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WO2014092474A1 - Catalyseur pour la fabrication de gaz de synthèse par reformage à la vapeur-au dioxyde de carbone et procédé de fabrication du gaz de synthèse par l'utilisation de celui-ci - Google Patents

Catalyseur pour la fabrication de gaz de synthèse par reformage à la vapeur-au dioxyde de carbone et procédé de fabrication du gaz de synthèse par l'utilisation de celui-ci Download PDF

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Publication number
WO2014092474A1
WO2014092474A1 PCT/KR2013/011516 KR2013011516W WO2014092474A1 WO 2014092474 A1 WO2014092474 A1 WO 2014092474A1 KR 2013011516 W KR2013011516 W KR 2013011516W WO 2014092474 A1 WO2014092474 A1 WO 2014092474A1
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Prior art keywords
catalyst
reforming
steam
carbon dioxide
zirconia
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Ceased
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English (en)
Korean (ko)
Inventor
조원준
정종태
모용기
유혜진
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Korea Gas Corp
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Korea Gas Corp
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Priority to CN201380071801.0A priority Critical patent/CN104955570B/zh
Priority to AU2013360529A priority patent/AU2013360529B2/en
Publication of WO2014092474A1 publication Critical patent/WO2014092474A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • 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
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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
    • C01B2203/02—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
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1094—Promotors or activators
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalyst for syngas production from natural gas using carbon dioxide, in particular a catalyst useful for syngas production by steam-carbon dioxide reforming (SCR) and a process for producing the same.
  • SCR steam-carbon dioxide reforming
  • the reforming process for producing a mixture of hydrogen and carbon monoxide, so-called syngas, from methane, which is the main component of natural gas, using a catalyst and an oxidant has been industrialized a long time ago and has become an important basic process of the chemical industry.
  • Synthetic gas produced by the methane reforming process is the basis of C1 chemistry and is applied to the process of producing methanol, hydrogen, ammonia, etc. Recently, the production of liquid fuels and oxygen-containing compounds through the synthesis gas production It is emerging as an important method of using natural gas.
  • Oxygen, water vapor, carbon dioxide, or a mixed gas thereof has been used as an oxidant for preparing synthesis gas from hydrocarbons, and many studies have been conducted to develop catalysts having different characteristics according to the type of oxidant.
  • Reforming methods for producing syngas from methane include steam reforming, carbon dioxide reforming, partial oxidation reforming, autothermal reforming, and triple reforming.
  • the steam reforming reaction proceeds according to the following Scheme 1, and mainly a nickel-based catalyst is used.
  • Some supported zirconia supported catalysts are known as steam reforming catalysts. That is, a zirconia-supported nickel catalyst in which cobalt is added to nickel has been disclosed as a steam reforming catalyst for hydrocarbons (US Pat. No. 4,026,823 (1975)). In another method, a titration of a metal such as lanthanum, cerium, and silver to a nickel catalyst A catalyst in which the ratio is added as a cocatalyst supported on common carriers such as alumina, silica, magnesia, zirconia and the like has been disclosed (US Pat. No. 4,060,498).
  • Korean Patent Registration No. 10-0394076 Ni-based reforming catalyst for syngas production and a method for producing syngas from natural gas by steam reforming using the same
  • the nickel-based reforming catalyst (Ni / Ce-Zr 2 ) for syngas production is characterized in that 5 to 20% by weight of nickel is supported on a zirconia carrier modified with cerium.
  • the catalyst was prepared by preparing a zirconia carrier or a zirconia carrier modified with cerium using a co-precipitation method or a sol-gel method and then supporting nickel by an impregnation method or a melting method.
  • DME dimethyl ether
  • an expensive noble metal catalyst has been proposed in which carbon deposition is not a problem.
  • US Pat. No. 5,068,057 discloses Pt / Al 2 O 3 and Pd / Al 2 O 3 catalysts
  • WO 92 / 11,199 discloses high noble metal supported alumina catalysts such as iridium, rhodium and ruthenium. It has been shown to exhibit activity and long lifespan.
  • the noble metal catalyst is unsuitable for industrial use because of its high resistance to carbon deposition and good activity compared to the nickel catalyst, while being expensive.
