WO2018048236A1 - Nickel-based catalyst molded body for steam methane reforming and use thereof - Google Patents
Nickel-based catalyst molded body for steam methane reforming and use thereof Download PDFInfo
- 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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- Prior art keywords
- catalyst
- smr
- steam methane
- methane reforming
- based catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 203
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000001991 steam methane reforming Methods 0.000 title claims abstract description 94
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 59
- 238000000748 compression moulding Methods 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 28
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000010304 firing Methods 0.000 claims abstract description 8
- 239000008188 pellet Substances 0.000 claims description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 229910000943 NiAl Inorganic materials 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 24
- 238000005453 pelletization Methods 0.000 abstract description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000454 talc Substances 0.000 description 9
- 229910052623 talc Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000003623 enhancer Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 halide salt Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- LQJMXNQEJAVYNB-UHFFFAOYSA-L dibromonickel;hydrate Chemical compound O.Br[Ni]Br LQJMXNQEJAVYNB-UHFFFAOYSA-L 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910017961 MgNi Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
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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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- B01J37/02—Impregnation, coating or precipitation
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
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- 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
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- 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
The present invention relates to a Ni-based catalyst molded body for steam methane reforming (SMR), the catalyst molded body being obtained by compression molding a catalyst powder, in which a nickel precursor is immersed in and supported on boehmite, and then firing the catalyst powder. The catalyst for SMR of the present invention, by using boehmite as a supporter, can achieve high strength through pelletization and molding and can exhibit improved reaction characteristics.
Description
본 발명은 수증기 메탄 개질용 니켈계 촉매 성형체 및 이의 이용에 관한 것이다.The present invention relates to nickel-based catalyst shaped bodies for steam methane reforming and their use.
연료전지는 연료의 화학에너지를 전기화학반응에 의해 전기에너지로 직접 변환시키는 에너지 전환 장치로서, 특히 고체 산화물 연료전지(solid oxide fuel cell: SOFC)는 고체 산화물을 전해질로 사용하고 고온에서 작동한다는 두 가지 특징을 지니고 있다. 연료전지에 흔히 사용되는 연료로서는 탄화수소 원료와, 산화제 혹은 수증기를 연료개질기에서 반응시켜 얻게 되는 수소가 있는데, 상업적으로 가장 많이 사용되는 수소 생산 방법은 촉매의 존재 하에서 메탄(CH4)을 수증기와 반응시켜 수소(H2), 일산화탄소(CO), 이산화탄소(CO2)로 전환하는 수증기 메탄 개질 공정(steam-methane reforming: SMR)이다.A fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy by an electrochemical reaction. In particular, a solid oxide fuel cell (SOFC) uses a solid oxide as an electrolyte and operates at high temperatures. It has three characteristics. 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 ).
[반응식 1]Scheme 1
CH4 + H2 → 3H2 + CO; ΔHθ = 206.1 kJ/molCH 4 + H 2 → 3H 2 + CO; ΔH θ = 206.1 kJ / mol
수소 제조를 위한 수증기 메탄 개질 공정(SMR: Steam Methane Reforming)은 몰 수가 증가하는 반응으로 압력에 큰 영향을 받는다. 반응 압력을 증가시키는 가장 큰 요인은 촉매의 파손 때문이며, 이를 방지하기 위해서는 고강도의 촉매를 제조해야 한다. Steam Methane Reforming (SMR) for hydrogen production is strongly influenced by pressure due to the increased molar number. The biggest factor that increases the reaction pressure is due to the breakage of the catalyst, in order to prevent it, a high strength catalyst must be prepared.
현재 수소 제조를 위한 수증기 메탄 개질 공정(SMR: Steam Methane Reforming) 촉매로 비교적 가격이 저렴한 세라믹 지지체에 Ni, Ru 등의 활성물질을 담지한 펠렛형 세라믹 지지체 촉매가 사용되고 있다. 그러나, 펠렛형 세라믹 지지체 촉매는 내충격성이 떨어져 쉽게 파손되고 반응기내 차압을 발생시키는 원인이 되었다. 또한, 수증기 메탄 개질 공정은 반응물 몰수보다 생성물 몰수가 증가하는 반응으로 도 1에서 보는 바와 같이 압력이 증가하면 반응 특성, 예컨대 압력에 따른 평형전환율이 하락하는 단점이 있었다. 또한 에너지(촉매가 활성화 되기 위한 힘: 온도)가 불충분하여 촉매의 활성화 에너지 및 촉매량에 의존하는 단점이 있었다. Currently, 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. However, the pellet-type ceramic support catalyst is poor in impact resistance and easily breaks, causing a differential pressure in the reactor. In addition, 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. In addition, there was a disadvantage in that the energy (force for the catalyst to be activated: temperature) is insufficient and depends on the activation energy and the amount of the catalyst.
