[go: up one dir, main page]

WO2019050335A1 - Catalyseur à base de nickel et système de production de gaz de synthèse l'utilisant - Google Patents

Catalyseur à base de nickel et système de production de gaz de synthèse l'utilisant Download PDF

Info

Publication number
WO2019050335A1
WO2019050335A1 PCT/KR2018/010505 KR2018010505W WO2019050335A1 WO 2019050335 A1 WO2019050335 A1 WO 2019050335A1 KR 2018010505 W KR2018010505 W KR 2018010505W WO 2019050335 A1 WO2019050335 A1 WO 2019050335A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
active
metal
oxide
hours
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/KR2018/010505
Other languages
English (en)
Korean (ko)
Inventor
김용태
전기원
박해구
곽근재
이윤조
민지은
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.)
Korea Research Institute of Chemical Technology KRICT
Original Assignee
Korea Research Institute of Chemical Technology KRICT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Korea Research Institute of Chemical Technology KRICT filed Critical Korea Research Institute of Chemical Technology KRICT
Publication of WO2019050335A1 publication Critical patent/WO2019050335A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J23/78—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 alkali- or alkaline earth metals
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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
    • 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 syngas production system for producing syngas by simultaneously modifying natural gas with steam and carbon dioxide using a reactor containing a catalyst for synthesis gas production.
  • the syngas produced in the reforming process is a mixture of hydrogen and carbon monoxide and can be used as a reactant for the synthesis of expensive chemical products such as ammonia and methanol.
  • the reforming process is an essential technology for the production of synthetic fuels because it is used as a reactant for next-generation DME (Dimethylesther) synthesis and FT (Fischer-Tropsch) synthesis process.
  • SRM steam reforming of methane
  • POM partial oxidation of methane
  • CDR carbon dioxide reforming reaction of methane and carbon dioxide reforming of methane
  • H 2 / CO carbon monoxide and hydrogen
  • H 2 / CO ratio of 3 or more can be obtained, which is a reforming reaction suitable for hydrogen production and ammonia synthesis reaction.
  • H 2 / CO ratio is about 2 Methanol reforming reaction and the Fischer-Tropsch reaction.
  • This individual reforming process is also called auto-thermal reforming (ATR) and tri-reforming in which POM and SRM are mixed for maintaining the proper H 2 / CO ratio with increasing energy and carbon efficiency
  • ATR auto-thermal reforming
  • POM, SRM and CDR three reforming reactions
  • synthetic gas having different H 2 / CO ratios can be prepared depending on the kind of the reforming reaction and the catalyst, and patents using the differentiation in which the subsequent synthesis process using the synthesis gas is appropriately changed are currently being filed [Korean Patent Open No. 2006-0132293; Korean Patent Publication No. 2005-0051820].
  • the present invention relates to a nickel-based catalyst capable of simultaneously carrying out SRM and CDR as a mixed reforming process, and to provide a catalyst for synthesizing a synthetic gas, which can be used for synthesis of methanol and Fischer- do.
  • Another object of the present invention is to provide a syngas production system for producing a syngas by simultaneously modifying natural gas with steam and carbon dioxide using a reactor containing the catalyst for synthesizing the synthesis gas.
  • the present invention relates to a catalyst for use in the production of syngas from natural gas, comprising at least a support material comprising magnesium (Mg) and aluminum (Al), an activation promoting material comprising at least cerium (Ce) Characterized in that the O 2 storage amount of the oxide of the metal and the activity promoting material, which is the active material exposed on the surface of the catalyst, is 60 to 70 ⁇ mol O 2 / g cat .
  • a catalyst for synthesis gas production is provided.
  • At least of the metal (M 1), the oxide of the active material (M 1 O), metal active promoting material (M 2) and the oxide of the active promoting material (M 2 O) the active substance in the catalyst surface of the syngas for preparing And is a catalyst for exposing a part of the catalyst.
