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WO2018048236A1 - Corps moulé de catalyseur à base de nickel pour le reformage de méthane à la vapeur et son utilisation - Google Patents

Corps moulé de catalyseur à base de nickel pour le reformage de méthane à la vapeur et son utilisation Download PDF

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Publication number
WO2018048236A1
WO2018048236A1 PCT/KR2017/009853 KR2017009853W WO2018048236A1 WO 2018048236 A1 WO2018048236 A1 WO 2018048236A1 KR 2017009853 W KR2017009853 W KR 2017009853W WO 2018048236 A1 WO2018048236 A1 WO 2018048236A1
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catalyst
smr
steam methane
methane reforming
based catalyst
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Korean (ko)
Inventor
이동채
조성종
민준석
최상현
김초균
안지혜
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Ecopro Co Ltd
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Ecopro Co Ltd
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/34—Mechanical properties
    • B01J35/36—Mechanical strength
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/647—2-50 nm
    • 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
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • 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
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to nickel-based catalyst shaped bodies for steam methane reforming and their use.
  • a fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy by an electrochemical reaction.
  • SOFC solid oxide fuel cell
  • Fuels commonly used in fuel cells include hydrocarbon raw materials and hydrogen obtained by reacting oxidants or steam in a fuel reformer. The most commonly used hydrogen production method reacts methane (CH 4 ) with steam in the presence of a catalyst. Steam methane reforming (SMR) to convert hydrogen (H 2 ), carbon monoxide (CO), and carbon dioxide (CO 2 ).
  • SMR Steam Methane Reforming
  • a pellet-type ceramic support catalyst having Ni, Ru and other active materials supported on a relatively inexpensive ceramic support is used as a steam methane reforming (SMR) catalyst for hydrogen production.
  • SMR steam methane reforming
  • the pellet-type ceramic support catalyst is poor in impact resistance and easily breaks, causing a differential pressure in the reactor.
  • the steam methane reforming process is a reaction in which the number of moles of the product is greater than the number of moles of the reactant, as shown in FIG.
  • the energy force for the catalyst to be activated: temperature
  • the present inventors have made an effort to improve the strength of the catalyst through compression molding, and as a result, when nickel is carried on the boehmite, which is a preliminary step of alumina, and then compression molding, pellets can be produced without damaging the molding module. It was confirmed that the present invention was completed.
  • the present invention is to provide a nickel-based catalyst compact for steam methane reforming to improve the strength of the catalyst through compression molding.
  • a first aspect of the present invention provides a Ni-based catalyst molded product for steam methane reforming (SMR), wherein the catalyst powder supported by impregnating boehmite with a nickel precursor is pressed and calcined.
  • SMR steam methane reforming
  • step 2) impregnating boehmite into the solution of step 1) to impregnate the boehmite with a nickel precursor;
  • Ni-based catalyst molded body for steam methane reforming including; 4) compression molding and calcining the powder of step 3).
  • a third aspect of the present invention provides a reactor which simultaneously performs a steam methane reforming process (SMR) and a hydrogen separation process, and uses the Ni-based catalyst shaped body of the first aspect as a catalyst for SMR.
  • SMR steam methane reforming process
  • a fourth aspect of the present invention provides a process for producing syngas or hydrogen gas from natural gas by performing steam methane reforming (SMR) and hydrogen separation in one reactor, wherein the SMR under the Ni-based catalyst shaped body of the first aspect It provides a method for producing syngas or hydrogen gas characterized in that the process is carried out.
  • SMR steam methane reforming
  • the inventors of the present invention have attempted to prepare 2 * 3 mm pellets, 2 mm pellets or bead type catalysts in order to fill the catalyst in the membrane for hydrogen production.
  • Pellet-type catalysts are generally known to be suitable for vacuum extrusion molding or compression molding.
  • Vacuum extrusion molding is a molding method in which the catalyst is kneaded through a binder and an additive to make it viscous, and then the vacuum is applied to the module to extract a desired shape.