  • the present invention provides a nickel-based reforming catalyst for syngas production which can produce syngas or hydrogen with high yield while maintaining long life by preventing catalyst deactivation due to coke formation because of excellent activity and stability of the steam-carbon dioxide reforming reaction catalyst. I would like to.
  • the present invention provides a method for producing a synthesis gas by steam-carbon dioxide reforming reaction using the catalyst.
  • the catalyst according to the present invention is effective in minimizing carbon deposition and producing synthetic petrochemical products (wax, naphtha, diesel, etc.) in producing syngas by steam-carbon dioxide (SCR) reforming reaction of methane (2.0). Syngas having a ⁇ 0.2) can be produced, thereby reducing the production cost of the synthetic material.
  • Catalyst and process using the same according to the present invention can be applied to gas to liquid (GTL) FPSO (floating production, storage and offloading; floating production storage and unloading equipment), furthermore DME FPSO, so that various industrial applications are easy in the future. You can expect to lose.
  • GTL gas to liquid
  • FPSO floating production, storage and offloading; floating production storage and unloading equipment
  • 1 is a graph showing the conversion of methane generated from natural gas as a function of time during the synthesis gas manufacturing process according to an embodiment of the present invention.
  • FIG. 2 is a graph showing the molar ratio of hydrogen and carbon monoxide as a function of time in the constituents of the synthesis gas produced according to an embodiment of the present invention.
  • the present invention relates to a nickel-based reforming catalyst prepared using magnesium and lanthanide series which are relatively excellent in carbon deposition in a reforming catalyst by steam.
  • the weight ratio of nickel and magnesium oxide powder in step 2) is 1: 1 to 20, more preferably 1: 1 to 3.
  • the weight ratio of cerium, zirconia and alumina in step 1) is 1: 5 to 10: 20 to 40, it is not preferable because the carbon deposition occurs outside the above range.
  • the firing of step 3) can be carried out in air at a temperature of 700 ⁇ 1200 °C.
  • the mixing of step 3) may be carried out by dry mixing and then kneading and extruding. It is one of the distinguishing features from the prior art that the impregnation method or the melting method which is generally used for preparing a catalyst is not used.
  • the reforming catalyst is preferably supported by 5 to 20% by weight of nickel and magnesium as active ingredients in a cerium-modified zirconia / alumina support (Ce-ZrO 2 / Al 2 O 3 ). If the supported amount is out of the above range, it may be difficult to produce a synthesis gas in which the hydrogen / carbon monoxide ratio is close to two.
  • the present invention is also characterized in that the reforming reaction is carried out by supplying carbon dioxide, steam and methane under the conditions of the reaction temperature 700 ⁇ 1200 °C, reaction pressure 15 ⁇ 20 bar, space velocity 4000 ⁇ 7000 h -1 using the catalyst It provides a method for producing a synthesis gas. Since the ratio of hydrogen / carbon monoxide in the synthesis gas produced through the reforming reaction is 2.0 ⁇ 0.2, it is possible to easily provide an efficient synthesis gas for producing synthetic petrochemical products (wax, naphtha, diesel, etc.).
  • a nickel reforming catalyst is prepared by supporting a predetermined amount of nickel / magnesium metal on a zirconia / alumina carrier modified with cerium, thereby producing steam-carbon dioxide reforming reaction of methane natural gas using the same. Synthesis gas, which is a mixture of carbon monoxide and hydrogen, can be produced in high yield.
  • the nickel reforming catalyst used for the steam-carbon dioxide reforming reaction of methane natural gas according to the present invention contains 5 to 20 wt% of nickel and magnesium as active ingredients in a cerium-modified zirconia / alumina support (Ce-ZrO 2 / Al 2 O 3 ). It is preferable that it is a reforming catalyst supported by%. If the supported amount of nickel / magnesium is out of the above range and less than 5 wt% with respect to the cerium-modified zirconia / alumina carrier, there is a problem of low activity. If it exceeds 20 wt%, deactivation of the catalyst due to deposition of coke occurs. I can't.
  • the zirconia / alumina carrier (Ce-ZrO 2 / Al 2 O 3 ) modified cerium used as a carrier is a mixture of zirconia / alumina and cerium, the cerium (Ce) is 0.01 0.01 based on 1 mol of zirconia / alumina It is contained in a ⁇ 1.0 molar ratio range, there is a problem that the activity of the catalyst is lowered if cerium is modified in excess in excess of 1.0 molar ratio.
  • a method of modifying cerium on a zirconia-based / alumina carrier or a method of supporting nickel / magnesium is generally known, that is, a coprecipitation method, a precipitation deposition method, a sol-gel method. Dry mixing, kneading, extrusion and baking after dry mixing are used instead of the melting method and the impregnation method.