  • the synthesis gas for producing the catalyst the active material of a metal (M 1) at least an oxide of some active promoting material of exposure to at least the surface of the catalyst portion is 1.3 to 5.6%, exposed to the catalyst surface of (M 2 O) and And is a catalyst which is in contact with the catalyst.
  • the synthesis gas for producing the catalyst the molar ratio of the active material of a metal (M 1) and activity promoting material is a metal (M 2) exposed on the surface (M 1 / M 2) is from 0.2 to 2 of catalyst.
  • the catalyst for synthesizing the synthesis gas is a catalyst having a molar ratio (M 1 / M 1 O) of the metal (M 1 ) as the active material to an oxide (M 1 O) of the active material in the range of 0.1 to 1.3.
  • the support material is a metal oxide mixed with the support material and is included in the form of a hydrotalcite crystal structure.
  • the crystal size of the support material is 14.4 to 64.3 nm.
  • the present invention also provides a synthesis gas production system for producing a synthesis gas from natural gas, comprising: a supply part for supplying the natural gas; And a reforming reactor for receiving the catalyst for synthesizing the synthesis gas, wherein the steam reforming reaction of methane and the carbon dioxide reforming reaction of methane proceed at the same time.
  • the present invention relates to a nickel-based catalyst capable of simultaneously carrying out SRM and CDR, and provides a shaped catalyst for synthesizing a synthetic gas, which can be used for synthesis and Fischer-Tropsch reaction, It is possible to provide a catalyst having excellent ability.
  • the present invention also provides a syngas production system for producing syngas by simultaneously modifying natural gas with steam and carbon dioxide using a reactor containing a catalyst for synthesizing a synthesis gas, It is possible to provide an effect of maintaining stability.
  • Fig. 1 shows images of catalysts according to Examples and Comparative Examples of the present invention.
  • a syngas production system is a syngas production system for converting natural gas into syngas.
  • the system includes a reactor for regulating the molar ratio of the reactants contained in the natural gas to obtain a synthesis gas containing the product of the required composition And a reforming reactor 20 for receiving a natural gas supply unit 10 for supplying natural gas and a catalyst for synthesis gas production and simultaneously performing a steam reforming reaction of methane and a carbon dioxide reforming reaction of methane.
  • the catalyst for synthesis gas production is a catalyst used for producing a synthesis gas containing hydrogen and carbon monoxide from a natural gas containing methane and includes a support material, an activity promoting material and an active material.
  • the catalyst for synthesizing a synthesis gas according to the present invention contains at least magnesium (Mg) and aluminum (Al) as a support material, at least cerium (Ce) as an activity promoting material and at least nickel .
  • the catalyst for synthesizing the synthetic gas is a catalyst in which the active material is exposed to the surface at 1.3 to 5.6%. In other respects, when measuring the number of moles of hydrogen (H 2 ) adsorbed per g of the catalyst, 1.3 to 5.6%.
  • the synthetic gas producing catalyst includes at least a part of an oxide of an active material and an oxide of an activity promoting material. More specifically, in the preparation of a catalyst for synthesizing a synthetic gas by impregnating a precursor of the precursor of the precursor and a precursor of the precursor of the precursor, followed by drying and firing, the precursor of the precursor and the precursor of the precursor are partially reduced and oxidized, At least a part of the metal (M 1 ) as the active material, the oxide (M 1 O) of the active material, the metal (M 2 ) as the activity promoting material and the oxide (M 2 O) as the activation promoting material are exposed.
  • the catalyst for synthesizing the syngas is characterized in that at least a part of the metal as the active material is exposed to the catalyst surface at an amount of 1.3 to 5.6% and is in contact with at least a part of the oxide of the active promoting material exposed on the surface.
  • the metal as the active material is exposed to less than 1.3% of the surface of the catalyst, the catalytic activity is too low.