  • Vacuum extrusion molding has the advantage of forming various types of catalysts by replacing the molding module in front of the molding apparatus.
  • the operation of finding the conditions of the dough using a binder and other additives is required.
  • Compression molding is a method of producing a physically desired shape through the transverse motion of the module using catalyst powder.
  • Compression molding has an advantage in that the manufacturing method is relatively simple compared to the vacuum extrusion that requires a process of kneading the catalyst powder.
  • the present inventors introduced two preparation methods, compression molding and extrusion molding, to evaluate the strength of the catalyst. As a result, as shown in FIG. 3, it was confirmed that the preparation of the MgNiAl 2 O 3 catalyst through compression molding was superior in strength of the catalyst by about 2 times or more.
  • the present inventors have attempted to prepare catalyst pellets through compression molding.
  • Compression molding of the catalyst to which alumina is added requires high strength force.
  • the molding module is not sustained and damaged.
  • the present inventors found that when a pellet-type Ni-based catalyst was prepared using boehmite as a support, pelletization and catalyst molding were possible without breaking the molding module, unlike using an alumina ( ⁇ -Al 2 O 3 ) support. (See Figure 2).
  • the Ni-based catalyst was prepared using the boehmite as a support, it was confirmed that the calcination resulted in the same crystal phase and structure as ⁇ -Al 2 O 3 , but the specific surface area and the acid point characteristics were excellent. The improvement was confirmed.
  • the present invention is based on this. Accordingly, the present invention is a Ni-based catalyst compact for steam methane reforming (SMR), characterized in that the catalyst powder supported by impregnating a boehmite with a nickel precursor is pressed and calcined.
  • SMR steam methane reforming
  • Boehmite is a hydroxyl group (-OH) is one individual first Ga ⁇ -AlO (OH) as compared to high strength, high acidity, high alumina crystal growth and (Al 2 O 3) existing in the alumina (Al 2 O 3) to be.
  • Boehmite is a good starting material for gamma / delta / theta / alpha Al 2 O 3 and has excellent thermal and structural properties. Since boehmite has various Al 2 O 3 phases according to heat treatment conditions and methods, it is possible to prepare an excellent Ni / Al 2 O 3 catalyst for SMR reaction through such adjustment.
  • boehmite is phase-converted to gamma alumina ( ⁇ -Al 2 O 3 ) at a high temperature of 500 ° C. or higher.
  • Boehmite can use a powder or a granule.
  • the boehmite support is immersed in a precursor solution in which a nickel precursor and optionally a promoter metal supply precursor are dissolved in a solvent according to the impregnation method to impregnate the catalyst precursor in the boehmite support. After compression molding, drying and firing can be prepared.
  • the nickel precursor may be in the form of nitrate (NO 3 ), acetate salt, halide salt (F, Cl, Br, I) or a mixture thereof, but is not limited thereto.
  • the nickel precursor is selected from the group consisting of Nickel Nitrate Hexahydrate, Nickel Chloride Hexahydrate, Nickel Acetate Tetrahydrate, and Nickel Bromide Hydrate. It may be one or more selected.
  • the nickel precursor is nickel, titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), aluminum (Al) ),
  • Magnesium (Mg), zirconium (Zr) and boron (B) may be a composite precursor consisting of one or more metals selected from the group.
  • the nickel-containing composite precursor comprises nickel and at least one metal selected from the group consisting of chromium (Cr), copper (Cu), aluminum (Al), magnesium (Mg) and boron (B). It may be a precursor.
  • Ni-based catalyst for steam methane reforming (SMR) of the present invention may be a Ni content of 20 to 40% by weight.
  • a cocatalyst precursor may be added to the nickel precursor-containing solution as an additive.
  • Non-limiting examples of cocatalysts impregnated with Ni include Ag, La, Mg, Pd, Ru, but Ag has a low methane conversion of less than 80% at 600 ° C., and Ru and Ag have a methane conversion rate of The hydrogen production amount was very low.