따라서, 니켈계 알루미나를 펠렛 또는 비드형태로 압축 성형하는 시도가 이루어지고 있다. 특히 2mm 펠렛의 경우 SMR 촉매 중 매우 소형의 사이즈로, 특수하게 제작된 반응기에 충진되기 적합하다. 그러나, 알루미나 계열의 파우더를 이용하여 2mm 펠렛을 압축성형하여 제조할 경우 성형 모듈의 손상으로 인해 제작이 불가능한 문제점이 있다. Accordingly, attempts have been made to compression-form nickel-based alumina into pellets or beads. In particular, 2mm pellets are very small in SMR catalysts and are suitable to be filled in specially manufactured reactors. However, when manufacturing by compression molding 2mm pellets using alumina-based powder, there is a problem that can not be manufactured due to damage to the molding module.
이러한 배경 기술 하에, 본 발명자들은 압축 성형을 통한 촉매의 강도 증진을 위한 노력을 경주한 결과, 알루미나의 전단계인 보헤마이트에 니켈을 담지한 후 압축 성형을 진행할 경우 성형 모듈의 손상없이 펠렛을 제조할 수 있음을 확인하고 본 발명을 완성하였다. Under this background, 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.
본 발명은 압축 성형을 통해 촉매의 강도를 향상시킨 수증기 메탄 개질용 니켈계 촉매 성형체를 제공하고자 한다.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.
본 발명의 제1양태는 보헤마이트(boehmite)에 니켈 전구체를 함침시켜 담지한 촉매 파우더를 압축성형하여 소성한 것인, 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체를 제공한다.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.
본 발명의 제2양태는 The second aspect of the present invention
1) 니켈 전구체 용액을 준비하는 단계; 1) preparing a nickel precursor solution;
2) 단계 1)의 용액에 보헤마이트를 침지하여 보헤마이트에 니켈 전구체를 함침시키는 단계; 2) impregnating boehmite into the solution of step 1) to impregnate the boehmite with a nickel precursor;
3) 보헤마이트에 나켈 전구체가 담지된 촉매 파우더를 수득하는 단계; 및 3) obtaining a catalyst powder having a nickel precursor supported on boehmite; And
4) 단계 3)의 분말을 압축 성형하고 소성하는 단계;를 포함하는 수증기 메탄 개질용 Ni계 촉매 성형체의 제조방법을 제공한다.It provides a method for producing a Ni-based catalyst molded body for steam methane reforming, including; 4) compression molding and calcining the powder of step 3).
본 발명의 제3양태는 수증기 메탄 개질 공정(SMR) 및 수소분리 공정을 동시에 수행하는 반응기로서, SMR 용 촉매로 제1양태의 Ni계 촉매 성형체를 사용하는 것이 특징인 반응기를 제공한다.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.
본 발명의 제4양태는 하나의 반응기에서 수증기 메탄 개질 공정(SMR) 및 수소분리 공정을 수행하여 천연가스로부터 합성가스 또는 수소가스를 제조하는 방법에 있어서, 제1양태의 Ni계 촉매 성형체 하 SMR 공정을 수행하는 것이 특징인 합성가스 또는 수소가스 제조방법을 제공한다.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.
이하, 본 발명을 자세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명자들은 수소 제조를 위한 분리막 내 촉매를 충진하기 위해 2*3 mm의 펠렛, 2 mm 펠렛 또는 비드형의 촉매를 제조하고자 하였다.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.
펠렛 타입 촉매는 보통 진공압출 성형 또는 압축성형이 적합한 것으로 알려져 있다.Pellet-type catalysts are generally known to be suitable for vacuum extrusion molding or compression molding.
진공압출 성형은 촉매를 바인더 및 첨가제를 통해 반죽 후 점성을 갖게 한 뒤 모듈에 진공압을 가해 원하는 형상으로 추출해내는 성형방법이다.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.
진공압출 성형은 성형 장치 앞단 성형 모듈 교체를 통해 다양한 형상의 촉매를 성형할 수 있는 장점이 있다. 그러나 바인더 및 기타 첨가제를 이용한 반죽의 조건을 찾는 작업이 필요한 단점이 있다.Vacuum extrusion molding has the advantage of forming various types of catalysts by replacing the molding module in front of the molding apparatus. However, there is a disadvantage in that the operation of finding the conditions of the dough using a binder and other additives is required.
압축 성형은 촉매 파우더를 사용하여 모듈의 횡축 운동을 통해 물리적으로 원하는 형상을 제작하는 방법이다. 압축 성형은 촉매 파우더를 반죽하는 과정을 거쳐야 하는 진공압출에 비해 비교적 제조 방법이 간편하다는 장점이 있다.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.
본 발명자들은 펠렛 형상의 SMR 촉매를 제조하기 위해 압축성형 및 압출성형의 두 가지 제법을 도입하여 촉매의 강도를 평가하였다. 그 결과 도 3에서 보는 바와 같이 압축 성형을 통해 MgNiAl2O3 촉매를 제조하는 것이 촉매의 강도가 약 2배 이상 우수한 것을 확인하였다. In order to prepare pellet-shaped SMR catalysts, 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.