  • the metal is exposed to more than 5.6%, the catalyst activity is too high, have.
  • the catalyst for synthesizing the synthesis gas is characterized in that the molar ratio (M 1 / M 1 O) of the metal (M 1 ) as the active material to the oxide (M 1 O) of the active material is 0.1 to 1.3.
  • the molar ratio is less than 0.1 or more than 1.3, the selectivity of the product is low and various by-products are produced. More preferably, the molar ratio of the active material, the metal (M 1) with the active material oxide (M 1 O) (M 1 / M 1 O) is 0.8 to 1.0.
  • the catalyst for synthesis gas is characterized in that the molar ratio of one (M 1 / M 2) of the active material of a metal (M 1) and activity promoting material is a metal (M 2) exposed at the surface it is 0.2 to 2.
  • the molar ratio (M 1 / M 2 ) is less than 0.2, there is a problem that oxygen is difficult to supply to the active metal during the reaction and the activity is lowered.
  • the mole ratio is more than 2, the metal oxide of the active promoter clogs the active metal .
  • the molar ratio (M 1 / M 2 ) is in the above range, the resistance of the catalyst material to the poisoning material that may be contained in the reactant is considered to be high, and the stability is high, and the lifetime of the catalyst is also good.
  • the activity promoting material is a substance that increases the oxygen storage ability and is included in the catalyst, so that the deactivation of the catalyst by carbon deposition during the reforming reaction can be suppressed.
  • the catalyst for synthesizing the synthesis gas includes a mesopore having an average pore size of 18.6 to 33.5 nm and a micropore having a pore size of 1 nm or less. And preferably has a mesopore / micropore volume ratio of 92 to 115. If the mesopore / micropore volume ratio is too low, there is a problem that the dispersion of the metal on the surface of the support becomes low due to the large particles of the active material metal. If the mesopore / micropore volume ratio is too high, It can fall.
  • the catalyst for synthesizing the synthesis gas includes a support having a hydrotalcite crystal structure as a metal oxide containing a support material.
  • the support material is at least magnesium (Mg) and aluminum comprises (Al), if the support is formed of a MgO / Al 2 O 3 weight ratio is 3/7 to 7/3 of the hydrotalcite crystal structure as the active substance and the active form Thereby providing a supporting structure to which the promoting substance can bind.
  • the crystal size of the metal oxide containing the support material is 14.4 to 64.3 nm.
  • the concentration of the total base point / acid point is increased and the catalytic activity is negatively affected. 64.3 nm, there is a problem that the concentration of the total base point / acid point is lowered, resulting in carbon deposition during the reaction.
  • the catalyst for synthesizing a synthetic gas is a catalyst which is formed into a form including at least two or more holes having a metal oxide storage amount of 60 to 70 ⁇ mol O 2 / g cat as a metal and an activity promoting material exposed to the surface.
  • the present invention provides a syngas production system for producing syngas by simultaneously modifying natural gas with steam and carbon dioxide using a reactor containing the catalyst for synthesizing a synthetic gas, Can be maintained. Preferably, it is molded in a 4-hole form.
  • a method for preparing a catalyst for synthesis gas production comprises first preparing a precursor of an activity promoting material containing at least cerium (Ce) on a support formed of a support material containing at least magnesium (Mg) and aluminum (Al) And at the same time or in turn carrying a precursor of an active material containing at least nickel (Ni). And then dried at 100 to 150 ° C to obtain a powdery catalyst.
  • the water and the catalyst of the powder type are mixed and ball-milling is carried out for 9 to 12 hours, followed by a spray drying process using a ball milled powder, followed by using a spherical spray-dried powder Thereby obtaining a catalyst-shaped body having at least two or more holes.
  • the obtained shaped catalyst is calcined at a temperature of 950 to 1050 ⁇ to produce a catalyst for synthesizing a synthetic gas having the above physical properties.