  • At least one selected promoter from the group consisting of La, Mg and Pd may be added.
  • the Ni-based catalyst for SMR according to the present invention may include calcium oxide as a catalyst enhancer. Since calcium oxide has a strong basicity, carbon dioxide is strongly adsorbed, and the adsorbed carbon dioxide reacts with carbon produced in the catalyst and is converted into carbon monoxide. That is, since it assists the gasification of the coke or the coke precursor, it serves to suppress coke formation on the catalyst.
  • the precursor solvent examples include water and lower alcohols of C 1 to C 6 , and particularly preferably distilled water or deionized water.
  • the precursor solution may be prepared at 80 ⁇ 130 °C. Drying process may be performed for 5 to 10 hours at 100 ⁇ 130 °C.
  • the drying method is not particularly limited and a rotary evaporator or oven may be used.
  • the number of times of supporting these precursor solutions is not limited.
  • the catalyst component may be supported by dividing it several times.
  • the present invention can optimize compression molding by controlling variables such as compressive strength, particle size, flowability of powder, viscosity, desorption degree and the like.
  • the present invention is characterized by controlling the mechanical strength of the catalyst by adjusting the compressive strength applied to the catalyst powder before compression molding.
  • the compressive strength may be 5 kN to 25 kN, specifically 10 kN to 20 kN, more specifically 13 kN to 17 kN, but is not limited thereto, and may be adjusted according to the dimensions of the pellets. If the compressive strength applied to the catalyst is abnormally high, it may cause damage to the molding module (Fig. 4 (a)).
  • the present invention is characterized in that the mechanical strength of the catalyst is controlled by adjusting the size of the catalyst powder before compression molding.
  • the size of the catalyst powder before compression molding is preferably 45 to 75 ⁇ . If the size of the catalyst powder is less than 45 ⁇ m can stick to the molding module may cause module damage.
  • the strength of the pellets formed using the catalyst powder of 45 to 75 ⁇ m size was the best (FIG. 4 (b)). Uneven catalyst powder size can damage the molding module and reduce the strength of the pellets.
  • the present invention can optimize the compression molding by controlling the flowability and viscosity, and the degree of desorption of the catalyst powder before compression molding during compression molding.
  • the flowability of the catalyst powder can be a variable that determines the amount of catalyst filled in the molding module.
  • the flowability of the catalyst powder can be controlled by controlling the size of the catalyst powder.
  • the present invention can increase the viscosity of the catalyst powder so that the catalyst has a formability.
  • an additive may be added to the catalyst powder during compression molding.
  • PVA, talc, etc. can be added as a viscosity agent which provides the moldability of a catalyst.
  • talc, graphite, or the like may be added as a lubricant to minimize the powder sandwiched between module gaps during molding of the pellets.
  • a pellet-type catalyst was prepared by adding 5% each of PVA, MC binder, talc, and graphite as additives (FIG. 5).
  • the PVA or MC binder can provide the formability of the catalyst, but may cause the catalyst cracking to reduce the strength.
  • Talc or graphite can minimize the powder sandwiched between module gaps when forming pellets, but can significantly reduce catalyst strength.
  • the firing temperature of the compression molded pellets in the present invention may be 500 ⁇ 1000 °C, preferably 800 ⁇ 900 °C, in particular may be 850 °C.
  • Ni-based catalyst for SMR according to the present invention may be a pellet having an average diameter of 2 to 3mm. Catalysts having a suitable filling rate should be used depending on the reactor size, with 2 mm pellets being preferred as the catalyst to be used in the reaction.
  • Ni-based catalyst molded article for SMR according to the present invention may have a mechanical strength of 8 to 20 kgf.
  • the Ni-based catalyst molded article for SMR according to the present invention may have a specific surface area of 50 to 200 m 2 / g, and preferably 75 to 150 m 2 / g.
  • Ni-based catalyst molded article for SMR according to the present invention may have an average pore diameter of 5 to 15 nm.