따라서 본 발명자들은 압축 성형을 통해 촉매 펠렛을 제조하고자 하였다. 알루미나가 첨가되는 촉매의 압축성형은 고강도의 힘이 요구된다. 특히, 알루미나를 사용하여 2mm 펠렛 형태로 성형할 경우 성형 모듈이 버티지 못하고 파손되는 현상을 확인하였다. Therefore, 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. In particular, when molding into a 2mm pellet form using alumina was confirmed that the molding module is not sustained and damaged.
본 발명자들은 보헤마이트를 지지체로 이용하여 펠렛형 Ni계 촉매를 제조하는 경우 알루미나(γ-Al2O3) 지지체로 사용하는 것과는 달리 성형 모듈의 파손없이 펠렛화 및 촉매 성형이 가능하다는 것을 발견하였다(도 2 참조).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 (γ-Al 2 O 3 ) support. (See Figure 2).
나아가, 보헤마이트를 지지체로 이용하여 Ni계 촉매를 제조하여도 소성을 거치면 γ-Al2O3와 동일한 결정 상 및 구조를 갖는 것을 확인하였으며, 오히려 비표면적 및 산점 특성이 우수하였고, 반응특성이 향상됨을 확인하였다.Furthermore, even when 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 γ-Al 2 O 3 , but the specific surface area and the acid point characteristics were excellent. The improvement was confirmed.
본 발명은 이에 기초한 것이다. 따라서, 본 발명은 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체로서, 보헤마이트(boehmite)에 니켈 전구체를 함침시켜 담지한 촉매 파우더를 압축성형하여 소성한 것을 특징으로 한다.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.
보헤마이트(Boehmite)는 수산화기(-OH)가 1개인 1가인 γ-AlO(OH)로서 기존의 알루미나(Al2O3)대비 고강도, 고산도, 고결정 및 고성장의 알루미나(Al2O3)이다. 보헤마이트는 감마/델타/세타/알파 Al2O3의 출발 물질로서 열적/구조적 성질이 우수하다. 보헤마이트는 열처리조건 및 방법에 따라서 다양한 Al2O3의 상을 갖게 되므로 이러한 조절을 통해 SMR 반응에 있어 우수한 Ni/Al2O3촉매를 제조할 수 있다.Boehmite (Boehmite) is a hydroxyl group (-OH) is one individual first Ga γ-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.
특히, 보헤마이트는 500 ℃ 이상의 고온에서 감마 알루미나(γ-Al2O3)로 상변환된다. In particular, boehmite is phase-converted to gamma alumina (γ-Al 2 O 3 ) at a high temperature of 500 ° C. or higher.
보헤마이트는 분말 또는 입상체인 것을 사용할 수 있다.Boehmite can use a powder or a granule.
본 발명의 수증기 메탄 개질(SMR)용 Ni계 촉매는 함침법에 따라 니켈 전구체 및 선택적으로 조촉매 금속 공급 전구체를 용매에 용해시킨 전구체 용액에 보헤마이트 지지체를 침지하여 보헤마이트 지지체에 촉매 전구체를 함침한 후 압축성형, 건조 및 소성하여 제조할 수 있다. In the Ni-based catalyst for steam methane reforming (SMR) of the present invention, 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.
상기 니켈 전구체는 질산염(NO3), 아세테이트염, 할라이드염(F, Cl, Br, I) 또는 이의 혼합물 형태일 수 있으나, 이에 한정되지는 않는다. 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.
바람직하게는 상기 니켈 전구체는 니켈 나이트레이트 헥사하이드레이트(Nickel Nitrate Hexahydrate), 니켈클로라이드 헥사하이드레이트(Nickel Chloride Hexahydrate), 니켈 아세테이트 테트라하이드레이트(Nickel Acetate Tetrahydrate) 및 니켈 브로마이드 하이드레이트(Nickel Bromide Hydrate)로 이루어진 군으로부터 선택된 1 종 이상일 수 있다.Preferably, 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.
더욱 바람직하게는, 상기 니켈 전구체는 니켈과, 티타늄(Ti), 바나듐(V), 크롬(Cr), 망간(Mn), 철(Fe), 코발트(Co), 구리(Cu), 알루미늄(Al), 마그네슘(Mg), 지르코늄(Zr) 및 보론(B)으로 이루어진 군으로부터 선택된 하나 이상의 금속으로 이루어진 복합체 전구체일 수 있다. 가장 바람직하게는, 상기 니켈 함유 복합체 전구체는 니켈과, 크롬(Cr), 구리(Cu), 알루미늄(Al), 마그네슘(Mg) 및 보론(B)으로 이루어진 군으로부터 선택된 하나 이상의 금속을 포함하는 복합체 전구체일 수 있다.More preferably, 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. 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.