  • ceria, zirconia and alumina may be mixed in a desired ratio to obtain a zirconia / alumina carrier modified with cerium.
  • the mixing method is not particularly limited as long as it is a dry mixing method generally used in the industry such as a ball mill method.
  • nickel and magnesium a mixture of nickel oxide and magnesium oxide is mixed in powder form, mixed with a zirconia / alumina carrier modified with cerium, and kneaded and then baked. It is preferable to perform baking for 5 to 8 hours in air at the temperature of 700-1200 degreeC.
  • the catalyst when measuring the reforming activity of the catalyst, a typical fixed bed catalyst reactor manufactured in a laboratory is used.
  • the catalyst is molded and pulverized to have a particle size of 1 to 2 mm as a pretreatment process before the reaction, and then charged in a reactor by a required amount, and then reduced with 5% hydrogen at 700 ° C. for 1 hour before use.
  • methane and water vapor are injected into the reactor as a reactant in a molar ratio of 1: 1 to 3 and carbon dioxide of 0.4 to 1, and nitrogen is added as a diluent gas if necessary.
  • the temperature of the reactor is controlled in the range of 700 ⁇ 1200 °C by an electric heater and a programmable thermostat, the reaction pressure is 15 ⁇ 20 bar, the mass flow controller so that the space velocity is 4000 ⁇ 7000 h -1
  • Synthetic gas can be manufactured by continuously injecting a gas while controlling a flow rate of the gas with a mass flow controller.
  • the composition of the gas before and after the reaction is analyzed by gas chromatograph directly connected to the reactor, whereby a poropak column is used for separation of the gas.
  • the activity was measured at 750 ° C. over time, and the initial activity and the activity after 200 minutes were determined by the yield of hydrogen in the product and the conversion rate of methane. Measured through.
  • the method for producing syngas from natural gas using the reforming catalyst according to the present invention shows better activity than the activity of the conventional zirconia-supported nickel reforming catalyst, and also improves the activity of the catalyst to maintain high activity even at high gas space velocity. This suggests the possibility of using it as an industrial catalyst.
  • Ceria, zirconia, and alumina were put in the amounts shown in Table 1 below and mixed in a dried state.
  • Magnesium, nickel, alumina was also processed in the same process and mixed to the content of Table 2 below.
  • Each was calcined at the final 900 °C for 6 hours to prepare a powder. After mixing two kinds of powders (mixing) sufficiently, the temperature was raised to 750 ° C at a rate of 3 ° C / min and calcined for 6 hours. Physical properties of the catalyst obtained are shown in Table 1 and Table 2.
  • Table 1 Sample name Analysis item Content (wt%) 1 hole type CeO 2 1 to 3 MgO 1 to 3 NiO 3 ⁇ 8 ZrO 2 2 ⁇ 8 5 hole type CeO 2 1-5 MgO 1-5 NiO 3 ⁇ 8 ZrO 2 2 ⁇ 8
  • Example 1 The catalyst prepared in Example 1 was used in an SCR process (Steam, Carbon dioxide Reforming). Operating conditions were kept at the same temperature 900 °C, 18bar pressure was carried out reforming of methane at a space velocity of injection by altering the flow rate of the water vapor, carbon dioxide, methane 4000hr -1 and 7000hr -1. The ratio of the injected gas and the reaction result are shown in Table 3 below, FIGS. 1 and 2.
  • the catalyst of the example is much larger than that of the comparative example. This means that the reactor size can be minimized so that the same CH 4 conversion can be achieved with a capacity of 1/3 to 1/5 when designing a commercialized reactor, that is, it is economical.
  • the CO 2 content in the reaction gas can be increased by more than two times compared to the comparative example. Therefore, it is advantageous to use a gas having a high CO 2 content in the reaction gas, and also, there is an advantage that the CO 2 treatment capacity is higher than that of other processes because a large amount of CO 2 remaining after the reaction can be recovered.
  • the catalyst according to the present invention is effective in minimizing carbon deposition and producing synthetic petrochemical products (wax, naphtha, diesel, etc.) in producing syngas by steam-carbon dioxide (SCR) reforming reaction of methane (2.0). Syngas having a ⁇ 0.2) can be produced, thereby reducing the production cost of the synthetic material.
  • Catalyst and process using the same according to the present invention can be applied to gas to liquid (GTL) FPSO (floating production, storage and offloading; floating production storage and unloading equipment), furthermore DME FPSO, so that various industrial applications are easy in the future. You can expect to lose.
  • GTL gas to liquid
  • FPSO floating production, storage and offloading; floating production storage and unloading equipment