  • the methane conversion rate in the steam methane reforming process (SMR) at 500 to 900 ° C., specifically 550 to 650 ° C. may be 80% or more compared to the equilibrium conversion rate.
  • Ni-based catalyst compact for SMR according to the present invention contains Ni species crystals even before the steam methane reforming reaction, and Ni peaks appear in the XRD of the catalyst after the reaction.
  • Non-limiting examples of the Ni species crystals include NiAl 2 O 3 and the like.
  • the steam methane reforming process for hydrogen production is strongly influenced by the pressure of increasing the number of moles of gas.
  • the breakage of the catalyst may be a factor of decreasing the reaction efficiency by increasing the reaction pressure, the catalyst compact for pellet-type SMR according to the present invention can prevent this.
  • the Ni-based catalyst compact for pellet-type SMR according to the present invention can be used in a reactor that simultaneously performs steam methane reforming process (SMR) and hydrogen separation process at 500 to 600 ° C. low temperature.
  • SMR steam methane reforming process
  • step 2) impregnating boehmite into the solution of step 1) to impregnate the boehmite with a nickel precursor;
  • Ni-based catalyst molded body for steam methane reforming including; 4) compression molding and calcining the powder of step 3).
  • Ni-based catalyst compact for pellet-type SMR according to the present invention may be prepared according to the above production method.
  • the nickel precursor may be in the form of nitrate (NO 3 ), acetate salt, halide salt (F, Cl, Br, I) or a mixture thereof, but is not limited thereto.
  • the nickel precursor is selected from the group consisting of Nickel Nitrate Hexahydrate, Nickel Chloride Hexahydrate, Nickel Acetate Tetrahydrate, and Nickel Bromide Hydrate. It may be one or more.
  • the nickel precursor is nickel, titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), aluminum (Al) It may be a composite precursor consisting of one or more metals selected from the group consisting of magnesium (Mg), zirconium (Zr) and boron (B). Most preferably, the nickel-containing composite precursor comprises nickel and at least one metal selected from the group consisting of chromium (Cr), copper (Cu), aluminum (Al), magnesium (Mg) and boron (B). It may be a precursor.
  • the nickel-containing composite precursor solution may be one containing a promoter metal supply precursor.
  • the promoter include Ag, La, Mg, Pd, Ru and the like.
  • the promoter may be one or more selected from the group consisting of La, Mg and Pd.
  • step 4 calcium oxide may be added as a catalyst enhancer. Specifically, after the catalyst enhancer is mixed with the powder obtained in step 3), compression molding and baking may be performed.
  • Examples of the solvent of the nickel precursor include water and C 1 to C 6 lower alcohols, and it is particularly preferable to use distilled water or deionized water.
  • the precursor solution may be prepared at 80 to 130 ° C.
  • Obtaining the catalyst powder in step 3) may be performed by drying the solution of step 2) in which boehmite is immersed, and drying may be performed at 100 to 130 ° C. for 5 to 10 hours.
  • the drying method is not particularly limited and a rotary evaporator or oven may be used.
  • the number of times of supporting these precursor solutions is not limited.
  • the catalyst component may be supported by dividing it several times.
  • Step 3) may further comprise the step of screening or pulverizing and screening the catalyst powder obtained to a predetermined size to control the size of the catalyst powder before compression molding.
  • the catalyst powder may have a size of 45 to 75 ⁇ m before compression molding.
  • the present invention is characterized in that the mechanical strength of the catalyst is controlled by adjusting the size of the catalyst powder before compression molding. If the size of the catalyst powder is less than 45 ⁇ m can stick to the molding module may cause module damage. The strength of the pellets formed using the catalyst powder of 45 to 75 ⁇ m size was the best (FIG. 4 (b)). Uneven catalyst powder size can damage the molding module and reduce the strength of the pellets.
  • Compression molding of step 4) may be 5 kN to 25 kN, specifically 10 kN to 20 kN, more specifically 13 kN to 17 kN, but is not limited thereto, and may be adjusted according to the dimensions of the pellets.