  • a Mg-Al metal oxide having a hydrotalcite structure having a MgO / Al 2 O 3 weight ratio of 3/7 to 7/3 as a support is used to prepare a Ce metal by impregnation using a cerium precursor
  • a mixture of 3 to 20% by weight based on the total catalyst weight and 5 to 20% by weight based on the weight of the total catalyst prepared using the nickel precursor is prepared. Thereafter, the mixture is stirred at 50 to 100 ° C for 10 to 15 hours by using a vacuum drier, then water as a solvent is removed and dried at 100 to 150 ° C for 24 hours or more to obtain a powdery catalyst.
  • the water and the catalyst of the powder type are mixed and ball-milling is carried out for 9 to 12 hours, followed by a spray drying process using a ball milled powder, followed by using a spherical spray-dried powder Thereby obtaining a catalyst-shaped body having at least two or more holes. And the obtained shaped catalyst is calcined at a temperature of 950 to 1050 ⁇ for 5 to 8 hours to prepare a synthetic gas producing catalyst having the above physical properties.
  • a syngas production system is a syngas production system for converting natural gas to syngas.
  • the natural gas supply unit 10 includes a natural gas supply unit 10 for supplying a natural gas To control the molar ratio of the reactants contained in the gas.
  • the natural gas supply unit 10 may include a pretreatment process for supplying the natural gas with an optimized natural gas composition.
  • the composition of the natural gas supplied through the natural gas supply unit is CH 4 , CO 2 , H 2 O and N 2 and is supplied such that the molar ratio of CH 4 / CO 2 / H 2 O / N 2 is in the range of 1 / 0.3-0.6 / 1.0-2.0 / 0.8-1.2.
  • the natural gas supply unit 10 is connected to the reforming reactor 20 at a rate of 4,000 to 6,000 L / kg cat / hr based on the volume of methane (CH 4 ) .
  • the feed rate may increase proportionally.
  • the natural gas of the above composition is supplied to the reforming reactor 20 containing the catalyst for producing synthesis gas according to the present invention through the supply portion 10.
  • the reaction conditions such as the reaction temperature and the reaction pressure are adjusted so that the steam reforming reaction of methane and the carbon dioxide reforming reaction of methane proceed simultaneously, thereby producing a synthesis gas having a desired composition.
  • the reforming reactor 20 maintains a reaction temperature of 700 to 900 DEG C and a reaction pressure of 0.5 to 20 atm.
  • the CH 4 conversion rate is 93% or more, and even when the reaction occurs at a relatively low temperature (700 to 800 ° C), the CH 4 conversion rate is 72% Can be confirmed by an experimental example to be described later.
  • the composition of the natural gas supplied through the natural gas supply unit can be controlled by the carbon deposition conditions (including CH 4 , CO 2 , and N 2 , and the molar ratio of CH 4 / CO 2 / N 2 being 1 / 0.8-1.2 / 0.8-1.2
  • the conversion rate is more than 87.1%, if the reaction at a relatively low temperature (700 to 800 °C) to take place even when the reaction 25 time, CH 4 conversion is The stability can be confirmed to be 79.5% or more by the following experimental examples.
  • the catalyst for synthesizing a synthetic gas according to the present invention has a good oxygen storage capacity, it is resistant to carbon deposition even when it is reacted under the carbon deposition conditions, thereby maintaining stability during multiple reforming. This can be confirmed by an example.
  • PURAL MG30 (a product of Sasol, having a specific surface area of at least 250 m 2 / g is Mg-Al metal oxide having a hydrotalcite structure with a weight ratio of MgO / Al 2 O 3 of 3/7 as a support of a catalyst for synthesis gas synthesis, hereinafter, "Mg-Al” means any) to use and also by using the cerium acetate precipitation and such that 6 wt% of the catalyst weight producing a Ce metal whole at the same time the nickel as nickel precursor nitrate (Ni (NO 3) 2 6H 2 O), and the mixture was stirred at 70 ° C for 12 hours using a vacuum drier.
  • Ni (NO 3) 2 6H 2 O) nickel as nickel precursor nitrate
  • a 4-hole catalyst was formed by using a spherical spray-dried powder and calcined at 1000 ° C for 6 hours to prepare a final catalyst, Ni-Ce / Mg-Al.
