WO2020004779A1 - Réacteur de reformage pour la production d'hydrogène à l'aide d'un chauffage à induction haute fréquence - Google Patents

Réacteur de reformage pour la production d'hydrogène à l'aide d'un chauffage à induction haute fréquence Download PDF

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Publication number
WO2020004779A1
WO2020004779A1 PCT/KR2019/003799 KR2019003799W WO2020004779A1 WO 2020004779 A1 WO2020004779 A1 WO 2020004779A1 KR 2019003799 W KR2019003799 W KR 2019003799W WO 2020004779 A1 WO2020004779 A1 WO 2020004779A1
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WO
WIPO (PCT)
Prior art keywords
reactor
methane gas
induction heating
reforming
supply flow
Prior art date
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/KR2019/003799
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English (en)
Korean (ko)
Inventor
서민호
채홍준
서석준
허성규
이다윗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DONGYANG INDUCTION MELTING FURNACE Co Ltd
Original Assignee
DONGYANG INDUCTION MELTING FURNACE Co Ltd
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Publication of WO2020004779A1 publication Critical patent/WO2020004779A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/342—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/12—Processes employing electromagnetic waves
    • B01J2219/1203—Incoherent waves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0855—Methods of heating the process for making hydrogen or synthesis gas by electromagnetic heating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane

Definitions

  • the present invention relates to a reforming reactor for producing hydrogen using high frequency induction heating.
  • the reforming reactor for hydrogen production is used to produce hydrogen (H 2 ) by reforming a hydrocarbon (C X H X ) such as methane (CH 4 ) with water vapor, and a catalyst for activating the reforming reaction therein. And a heater to support the endothermic reforming reaction inside the reactor.
  • a heater such as a gas burner provides heat to a reactor that is shaped into a pipe shape of a predetermined diameter and length.
  • gas burners that burn heat to provide heat are mainly used as heaters. Therefore, in the related art, not only a problem in which exhaust gas is generated in the combustion process of the gas in the gas burner, but also a very local heating is performed on the part in contact with the flame generated by the combustion of the gas, so that the overall temperature control is not easy. This, in turn, leads to the disadvantage that the production efficiency of hydrogen is lowered.
  • the reforming reaction in the reactor requires preheating of the supplied steam and source gas.
  • the steam and the source gas are heated to a temperature of approximately 400 ° C. using a separate preheater. After preheating, it is fed to the reactor. Therefore, according to the prior art, it is cumbersome to be provided with a preheater in addition to the heater for the reforming reaction.
  • the present invention has been made to solve the problems caused by the prior art, and an object of the present invention is to provide a reforming reaction apparatus for producing hydrogen using high frequency induction heating, which is configured to enable more efficient hydrogen production.
  • Another object of the present invention is to provide a reforming reaction apparatus for producing hydrogen using high frequency induction heating configured to enable preheating of methane gas and steam with a simpler configuration.
  • Still another object of the present invention is to provide a reforming apparatus for producing hydrogen using high frequency induction heating, which is configured to enable cooling of a coil for induction heating with a simpler configuration.
  • One aspect of the reforming reactor for producing hydrogen using high frequency induction heating is a reforming reactor for producing hydrogen: a catalyst for activating the reforming reaction of methane gas and steam A reactor defining a reaction space in which is filled; A heater including a coil wound on an outer surface of the reactor and inductively heating the reactor when power is applied; And a supply flow path through which methane gas and water vapor supplied to the reaction space flow; And methane gas and steam flowing through the supply flow path are heat exchanged with hydrogen gas produced by the reforming reaction of methane gas and steam in the coil or the reaction space which generates heat by induction heating.
  • the heater comprises a coil for induction heating arranged to surround the outer surface of the reactor. Therefore, according to the embodiment of the present invention, it is possible to more efficiently provide the heat required for the reforming reaction for the production of hydrogen inside the reactor, substantially.
  • the reforming reaction is carried out after the methane gas and steam for the production of hydrogen is preheated by a relatively high temperature coil and / or produced hydrogen and the like. Therefore, according to the embodiment of the present invention, by preheating methane gas and steam without using a separate preheater, it is possible to eventually improve the production efficiency of hydrogen.
  • the coil for induction heating is cooled by relatively low temperature methane gas and water vapor. Therefore, according to the embodiment of the present invention, it is possible to prevent the separate configuration or the time required for cooling the coil.
  • FIG. 1 is a longitudinal sectional view schematically showing a first embodiment of a reforming apparatus for producing hydrogen using high frequency induction heating according to the present invention
  • Figure 2 is a longitudinal sectional view schematically showing a second embodiment of a reforming apparatus for producing hydrogen using high frequency induction heating according to the present invention.
  • FIG. 1 is a longitudinal sectional view schematically showing a first embodiment of a reforming apparatus for producing hydrogen using high frequency induction heating according to the present invention.
  • the reforming reactor 1 for producing hydrogen using high frequency induction heating includes a reactor 100, a heater 200, and a supply flow path 401. Hydrogen is produced by the reforming reaction of methane gas (CH 4 ) and water vapor (H 2 O) flowing substantially inside the reactor 100. At this time, the inside of the reactor 100 is filled with a catalyst (C) for the activation of the reforming reaction, the heater 100 is heated by the heater 200 to provide heat for the endothermic reforming reaction.
  • CH 4 methane gas
  • H 2 O water vapor
  • the reactor 100 defines a reaction space 100S filled with the catalyst C for activating the reforming reaction of methane gas and steam.
  • a supply port 100P and an outlet 100D are formed in the reactor 100.
  • the supply port 100P is a place where methane gas and water vapor reformed and reacted in the reaction space 100S are supplied, and the discharge port 100D is hydrogen gas produced by reforming reaction of methane gas and water vapor. Is where it is discharged. Of course, the remaining methane gas and water vapor may also be discharged through the outlet 100D.
  • the discharge port 100D communicates with the discharge flow path 120 through which hydrogen gas produced by the reforming reaction in the reaction space 100S flows.
  • the discharge passage 120 may be defined by the discharge duct 120D.
  • a heat insulating material 130 is disposed on the outer surface of the reactor 100. Substantially, the heat insulator 130 will be disposed between the outer surface of the reactor 100 and the heater 200. The heat insulator 130 serves to insulate the reactor 100 that is induction heated by the heater 200.
  • the heater 200 induction heating the reactor 100 for the endothermic reforming reaction of methane gas and steam.
  • the heater 200 includes a coil 201 wound on the outer surface of the reactor 100. Thus, when power is applied to the coil 201, the reactor 100 will be induction heated.
  • a first supply flow passage 410 to be described later is defined inside at least part of the coil 201.