  • the present invention is characterized by adjusting the mechanical strength of the catalyst by adjusting the compressive strength applied to the catalyst powder. If the compressive strength applied to the catalyst is abnormally high, it may cause damage to the molding module (Fig. 4 (a)).
  • the present invention can increase the viscosity of the catalyst powder so that the catalyst has a formability.
  • an additive may be added to the catalyst powder during compression molding in step 4).
  • PVA, talc, etc. can be added as a viscosity agent which provides the moldability of a catalyst.
  • talc, graphite, or the like may be added as a lubricant to minimize the powder sandwiched between module gaps during molding of the pellets.
  • the firing temperature of the pellets compressed in the step 4) may be 500 to 1000 ° C, specifically 800 to 900 ° C, in particular 850 ° C.
  • the catalyst prepared according to the preparation method may be in the form of pellets, pellets having an average diameter of 2 to 3mm. Catalysts having a suitable filling rate should be used depending on the reactor size, with 2 mm pellets being preferred as the catalyst to be used in the reaction.
  • the present invention provides a reactor which performs a steam methane reforming process (SMR) and a hydrogen separation process at the same time, using a Ni-based catalyst compact for pellet-type SMR according to the present invention.
  • SMR steam methane reforming process
  • the reactor may further include a catalyst for water gas shift reaction.
  • Ni-based catalyst molded body for SMR can be used in a method for producing syngas or hydrogen gas from natural gas by performing a steam methane reforming process (SMR) and a hydrogen separation process in one reactor.
  • SMR steam methane reforming process
  • the method may also perform a water gas shift reaction after the hydrogen separation process in the reactor.
  • the separation structure used in the present invention it is preferable to use a separation membrane having a high hydrogen permeability.
  • the separation structure is hydrogen selectivity in the synthesis gas, a ceramic containing silica, alumina, zirconia, YSZ, or a combination thereof; Or a metal composed of nickel, copper, iron, palladium, ruthenium, rhodium, platinum, or a combination thereof; Alternatively, the composite composition may be a mixture of the metal and the ceramic.
  • the structure of the separation structure may vary, and non-limiting examples may be in the form of flat membrane, tube, hollow fiber membrane.
  • a high-strength nickel-based catalyst molded body may be manufactured through compression molding and used in steam methane reforming process (SMR) at 500 to 600 ° C. low temperature.
  • SMR steam methane reforming process
  • the catalyst shaped body for SMR of the present invention is capable of high strength of the catalyst through pelletization and molding by using boehmite as a support, and can exhibit improved reaction characteristics.
  • Figure 1 shows the shrinkage expansion of the reactor according to (a) temperature and (b) equilibrium conversion rate according to the pressure.
  • Figure 3 shows the compressive strength of the 2mm pellet catalyst according to the molding method.
  • Figure 4 shows the mechanical strength of the catalyst for each variable of compression molding ((a) by compressive strength, (b) by catalyst size).
  • Figure 5 shows the molding strength according to various additives (0 is a non-molding catalyst).
  • Figure 6 shows the methane conversion and the equilibrium conversion of methane conversion of the pellet forming catalyst.
  • a nickel-containing composite precursor (MgNiAl 2 O 4 ) was dissolved in distilled water at 1.0 mol / L and ultrasonically dispersed for 1 hour to prepare a precursor solution in which metal was dispersed.
  • Catalyst powders were selected by size (45-75 ⁇ m, 75-180 ⁇ m, 180-250 ⁇ m and 250-300 ⁇ m). Without using additives in the selected catalyst powders, 2 * 3 mm catalyst pellets were compression molded at a compression strength of 10, 15, or 20 kN at 850 ° C. Ni-based catalyst pellets for steam methane reforming were prepared by firing at 850 ° C. for 6 hours in an air atmosphere.
  • Example 1 Evaluation of the mechanical strength of the catalyst pellets according to the compressive strength of the compression molding applied when preparing the catalyst pellets according to Example 1 was carried out.