본 발명의 수증기 메탄 개질(SMR)용 Ni계 촉매는 Ni 함량이 20 내지 40 중량%인 것일 수 있다.Ni-based catalyst for steam methane reforming (SMR) of the present invention may be a Ni content of 20 to 40% by weight.
한편, 니켈 전구체 함유 용액에는 첨가제로 조촉매 전구체를 추가할 수 있다. Meanwhile, a cocatalyst precursor may be added to the nickel precursor-containing solution as an additive.
Ni과 함께 함침되는 조촉매의 비제한적인 예로는 Ag, La, Mg, Pd, Ru 등이 있으나, Ag의 경우 600℃에서 메탄 전환율이 80% 미만으로 낮았으며, Ru 및 Ag의 경우 메탄 전환율 및 수소 생성량이 매우 낮았다.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.
바람직하게는 La, Mg 및 Pd로 구성된 군에서 1종 이상 선택된 조촉매를 추가할 수 있다.Preferably at least one selected promoter from the group consisting of La, Mg and Pd may be added.
일반적으로 리포밍 반응에서 생성되는 코크는 촉매활성을 떨어뜨리고, 촉매를 부숴 반응기 내에서 차압을 증가시키는 부작용을 야기하므로, 코크 생성을 억제하는 것이 매우 중요하다. 따라서, 본 발명에 따른 SMR용 Ni계 촉매는 촉매 증진제로서 산화칼슘을 포함할 수 있다. 산화칼슘은 강한 염기성을 갖기 때문에 이산화탄소를 강하게 흡착하는데, 흡착된 이산화탄소는 촉매에 생성된 탄소와 반응하여 일산화탄소로 전환된다. 즉, 코크 또는 코크 전구체의 가스화를 돕게 되므로, 촉매상의 코크 생성을 억제하는 역할을 한다. In general, coke produced in the reforming reaction deteriorates the catalytic activity and causes side effects of increasing the differential pressure in the reactor that breaks down the catalyst, so it is very important to suppress coke formation. Therefore, 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.
상기 전구체용 용매로는 물, C1~C6의 저급 알콜 등이 있으며, 특히 증류수, 탈이온수를 사용하는 것이 바람직하다.Examples of the precursor solvent include water and lower alcohols of C 1 to C 6 , and particularly preferably distilled water or deionized water.
상기 전구체 용액은 80~130 ℃에서 제조될 수 있다. 건조과정은 100~130 ℃에서 5~10 시간 수행될 수 있다. 건조 방법은 특별히 한정하지 않으며 회전진공 증발기(rotatory evaporator) 또는 오븐을 사용할 수 있다. 지지체의 개질이나 촉매 또는 촉매 증진제의 담지시, 이들 전구체 용액을 담지하는 횟수는 제한하지 않는다. 예들 들면, 촉매성분 담지시 여러 번에 걸쳐 나누어서 담지할 수 있다. The precursor solution may be prepared at 80 ~ 130 ℃. Drying process may be performed for 5 to 10 hours at 100 ~ 130 ℃. The drying method is not particularly limited and a rotary evaporator or oven may be used. When modifying the support or supporting the catalyst or catalyst enhancer, the number of times of supporting these precursor solutions is not limited. For example, the catalyst component may be supported by dividing it several times.
본 발명은 압축 강도, 입자 사이즈, 파우더의 흐름성, 점도, 탈착 정도 등의 변수를 제어하여 압축 성형을 최적화할 수 있다.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.
본 발명은 압축성형 전 촉매 파우더에 가해지는 압축 강도를 조절하여 촉매의 기계적 강도를 조절하는 것을 특징으로 한다.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.
압축 강도는 5 kN 내지 25 kN, 구체적으로 10 kN 내지 20 kN, 보다 구체적으로 13 kN 내지 17 kN일 수 있으나, 이에 제한되지는 않으며, 펠렛의 치수에 따라 조절될 수 있다. 촉매에 가해지는 압축강도가 비정상적으로 높을 경우, 성형 모듈 손상의 원인이 될 수 있다(도 4(a)).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)).
본 발명은 압축성형 전 촉매 파우더의 사이즈를 조절하여 촉매의 기계적 강도를 조절하는 것을 특징으로 한다. 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.
압축성형 전 촉매 파우더의 사이즈는 45 내지 75㎛인 것이 바람직하다. 촉매 파우더의 사이즈가 45㎛ 이하일 경우 성형 모듈에 달라붙어 모듈 파손 원인이 될 수 있다. 45 내지 75㎛ 사이즈의 촉매 파우더를 이용해 성형한 펠렛의 강도가 가장 우수하였다(도 4(b)). 불균일한 촉매 파우더 사이즈는 성형 모듈을 손상시키고 펠렛의 강도를 저하시킬 수 있다.The size of the catalyst powder before compression molding is preferably 45 to 75 탆. If the size of the catalyst powder is less than 45㎛ can stick to the molding module may cause module damage. The strength of the pellets formed using the catalyst powder of 45 to 75 μm size was the best (FIG. 4 (b)). Uneven catalyst powder size can damage the molding module and reduce the strength of the pellets.