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un catalyseur pour la fabrication d'un gaz de synthèse à partir d'un gaz naturel par l'utilisation de dioxyde de carbone, ou de façon plus spécifique, l'invention concerne un catalyseur utile pour la fabrication d'un gaz de synthèse au moyen de reformage à la vapeur-au dioxyde de carbone. Le catalyseur selon la présente invention est fabriqué par un procédé comprenant les étapes de : 1) fabrication d'un support de zircone et d'alumine revêtu par du cérium par utilisation de mélange à sec ; 2) préparation de poudres d'oxyde de nickel et de magnésium ; et 3) mélange et cuisson d'une poudre du support dans l'étape 1) et des poudres de métaux de l'étape 2). Le rapport de l'hydrogène au monoxyde de carbone dans le gaz de synthèse qui est fabriqué par l'utilisation du catalyseur selon la présente invention, peut être contrôlé à 2,0±0,2, ce qui permet de fournir facilement du gaz de synthèse qui est efficace pour la production de produits pétrochimiques de synthèse (tels qu'une cire, un naphta et un diesel).
PCT/KR2013/011516 2012-12-12 2013-12-12 Catalyseur pour la fabrication de gaz de synthèse par reformage à la vapeur-au dioxyde de carbone et procédé de fabrication du gaz de synthèse par l'utilisation de celui-ci Ceased WO2014092474A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201380071801.0A CN104955570B (zh) 2012-12-12 2013-12-12 用于通过水蒸气‑二氧化碳重整生产合成气的催化剂及使用其生产合成气的方法
AU2013360529A AU2013360529B2 (en) 2012-12-12 2013-12-12 Catalyst for manufacturing synthetic gas through steam-carbon dioxide reforming, and method for manufacturing synthetic gas by using same