  • the catalyst of Example 1 was prepared by compression molding the catalyst powder by applying a force of 10, 15 and 20 kN, respectively, and the mechanical strength of the prepared catalyst was measured and shown in FIG. 4 (a).
  • Example 1 mechanical strength evaluation of the catalyst pellets according to the size of the catalyst powder was carried out.
  • the catalyst of Example 1 was prepared by compression molding catalyst powders having sizes of 45 to 75 ⁇ m, 75 to 180 ⁇ m, 180 to 250 ⁇ m, and 250 to 300 ⁇ m with a compressive strength of 15 kN, respectively. The mechanical strength of each was measured and shown in FIG. 4 (b).
  • the mechanical strength of the catalyst pellets formed using the catalyst powder of 45 ⁇ 75 ⁇ m size was found to be the most excellent.
  • the size of the catalyst is 45 ⁇ m or less, it was confirmed that the cause of module damage by sticking to the molding module.
  • Catalyst pellets were prepared in the same manner as in Example 1 except that the extrusion pellets were used to prepare the catalyst pellets.
  • the mechanical strengths of the catalyst pellets and the catalyst pellets prepared according to Example 1 were measured and shown in FIG. 3. At this time, all of the catalyst powder used a size of 45 ⁇ 75 ⁇ m, the compression strength at the time of compression molding was 15kN.
  • PVA polyvinyl styrene
  • MC binder polymethyl methacrylate
  • talc talc
  • graphite may be used as an additive during compression molding of the catalyst.
  • the PVA or MC binder may act as a viscous agent to provide the formability of the catalyst, but may cause the catalyst to be cracked, thereby reducing the strength.
  • talc or graphite as a lubricant can minimize the powder sandwiched between the module gaps when forming the pellets, it was found that the catalyst strength can be very low.
  • the catalyst of Example 1 was prepared by compression molding a catalyst powder of 45-75 ⁇ m with a compressive strength of 15kN.
  • the result of the steam methane reforming reaction showed that the catalyst pellets prepared according to the present example showed higher conversion of methane conversion and equilibrium conversion ratio than those of commercial catalysts based on nickel alumina (BSF's MCFC fuel reforming catalyst). You can see that.

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Abstract

La présente invention concerne un corps moulé de catalyseur à base de Ni pour le reformage de méthane à la vapeur (SMR). Le corps moulé de catalyseur est obtenu par moulage par compression d'une poudre de catalyseur, dans laquelle un précurseur de nickel est immergé et supporté sur de la boehmite, puis cuisson de la poudre de catalyseur. Le catalyseur pour SMR de la présente invention, en utilisant de la boehmite comme support, peut atteindre une résistance élevée par pastillage et moulage et peut présenter des caractéristiques de réaction améliorées.
PCT/KR2017/009853 2016-09-09 2017-09-08 Corps moulé de catalyseur à base de nickel pour le reformage de méthane à la vapeur et son utilisation Ceased WO2018048236A1 (fr)

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CN112871173A (zh) * 2021-02-03 2021-06-01 河南省科学院 一种甲烷二氧化碳干重整制合成气反应催化剂的制备方法

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EP4129470A4 (fr) * 2020-03-31 2024-04-17 Osaka Gas Co., Ltd. Catalyseur de conversion inverse eau-gaz, système de réaction électrolytique, système de fabrication d'hydrocarbures et procédés de fabrication et procédé d'utilisation associés
KR20220052099A (ko) 2020-10-20 2022-04-27 한국화학연구원 메탄의 수증기 개질용 니켈계 촉매 및 이를 이용한 메탄의 수증기 개질 반응
KR102616015B1 (ko) * 2021-12-28 2023-12-20 한국화학연구원 결정성 그래피틱 탄소계 물질이 무기물 매트릭스 내에 고 분산된 메탄 염소화 반응용 촉매
KR20240159086A (ko) * 2023-04-28 2024-11-05 한화솔루션 주식회사 메탄 개질용 촉매 및 이의 제조방법

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