  • the first supply passage 410 may be defined. That is, a portion of the coil 201 except for both ends of the coil 201 connected to a power source (not shown) may be substantially formed by a portion of the coil 201 wound around the outer surface of the reactor 100.
  • One supply flow path 410 may be defined.
  • the supply flow path 401 is a place where methane gas and water vapor supplied to the reaction space 100S flow.
  • the supply flow passage 401 includes first and second supply flow passages 410 and 421.
  • the first supply channel 410 is defined inside at least part of the coil 201.
  • the second supply flow path 421 is defined in the supply duct 421D to be connected to the reaction space 100S, the supply port 100P, and the first supply flow path 410. Therefore, the methane gas and the water vapor supplied to the reaction space 100S will flow through the first and second supply flow passages 410 and 421 in order.
  • methane gas and water vapor are supplied to the reaction space 100S at about 150 ° C, and the temperature of the coil 201 is increased to about 300 ° C or more during induction heating. Therefore, in the process of flowing methane gas and water vapor through the said supply flow path 401 and the said 1st supply flow path 410, methane gas and water vapor by heat exchange between the methane gas and water vapor, and the coil 201, Is preheated, and the coil 201 may be cooled. That is, in the present embodiment, the methane gas and water vapor substantially flows inside the coil 201, so that the preheating of the methane gas and water vapor and the cooling of the coil 201 can be simultaneously performed.
  • FIG. 2 is a longitudinal sectional view schematically showing a second embodiment of a reforming apparatus for producing hydrogen using high frequency induction heating according to the present invention.
  • reference numerals of FIG. 1 are used, and detailed description thereof will be omitted.
  • the reforming reaction apparatus 2 for producing hydrogen using high frequency induction heating at least a part of the supply duct 422D reforms methane gas and steam in the reaction space 100S. Hydrogen gas produced by the is disposed on the discharge passage 120 is discharged.
  • a part of the second supply passage 422, that is, the supply passage 402, defined by the supply duct 422D is disposed on the discharge passage 120. Therefore, in this embodiment, methane gas and water vapor flowing through the second supply flow passage 422 are heat-exchanged with hydrogen gas flowing through the discharge flow passage 120.
  • the temperature of the methane gas and steam preheated by the heat exchange with the coil 201 is about 200 ⁇ 250 °C, and in general, the temperature of the hydrogen produced by the reforming reaction in the reaction space (100S) is about 800 °C is around. Therefore, in this embodiment, the methane gas and water vapor preheated by the heat exchange with the coil 201 while flowing the first supply flow path 410 flows through the second supply flow path 422, the discharge flow path. It may be further preheated by the hydrogen gas flowing through the 120.
  • the supply flow passage 402 further includes a connection flow passage 430.
  • the connection passage 430 is defined inside the connection duct 430D to connect the first and second supply passages 410 and 422.
  • the connection duct 430D is formed of a material having a relatively low thermal conductivity than the coil 201 and the supply duct 422D. This is to prevent a phenomenon in which heat of hydrogen gas flowing through the discharge passage 120 is transferred to the coil 201 through the supply duct 422D.
  • the reforming reactor (1) (2) for producing hydrogen using high frequency induction heating power is applied to the heater (200) and the coil (201) substantially.
  • the reactor 100 is then induction heated.
  • methane gas and water vapor for the production of hydrogen flows through the supply flow path (401, 402) is supplied to the reactor (100). Therefore, the reforming reaction of the methane gas and steam delivered to the reactor 100, that is, the reaction space 110S is activated by the catalyst C packed in the reactor 100 to produce hydrogen.
  • the hydrogen gas produced in the reactor 100, the remaining methane gas, and water vapor are discharged through the discharge port 100D to flow through the discharge flow path 120.
  • a part of the supply flow passage 401 that is, the first supply flow passage 410 is defined inside at least part of the coil 201, and the second embodiment of the present invention.
  • another portion of the supply passage 402, that is, a portion of the second supply passage 422 is disposed on the discharge passage 120. Therefore, in the first and second embodiments of the present invention, methane gas and water vapor flowing through the supply flow passages 401 and 402 are the coil 201 or the coil 201 and the discharge passage 120. Heat exchanged with the flowing hydrogen gas is preheated, it is supplied to the reactor (100).
  • an inconel circular pipe having an inner diameter of 80 mm, a thickness of 20 mm, and a length of 2,000 mm was used as the reactor 100.
  • the coil 201 a coil including a core made of copper having an outer diameter of 15 mm and an inner diameter of 10 mm and a coating layer provided on the outer circumferential surface of the core was used.
  • Ni / Al 2 O 3 was charged inside the reactor 100.
  • a glass insulation material 130 having a thickness of 50 mm is disposed on an outer surface of the reactor 100.
  • a 3: 1 ratio of water vapor (H 2 O) and methane gas (CH 4 ) were supplied at a space velocity of 6,000 h ⁇ 1 , and the coil 201 had a frequency of 1 kHz. And a current density of 256 A / mm 2 .
  • ⁇ Comparative Example 1> and ⁇ Comparative Example 2> the first and second supply flow passages 410, 421, and 422 were deleted in comparison with Experimental Example 1 and Experimental Example 2. That is, in ⁇ Comparative Example 1> and ⁇ Comparative Example 2>, methane gas and water vapor not heat-exchanged with the produced hydrogen gas were supplied to the reactor 100. In ⁇ Comparative Example 1>, methane gas and steam not preheated were supplied, and in ⁇ Comparative Example 2>, methane gas and steam preheated to about 400 ° C. by a separate preheater were supplied. In Comparative Example 2, the cooling water was circulated inside the coil 201 to cool the coil 201.
  • Experimental Example 1 Experimental Example 2 Comparative Example 1 Comparative Example 2 Coil temperature (°C) 300 305 70 70 H 2 temperature (°C) 250 405 135 400 CH 4 % Conversion 89 95 85 95 H 2 fraction (%) 70 75 67 75 H 2 Production (Nm3 / h) 38 42 35 42