  • PURAL MG30 (a product of Sasol, having a specific surface area of at least 250 m 2 / g is Mg-Al metal oxide having a hydrotalcite structure with a weight ratio of MgO / Al 2 O 3 of 3/7 as a support of a catalyst for synthesis gas synthesis, hereinafter, "Mg-Al” means any) to use and also by using the cerium acetate precipitation and such that 6 wt% of the catalyst weight producing a Ce metal whole at the same time the nickel as nickel precursor nitrate (Ni (NO 3) 2 6H 2 O), and the mixture was stirred at 70 ° C for 12 hours using a vacuum drier.
  • Ni (NO 3) 2 6H 2 O) nickel as nickel precursor nitrate
  • PURAL MG30 (a product of Sasol, having a specific surface area of at least 250 m 2 / g is Mg-Al metal oxide having a hydrotalcite structure with a weight ratio of MgO / Al 2 O 3 of 3/7 as a support of a catalyst for synthesis gas synthesis, hereinafter, "Mg-Al” means any) to use and also by using the cerium acetate precipitation and such that 6 wt% of the catalyst weight producing a Ce metal whole at the same time the nickel as nickel precursor nitrate (Ni (NO 3) 2 6H 2 O), and the mixture was stirred at 70 ° C for 12 hours using a vacuum drier.
  • Ni (NO 3) 2 6H 2 O) nickel as nickel precursor nitrate
  • the final catalyst, Ni-Ce / Mg-Al, was prepared by forming a 4-hole catalyst using a spherical spray-dried powder and calcining at 1200 ° C for 6 hours.
  • PURAL MG30 product of Sasol having a hydrotalcite structure MgO Al metal oxide having a MgO / Al 2 O 3 weight ratio of 3/7 and a specific surface area of at least 250 m 2 / g (Hereinafter, referred to as " Mg-Al-O ") by means of impregnation method using cerium acetate so that the Ce metal is 6 wt% 3 ) 2 .6H 2 O), and the mixture was stirred at 70 ° C for 12 hours using a vacuum drier. Thereafter, water as a solvent was removed, and the mixture was heated in an oven at 100 ° C for 24 hours or more And dried.
  • pellets of 1-hole were formed using the dried powder, and the obtained catalyst compact was sintered at 1000 ° C for 6 hours to obtain a compacted compact having a compacting density of 1.57 g / cc.
  • the final catalyst Ni-Ce / Mg -Al.
  • PURAL MG30 product of Sasol
  • Mg-Al-O &quot a hydrotalcite structure MgO Al metal oxide having a MgO / Al 2 O 3 weight ratio of 3/7 and a specific surface area of at least 250 m 2 / g
  • FIG. 1 shows an image of the catalyst prepared through the above Examples and Comparative Examples.
  • Oxygen storage amount measurement is 750 o C in a hydrogen reduction and by measuring the oxygen consumption at 400 o C] After lowering the temperature after a 400 o C, to measure the oxygen reserves of oxygen consumption and cerium to the Ni NiO. After the reduction process, the oxygen consumption at NiO was measured at 400 ° C, and the difference in oxygen consumption between Ni and NiO was calculated as the oxygen content of cerium. Other physical properties measurement results are shown in Table 1 below.
  • the molar ratio of CH 4 : CO 2 : H 2 O: N 2 as a reactant was fixed at a ratio of 1: 0.4: 1.6: 1 as a reactant in the feed part, and the reforming reaction was carried out by injecting into the reactor.
  • 0.5 g of the catalyst and 0.5 g of alpha-alumina as a diluent were uniformly mixed, charged into a reforming reactor, reduced under hydrogen atmosphere (5 vol% H 2 / N 2 ) at 700 ° C for 3 hours, The reaction was carried out at 730 ° C. or 830 ° C. under a reaction pressure of 0.5 MPa and a space velocity of 5000 L (CH 4 ) / kgcat / hr.
  • the conversion ratios were measured in the following Table 2 (reaction temperature 730 ° C.) 830 ⁇ ).
  • the reforming reaction was carried out by injecting the reactant at a feed ratio of 1: 1: 1 in the molar ratio of CH 4 : CO 2 : N 2 to the reactor.
  • 0.5 g of the catalyst and 0.5 g of alpha-alumina as a diluent were uniformly mixed, charged into a reforming reactor, reduced under hydrogen atmosphere (5 vol% H 2 / N 2 ) at 700 ° C for 3 hours, The reaction was carried out at 730 ° C. or 830 ° C. under a reaction pressure of 0.5 MPa and a space velocity of 5000 L (CH 4 ) / kg cat / hr.
  • the conversion ratios were measured in the following Table 4 (reaction temperature 730 ° C.) 830 ⁇ ).
  • Example 3 A thermogravimetric analyzer (SDT 600, TA instruments (USA)) was used to analyze the carbon deposition amount of the experimental catalyst. The weight loss of the sample was measured by supplying air from 30 ° C to 1000 ° C to calculate the carbon deposition amount. The results are shown in Table 6 (reaction temperature 730 ° C) and Table 7 (reaction temperature 830 ° C).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Nanotechnology (AREA)