본 발명은 압축성형시 압축성형 전 촉매 파우더의 흐름성 및 점도, 그리고 탈착정도를 제어하여 압축 성형을 최적화할 수 있다.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.
촉매 파우더의 흐름성은 성형 모듈에 채워지는 촉매의 양을 결정하는 변수가 될 수 있다. 촉매 파우더의 흐름성은 상기 촉매 파우더의 사이즈를 제어함에 의해 제어할 수 있다.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.
본 발명은 촉매 파우더의 점도를 높여 촉매가 성형성을 갖도록 할 수 있다. 이를 위해 압축성형시 촉매 파우더에 첨가제를 첨가할 수 있다. The present invention can increase the viscosity of the catalyst powder so that the catalyst has a formability. To this end, an additive may be added to the catalyst powder during compression molding.
일례로 촉매의 성형성을 갖추게 하는 점도제로서 PVA, 탈크 등을 첨가할 수 있다. As an example, PVA, talc, etc. can be added as a viscosity agent which provides the moldability of a catalyst.
또한, 펠렛의 성형시 모듈 틈 사이에 끼는 파우더를 최소화하기 위해 윤활제로서 탈크, 그라파이트 등을 첨가할 수 있다.In addition, talc, graphite, or the like may be added as a lubricant to minimize the powder sandwiched between module gaps during molding of the pellets.
본 발명의 일 실시예에서는, 첨가제로서 PVA, MC 바인더, 탈크, 그라파이트를 각각 5%씩 첨가하여 펠렛형 촉매를 제조하였다(도 5).In one embodiment of the present invention, a pellet-type catalyst was prepared by adding 5% each of PVA, MC binder, talc, and graphite as additives (FIG. 5).
PVA 또는 MC 바인더는 촉매의 성형성을 갖추게 할 수 있으나, 촉매 균열의 원인이 되어 강도를 하락시킬 수 있다. 탈크나 그라파이트는 펠렛의 성형 시 모듈 틈 사이에 끼는 파우더를 최소화할 수 있으나, 촉매 강도를 매우 떨어뜨릴 수 있다.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.
본 발명에서 압축성형된 펠렛의 소성 온도는 500 ~ 1000 ℃일 수 있으며, 바람직하게는 800 ~ 900 ℃, 특히 850 ℃일 수 있다.The firing temperature of the compression molded pellets in the present invention may be 500 ~ 1000 ℃, preferably 800 ~ 900 ℃, in particular may be 850 ℃.
상기 온도로 소성하여 제조된 촉매는 γ-Al2O3와 동일한 결정 상 및 구조를 갖게 되고, 오히려 γ-Al2O3을 출발 물질로 제조한 촉매보다 비표면적 및 산점 특성이 우수하고, 반응특성이 향상되는 장점이 있다.Prepared by firing at the temperature of the catalyst is γ-Al 2 O 3 and have the same crystal phase and a structure and a rather γ-Al 2 O 3 a excellent in the specific surface area and acid site characteristics than the catalyst made of the starting material, the reaction There is an advantage that the characteristics are improved.
본 발명에 따른 SMR용 Ni계 촉매는 평균 직경이 2 내지 3mm인 펠렛일 수 있다. 반응기 크기에 따라 적합한 충진율을 갖는 촉매를 사용해야 하며, 본 반응에 사용할 촉매로서는 2mm 펠렛이 바람직하다.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.
본 발명에 따른 SMR용 Ni계 촉매 성형체는 기계적 강도가 8 내지 20 kgf일 수 있다.Ni-based catalyst molded article for SMR according to the present invention may have a mechanical strength of 8 to 20 kgf.
본 발명에 따른 SMR용 Ni계 촉매 성형체는 비표면적이 50 내지 200 m2/g일 수 있으며, 바람직하게는 75 내지 150 m2/g일 수 있다.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.
본 발명에 따른 SMR용 Ni계 촉매 성형체는 평균 기공 직경이 5 내지 15 nm일 수 있다.Ni-based catalyst molded article for SMR according to the present invention may have an average pore diameter of 5 to 15 nm.
본 발명에 따른 SMR용 Ni계 촉매 성형체는 500 내지 900 ℃, 구체적으로 550 내지 650℃에서의 수증기 메탄 개질 공정(SMR)에서 메탄전환율이 평형전환율 대비 80%이상일 수 있다.In the Ni-based catalyst molded body for SMR according to the present invention, 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.