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Mechanical Engineering (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

La présente invention concerne un réacteur de reformage pour produire de l'hydrogène à l'aide d'un chauffage à induction haute fréquence. Un aspect d'un réacteur de reformage pour produire de l'hydrogène à l'aide d'un chauffage à induction haute fréquence, selon un mode de réalisation de la présente invention, est un réacteur de reformage pour produire de l'hydrogène, comprenant : un réacteur définissant un espace de réaction dans lequel un catalyseur d'activation d'une réaction de reformage de gaz de méthane et de vapeur d'eau est rempli; un dispositif de chauffage comprenant une bobine enroulée sur une surface externe du réacteur et chauffant par induction le réacteur lorsqu'un courant est appliqué; et un trajet d'écoulement d'alimentation à travers lequel le gaz de méthane et la vapeur d'eau fournis à l'espace de réaction s'écoulent, le gaz de méthane et la vapeur d'eau s'écoulant à travers le trajet d'écoulement d'alimentation échangeant de la chaleur avec l'hydrogène gazeux produit par la réaction de reformage du gaz de méthane et de la vapeur d'eau, dans la bobine générant de la chaleur par chauffage à induction ou dans l'espace de réaction.
PCT/KR2019/003799 2018-06-28 2019-04-01 Réacteur de reformage pour la production d'hydrogène à l'aide d'un chauffage à induction haute fréquence Ceased WO2020004779A1 (fr)

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KR10-2018-0075032 2018-06-28
KR1020180075032A KR20200001917A (ko) 2018-06-28 2018-06-28 고주파 유도 가열을 이용한 수소 생산용 개질 반응 장치

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111692885A (zh) * 2020-06-24 2020-09-22 广州汤姆逊电气有限公司 一种高温浇注一体互感三用加热功能炉
US20240051821A1 (en) * 2021-04-25 2024-02-15 China University Of Petroleum-Beijing Steel smelting method

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JP2003206102A (ja) * 2002-01-10 2003-07-22 Matsushita Electric Ind Co Ltd 水素生成装置および燃料電池システム
KR100423544B1 (ko) * 2001-04-23 2004-03-18 주식회사 경동도시가스 컴팩트형 수증기 개질장치
KR101194244B1 (ko) * 2010-09-01 2012-10-29 (주)알티아이엔지니어링 수증기 개질기
KR101466881B1 (ko) * 2013-05-21 2014-12-02 한국과학기술연구원 액체 수소를 이용하는 무인 항공기 동력 공급 장치
WO2017036794A1 (fr) * 2015-08-28 2017-03-09 Haldor Topsøe A/S Chauffage par induction de réactions endothermiques

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KR101293856B1 (ko) 2011-10-07 2013-08-07 현대하이스코 주식회사 물 예열 온도 상승을 통하여 개질 효율이 우수한 연료전지용 개질기
KR101353917B1 (ko) 2012-04-05 2014-01-23 한국에너지기술연구원 원료의 혼합과 분배가 개선된 연료 개질기
KR101403699B1 (ko) 2012-07-10 2014-06-05 한국에너지기술연구원 열교환 장치를 내장한 일산화탄소 선택적 산화반응기 및 연료 개질 시스템

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Publication number Priority date Publication date Assignee Title
KR100423544B1 (ko) * 2001-04-23 2004-03-18 주식회사 경동도시가스 컴팩트형 수증기 개질장치
JP2003206102A (ja) * 2002-01-10 2003-07-22 Matsushita Electric Ind Co Ltd 水素生成装置および燃料電池システム
KR101194244B1 (ko) * 2010-09-01 2012-10-29 (주)알티아이엔지니어링 수증기 개질기
KR101466881B1 (ko) * 2013-05-21 2014-12-02 한국과학기술연구원 액체 수소를 이용하는 무인 항공기 동력 공급 장치
WO2017036794A1 (fr) * 2015-08-28 2017-03-09 Haldor Topsøe A/S Chauffage par induction de réactions endothermiques

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111692885A (zh) * 2020-06-24 2020-09-22 广州汤姆逊电气有限公司 一种高温浇注一体互感三用加热功能炉
US20240051821A1 (en) * 2021-04-25 2024-02-15 China University Of Petroleum-Beijing Steel smelting method

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