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KR20120144029A KR101421825B1 (ko) 2012-12-12 2012-12-12 수증기-이산화탄소 개질에 의한 합성가스 제조용 촉매 및 이를 이용한 합성가스 제조방법
KR10-2012-0144029 2012-12-12

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105944733A (zh) * 2016-05-12 2016-09-21 中国科学院福建物质结构研究所 一种稀土改性的多级孔负载型镍基催化剂、制备方法及应用
WO2020053715A1 (fr) * 2018-09-12 2020-03-19 Sabic Global Technologies B.V. Bi-reformage d'hydrocarbures pour produire un gaz de synthèse
US11104575B2 (en) 2016-05-12 2021-08-31 Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Science Nanocatalysts, preparation methods and applications for reforming carbon dioxide and methane to syngas

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107098312B (zh) * 2017-05-05 2021-04-13 湖南大学 一种利用烟气制备合成气的方法
CN110589765A (zh) * 2019-10-09 2019-12-20 中石化南京工程有限公司 一种利用天然气制备不同比例合成气的方法及系统
KR102540205B1 (ko) * 2022-11-04 2023-06-09 (주)바이오프랜즈 배연가스 내 이산화탄소를 일산화탄소로의 이중 개질 전환법, 이를 이용한 시멘트 킬른보일러 발생 배연가스로부터 다이메틸에테르 생산 시스템 및 이시스템을 이용한 시멘트 킬른보일러 발생 배연가스로부터 다이메틸에테르를 제조하는 방법
KR102784469B1 (ko) * 2024-04-29 2025-03-24 (주)세라컴 암모니아분해촉매 및 이의 제조방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08109021A (ja) * 1994-10-05 1996-04-30 Santoku Kinzoku Kogyo Kk 酸素吸収・放出能を有する複合酸化物及びその製造法
KR20060132446A (ko) * 2005-06-17 2006-12-21 한국가스공사 탄화수소로부터 디메틸에테르를 제조하는 방법
KR100892033B1 (ko) * 2007-10-08 2009-04-07 한국에너지기술연구원 고표면적 스핀넬 구조의 나노크기 결정을 가지는ｙＭｇＯ(1-ｙ)Ａｌ₂Ｏ₃에 나노크기로 담지된 니켈계개질촉매 및 이를 이용한 수증기-이산화탄소 복합개질에의한 천연가스로부터 합성가스의 제조방법
KR100991263B1 (ko) * 2008-08-01 2010-11-01 현대중공업 주식회사 천연가스를 수증기와 이산화탄소로 동시에 개질하는 혼합개질 반응용 니켈계 촉매

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050096215A1 (en) * 2003-10-31 2005-05-05 Conocophillips Company Process for producing synthesis gas using stabilized composite catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08109021A (ja) * 1994-10-05 1996-04-30 Santoku Kinzoku Kogyo Kk 酸素吸収・放出能を有する複合酸化物及びその製造法
KR20060132446A (ko) * 2005-06-17 2006-12-21 한국가스공사 탄화수소로부터 디메틸에테르를 제조하는 방법
KR100892033B1 (ko) * 2007-10-08 2009-04-07 한국에너지기술연구원 고표면적 스핀넬 구조의 나노크기 결정을 가지는ｙＭｇＯ(1-ｙ)Ａｌ₂Ｏ₃에 나노크기로 담지된 니켈계개질촉매 및 이를 이용한 수증기-이산화탄소 복합개질에의한 천연가스로부터 합성가스의 제조방법
KR100991263B1 (ko) * 2008-08-01 2010-11-01 현대중공업 주식회사 천연가스를 수증기와 이산화탄소로 동시에 개질하는 혼합개질 반응용 니켈계 촉매

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105944733A (zh) * 2016-05-12 2016-09-21 中国科学院福建物质结构研究所 一种稀土改性的多级孔负载型镍基催化剂、制备方法及应用
CN105944733B (zh) * 2016-05-12 2019-04-16 中国科学院福建物质结构研究所 一种稀土改性的多级孔负载型镍基催化剂、制备方法及应用
US11104575B2 (en) 2016-05-12 2021-08-31 Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Science Nanocatalysts, preparation methods and applications for reforming carbon dioxide and methane to syngas
WO2020053715A1 (fr) * 2018-09-12 2020-03-19 Sabic Global Technologies B.V. Bi-reformage d'hydrocarbures pour produire un gaz de synthèse

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