본 발명에 따른 SMR용 Ni계 촉매 성형체는 수증기 메탄 개질 반응 전에도 Ni종 결정(結晶)을 포함하고, 반응 후 촉매의 XRD에서 Ni peak가 나타난다. The 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.
상기 Ni종 결정의 비제한적인 예로는 NiAl2O3등이 있다.Non-limiting examples of the Ni species crystals include NiAl 2 O 3 and the like.
수소 제조를 위한 수증기 메탄 개질 공정은 기체 몰 수가 증가하는 반응으로 압력에 큰 영향을 받는다. 촉매의 파손은 반응 압력을 증가시켜 반응 효율을 낮추는 요인이 될 수 있는데, 본 발명에 따른 펠렛형 SMR 용 촉매 성형체는 이를 방지할 수 있다.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.
따라서, 본 발명에 따른 펠렛형 SMR용 Ni계 촉매 성형체는 500~600 ℃ 저온에서의 수증기 메탄 개질 공정(SMR) 및 수소분리 공정을 동시에 수행하는 반응기에 사용될 수 있다.Therefore, 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.
다른 하나의 양태로서 본 발명은 In another aspect, the present invention
1) 니켈 전구체 용액을 준비하는 단계; 1) preparing a nickel precursor solution;
2) 단계 1)의 용액에 보헤마이트를 침지하여 보헤마이트에 니켈 전구체를 함침시키는 단계; 2) impregnating boehmite into the solution of step 1) to impregnate the boehmite with a nickel precursor;
3) 보헤마이트에 나켈 전구체가 담지된 촉매 파우더를 수득하는 단계; 및 3) obtaining a catalyst powder having a nickel precursor supported on boehmite; And
4) 단계 3)의 분말을 압축 성형하고 소성하는 단계;를 포함하는 수증기 메탄 개질용 Ni계 촉매 성형체의 제조방법을 제공한다.It provides a method for producing a Ni-based catalyst molded body for steam methane reforming, including; 4) compression molding and calcining the powder of step 3).
본 발명에 따른 펠렛형 SMR용 Ni계 촉매 성형체는 상기 제조방법에 따라 제조되는 것일 수 있다. Ni-based catalyst compact for pellet-type SMR according to the present invention may be prepared according to the above production method.
상기 니켈 전구체는 질산염(NO3), 아세테이트염, 할라이드염(F, Cl, Br, I) 또는 이의 혼합물 형태일 수 있으나, 이에 한정되지는 않는다. 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.
구체적으로 상기 니켈 전구체는 니켈 나이트레이트 헥사하이드레이트(Nickel Nitrate Hexahydrate), 니켈클로라이드 헥사하이드레이트(Nickel Chloride Hexahydrate), 니켈 아세테이트 테트라하이드레이트(Nickel Acetate Tetrahydrate) 및 니켈 브로마이드 하이드레이트(Nickel Bromide Hydrate)로 이루어진 군으로부터 선택된 1 종 이상일 수 있다.Specifically, 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.
더욱 구체적으로, 상기 니켈 전구체는 니켈과, 티타늄(Ti), 바나듐(V), 크롬(Cr), 망간(Mn), 철(Fe), 코발트(Co), 구리(Cu), 알루미늄(Al), 마그네슘(Mg), 지르코늄(Zr) 및 보론(B)으로 이루어진 군으로부터 선택된 하나 이상의 금속으로 이루어진 복합체 전구체일 수 있다. 가장 바람직하게는, 상기 니켈 함유 복합체 전구체는 니켈과, 크롬(Cr), 구리(Cu), 알루미늄(Al), 마그네슘(Mg) 및 보론(B)으로 이루어진 군으로부터 선택된 하나 이상의 금속을 포함하는 복합체 전구체일 수 있다.More specifically, 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.
상기 니켈 함유 복합체 전구체 용액은 조촉매 금속 공급 전구체를 함께 포함하는 것일 수 있다. 상기 조촉매의 비제한적인 예로는 Ag, La, Mg, Pd, Ru 등이 있다. 구체적으로 조촉매는 La, Mg 및 Pd로 구성된 군에서 1종 이상 선택된 것일 수 있다.The nickel-containing composite precursor solution may be one containing a promoter metal supply precursor. Non-limiting examples of the promoter include Ag, La, Mg, Pd, Ru and the like. Specifically, the promoter may be one or more selected from the group consisting of La, Mg and Pd.
상기 단계 4)에서 촉매 증진제로서 산화칼슘을 첨가할 수 있다. 구체적으로 단계 3)에서 수득된 분말에 촉매 증진제를 혼합한 후 압축 성형하고 소성하는 과정을 수행할 수 있다.In 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.
상기 니켈 전구체의 용매로는 물, C1~C6의 저급 알콜 등이 있으며, 특히 증류수, 탈이온수를 사용하는 것이 바람직하다. 상기 전구체 용액은 80 내지 130 ℃에서 제조될 수 있다. 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.