Abstract

La présente invention concerne un système de production de gaz de synthèse pour transformer un gaz naturel en gaz de synthèse, et peut fournir un système de production de gaz de synthèse comprenant : une partie d'alimentation pour fournir un gaz naturel; et un réacteur de reformage qui reçoit un catalyseur pour produire un gaz de synthèse, et dans lequel le reformage à la vapeur du méthane et le reformage au dioxyde de carbone du méthane se produisent simultanément, le catalyseur étant formé pour inclure au moins deux trous et comprenant : un matériau de support comprenant au moins du magnésium (Mg) et de l'aluminium (Al); un matériau favorisant l'activité comprenant au moins du cérium (Ce); et un matériau actif comprenant au moins du nickel (Ni), la quantité de stockage d'O2 d'un métal, qui est le matériau actif exposé sur la surface du catalyseur, et d'un oxyde du matériau favorisant l'activité exposé sur la surface du catalyseur étant de 60 à 70 μmol O2/gcat.
PCT/KR2018/010505 2017-09-07 2018-09-07 Catalyseur à base de nickel et système de production de gaz de synthèse l'utilisant Ceased WO2019050335A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20170114245 2017-09-07
KR10-2017-0114245 2017-09-07

Publications (1)

Publication Number Publication Date
WO2019050335A1 true WO2019050335A1 (fr) 2019-03-14

Family

ID=65635012

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/010505 Ceased WO2019050335A1 (fr) 2017-09-07 2018-09-07 Catalyseur à base de nickel et système de production de gaz de synthèse l'utilisant

Country Status (2)

Country Link
KR (1) KR102178146B1 (fr)
WO (1) WO2019050335A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112206789A (zh) * 2020-09-03 2021-01-12 天津大学 一种甲烷二氧化碳重整制合成气的催化剂及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20250149813A (ko) * 2024-04-09 2025-10-17 에스케이이노베이션 주식회사 탄화수소 제조방법 및 시스템

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1013603A1 (fr) * 1998-12-22 2000-06-28 Haldor Topsoe A/S Procédé de reformage à la vapeur catalytique d'une charge d'hydrocarbures
US20040043900A1 (en) * 2002-08-12 2004-03-04 Combs Glenn A. Heterogeneous gaseous chemical reactor catalyst
KR20100014012A (ko) * 2008-08-01 2010-02-10 한국화학연구원 천연가스와 이산화탄소로부터 합성가스 제조를 위한 촉매및 이의 제조방법
KR20110057228A (ko) * 2008-09-12 2011-05-31 존슨 맛쎄이 퍼블릭 리미티드 컴파니 성형된 불균일 촉매
KR20130028024A (ko) * 2011-09-08 2013-03-18 한국에너지기술연구원 합성가스 제조용 개질 촉매, 이를 이용한 합성가스 제조 방법 및 합성가스 제조 반응기

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002126528A (ja) 2000-10-18 2002-05-08 Japan National Oil Corp リホーミング用触媒の製造方法
JP4316323B2 (ja) 2002-10-04 2009-08-19 独立行政法人石油天然ガス・金属鉱物資源機構 炭化水素リフォーミング用触媒及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1013603A1 (fr) * 1998-12-22 2000-06-28 Haldor Topsoe A/S Procédé de reformage à la vapeur catalytique d'une charge d'hydrocarbures
US20040043900A1 (en) * 2002-08-12 2004-03-04 Combs Glenn A. Heterogeneous gaseous chemical reactor catalyst
KR20100014012A (ko) * 2008-08-01 2010-02-10 한국화학연구원 천연가스와 이산화탄소로부터 합성가스 제조를 위한 촉매및 이의 제조방법
KR20110057228A (ko) * 2008-09-12 2011-05-31 존슨 맛쎄이 퍼블릭 리미티드 컴파니 성형된 불균일 촉매
KR20130028024A (ko) * 2011-09-08 2013-03-18 한국에너지기술연구원 합성가스 제조용 개질 촉매, 이를 이용한 합성가스 제조 방법 및 합성가스 제조 반응기

