPS6426353U (fr) * 1987-08-05 1989-02-14
JPH08295890A (ja) * 1995-04-25 1996-11-12 Mitsubishi Heavy Ind Ltd 噴流床石炭ガス化炉
JPH11269471A (ja) * 1998-03-23 1999-10-05 Nippon Steel Corp 石炭急速熱分解炉およびチャー付着の防止方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140083916A (ko) * 2012-12-26 2014-07-04 에스케이이노베이션 주식회사 탄소연료 기류건조기
KR102178465B1 (ko) * 2012-12-26 2020-11-16 에스케이이노베이션 주식회사 탄소연료 기류건조기

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