상기 단계 3)에서 촉매 파우더를 수득하는 단계는 보헤마이트가 침지된 단계 2)의 용액을 건조함으로써 수행될 수 있으며, 건조는 100 내지 130 ℃에서 5 내지 10 시간동안 수행될 수 있다. 건조 방법은 특별히 한정하지 않으며 회전진공 증발기(rotatory evaporator) 또는 오븐을 사용할 수 있다. 지지체의 개질이나 촉매 또는 촉매 증진제의 담지시, 이들 전구체 용액을 담지하는 횟수는 제한하지 않는다. 예들 들면, 촉매성분 담지시 여러 번에 걸쳐 나누어서 담지할 수 있다. 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. When modifying the support or supporting the catalyst or catalyst enhancer, the number of times of supporting these precursor solutions is not limited. For example, the catalyst component may be supported by dividing it several times.
상기 단계 3)은 압축 성형 전에 촉매 파우더의 사이즈를 조절하기 위해 얻어진 촉매 파우더를 일정 크기로 선별하거나 분쇄 및 선별하는 단계를 추가로 포함할 수 있다. 압축 성형 전 촉매 파우더의 크기는 45 내지 75㎛일 수 있다. 본 발명은 압축성형 전 촉매 파우더의 사이즈를 조절하여 촉매의 기계적 강도를 조절하는 것을 특징으로 한다. 촉매 파우더의 사이즈가 45㎛ 이하일 경우 성형 모듈에 달라붙어 모듈 파손 원인이 될 수 있다. 45 내지 75㎛ 사이즈의 촉매 파우더를 이용해 성형한 펠렛의 강도가 가장 우수하였다(도 4(b)). 불균일한 촉매 파우더 사이즈는 성형 모듈을 손상시키고 펠렛의 강도를 저하시킬 수 있다.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 μm 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㎛ can stick to the molding module may cause module damage. The strength of the pellets formed using the catalyst powder of 45 to 75 μm size was the best (FIG. 4 (b)). Uneven catalyst powder size can damage the molding module and reduce the strength of the pellets.
상기 단계 4)의 압축 성형은 5 kN 내지 25 kN, 구체적으로 10 kN 내지 20 kN, 보다 구체적으로 13 kN 내지 17 kN일 수 있으나, 이에 제한되지는 않으며, 펠렛의 치수에 따라 조절될 수 있다. 본 발명은 촉매 파우더에 가해지는 압축 강도를 조절하여 촉매의 기계적 강도를 조절하는 것을 특징으로 한다. 촉매에 가해지는 압축강도가 비정상적으로 높을 경우, 성형 모듈 손상의 원인이 될 수 있다(도 4(a)).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)).
본 발명은 촉매 파우더의 점도를 높여 촉매가 성형성을 갖도록 할 수 있다. 이를 위해 단계 4)의 압축성형시 촉매 파우더에 첨가제를 첨가할 수 있다. 일례로 촉매의 성형성을 갖추게 하는 점도제로서 PVA, 탈크 등을 첨가할 수 있다. 또한, 펠렛의 성형시 모듈 틈 사이에 끼는 파우더를 최소화하기 위해 윤활제로서 탈크, 그라파이트 등을 첨가할 수 있다.The present invention can increase the viscosity of the catalyst powder so that the catalyst has a formability. For this purpose, an additive may be added to the catalyst powder during compression molding in step 4). As an example, PVA, talc, etc. can be added as a viscosity agent which provides the moldability of a catalyst. In addition, talc, graphite, or the like may be added as a lubricant to minimize the powder sandwiched between module gaps during molding of the pellets.
상기 단계 4)에서 압축성형된 펠렛의 소성 온도는 500 내지 1000 ℃일 수 있으며, 구체적으로 800 ~ 900 ℃, 특히 850℃일 수 있다.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.
상기 제조방법에 따라 제조된 촉매는 펠렛 형태일 수 있으며, 평균 직경이 2 내지 3mm인 펠렛일 수 있다. 반응기 크기에 따라 적합한 충진율을 갖는 촉매를 사용해야 하며, 본 반응에 사용할 촉매로서는 2mm 펠렛이 바람직하다.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.
다른 하나의 양태로서 본 발명은 수증기 메탄 개질 공정(SMR) 및 수소분리 공정을 동시에 수행하는 반응기로서, 본 발명에 따른 펠렛형 SMR용 Ni계 촉매 성형체를 사용하는 것이 특징인 반응기를 제공한다.In another aspect, 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.
상기 반응기는 수성가스 전환반응용 촉매를 더 포함할 수 있다.The reactor may further include a catalyst for water gas shift reaction.
또한, 본 발명에 따른 SMR용 Ni계 촉매 성형체는 하나의 반응기에서 수증기 메탄 개질 공정(SMR) 및 수소분리 공정을 수행하여 천연가스로부터 합성가스 또는 수소가스를 제조하는 방법에 사용될 수 있다.In addition, the Ni-based catalyst molded body for SMR according to the present invention 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.