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112206789A (zh) * 2020-09-03 2021-01-12 天津大学 一种甲烷二氧化碳重整制合成气的催化剂及其制备方法和应用

Also Published As

Publication number Publication date
KR20190027762A (ko) 2019-03-15
KR102178146B1 (ko) 2020-11-13

Similar Documents

Publication Publication Date Title
EP0974551B1 (fr) Procede de preparation d'un gaz de synthese
WO2010013958A2 (fr) Catalyseur pour la fabrication de gaz de synthèse à partir de gaz naturel et de dioxyde de carbone, et procédé de préparation correspondant
JP3345782B2 (ja) 合成ガス製造用触媒及び一酸化炭素の製造方法
US6749828B1 (en) Process for reforming hydrocarbon
US20050164890A1 (en) Supported perovskite-type oxides and methods for preparation thereof
EP3685916A1 (fr) Catalyseur d'oxyde métallique de pérovskite, dans lequel un ion métallique est substitué, pour réduire le dépôt de carbone, son procédé de préparation, et procédé de réaction de reformage du méthane l'utilisant
WO2010067945A1 (fr) Procédé de synthèse de méthanol utilisant un gaz de synthèse généré par un reformage mixte de gaz naturel et de dioxyde de carbone
JPWO1998046525A1 (ja) オートサーマルリフォーミング法による合成ガスの製造方法
WO2015183061A1 (fr) Procédé de préparation d'un catalyseur fischer-tropsch hautement actif
WO2014092278A1 (fr) Procédé de préparation de catalyseur fisher-tropsch
US20060111456A1 (en) Process for the selective methanation of carbonmonoxide (CO) contained in a hydrogen-rich reformate gas
WO2014092474A1 (fr) 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
WO2015183059A1 (fr) Procédé de préparation de catalyseur fischer-tropsch ayant une activité et des propriétés de durée de vie améliorées
WO2019050337A1 (fr) Catalyseur à base de nickel soumis à un traitement alcalin, et son procédé de production
WO2019050335A1 (fr) Catalyseur à base de nickel et système de production de gaz de synthèse l'utilisant
WO2018048236A1 (fr) Corps moulé de catalyseur à base de nickel pour le reformage de méthane à la vapeur et son utilisation
US6242380B1 (en) Process for preparing supported nickel catalyst for reforming hydrocarbons
WO2014092482A1 (fr) Catalyseur contenant du lanthane pour la fabrication de gaz de synthèse par reformage à la vapeur-au dioxyde de carbone et procédé de fabrication de gaz de synthèse par utilisation de celui-ci
KR101386418B1 (ko) 메탄의 수증기 개질용 촉매, 상기 촉매의 제조방법 및 제철 부생가스 내에 포함된 메탄의 수증기 개질 방법
KR20210054163A (ko) 메탄의 수증기-이산화탄소 개질반응용 니켈계 촉매 및 이를 이용한 합성가스의 제조방법
WO2017090864A1 (fr) Catalyseur supporté par cobalt pour réaction de reformage à basse température, et son procédé de production
WO2019050336A1 (fr) Réacteur à double couche de catalyseur et système de préparation de gaz de synthèse l'utilisant
KR20170047815A (ko) 수증기 개질 촉매
KR20150129566A (ko) 천연가스의 복합 개질반응용 니켈계 촉매
JP4163302B2 (ja) 炭化水素の改質用触媒の調製方法及びその触媒担体形成用酸化マグネシウム成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18853544

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18853544

Country of ref document: EP

Kind code of ref document: A1