상기 방법은 상기 반응기에서 수소분리 공정 이후 수성가스 전환반응도 수행할 수 있다.The method may also perform a water gas shift reaction after the hydrogen separation process in the reactor.
본 발명에 따른 SMR용 Ni계 촉매 성형체 존재 하에 수증기 메탄 개질 공정(SMR)을 수행하는 반응기에, 수소 투과도가 있는 분리구조체를 탑재시키면 수소 투과도가 다른 기체들에 비하여 높기 때문에 반응과 동시에 생성물인 수소가 선택적으로 제거될 수 있으며, 따라서 르샤틀리에 원리에 따라 개질 반응에서의 정반응이 더욱 우세하게 진행될 수 있으므로, 낮은 온도범위에서도 높은 메탄 전환율을 얻을 수 있다.In the reactor performing the steam methane reforming process (SMR) in the presence of a Ni-based catalyst molded body for SMR according to the present invention, since the separation structure having hydrogen permeability is high, the hydrogen permeability is higher than other gases. Can be selectively removed, and according to the LeChatlier principle, the forward reaction in the reforming reaction can be more predominant, so that a high methane conversion can be obtained even at a low temperature range.
본 발명에 사용되는 상기 분리구조체는 수소투과도가 높은 분리막을 사용하는 것이 바람직하다. As the separation structure used in the present invention, it is preferable to use a separation membrane having a high hydrogen permeability.
상기 분리구조체는 합성가스에서 수소 선택성이 있는 것으로, 실리카, 알루미나, 지르코니아, YSZ, 또는 이의 조합을 포함하는 세라믹; 혹은, 니켈, 구리, 철, 팔라듐, 루테늄, 로듐, 백금, 또는 이의 조합으로 구성된 금속; 혹은 상기 금속과 세라믹이 혼합된 복합조성일 수 있다. 상기 분리구조체 구조는 다양할 수 있으며, 비제한적인 예로는 평막, 튜브, 중공사막 형태일 수 있다.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.
본 발명에 따르면 압축성형을 통해 고강도의 니켈계 촉매 성형체를 제조하여 500~600 ℃ 저온에서의 수증기 메탄 개질 공정(SMR)에 사용할 수 있다. According to the present invention, 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.
본 발명의 SMR 용 촉매 성형체는 보헤마이트를 지지체로 사용함으로써 펠렛화 및 성형화를 통한 촉매의 고강도화가 가능하며 향상된 반응 특성을 나타낼 수 있다.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.
도 1은 (a)온도에 따른 반응기의 수축팽창 및 (b)압력에 따른 평형전환율을 나타낸 것이다.Figure 1 shows the shrinkage expansion of the reactor according to (a) temperature and (b) equilibrium conversion rate according to the pressure.
도 2는 (a)MgNiAl2O3 파우더 촉매, (b) 압축성형 펠렛 촉매를 촬영한 사진이다.2 is a photograph of (a) MgNiAl 2 O 3 powder catalyst, (b) compression molding pellet catalyst.
도 3은 성형방법에 따른 2mm 펠렛 촉매의 압축강도를 나타낸 것이다.Figure 3 shows the compressive strength of the 2mm pellet catalyst according to the molding method.
도 4는 압축성형의 변수별 촉매의 기계적 강도를 나타낸 것이다((a) 압축강도 별, (b) 촉매 사이즈별).Figure 4 shows the mechanical strength of the catalyst for each variable of compression molding ((a) by compressive strength, (b) by catalyst size).
도 5는 다양한 첨가제에 따른 성형 강도를 나타낸 것이다(0은 성형 불가 촉매).Figure 5 shows the molding strength according to various additives (0 is a non-molding catalyst).
도 6은 펠렛 성형 촉매의 메탄전환율 및 평형전환율 대비 메탄전환율을 나타낸 것이다.Figure 6 shows the methane conversion and the equilibrium conversion of methane conversion of the pellet forming catalyst.
이하 본 발명을 하기 예에 의해 상세히 설명한다. 다만, 하기 예는 본 발명을 예시하기 위한 것일 뿐, 하기 예에 의해 본 발명의 범위가 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited by the following examples.
실시예Example
1 One
증류수에 니켈 함유 복합체 전구체(MgNiAl2O4)를 1.0 mol/L로 녹여 1시간 동안 초음파 분산시켜 금속이 분산된 전구체 용액을 제조하였다. 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.
상기 전구체 용액에 Boehmite(A사) 분말를 담근 후 40~70℃에서 2단계 rpm으로 교반 후 100℃ 건조기에서 24시간 동안 건조시켜, 촉매 파우더를 얻었다. After dipping Boehmite (A) powder in the precursor solution, the mixture was stirred at 40 ° C. to 70 ° C. at 2 rpm and dried in a 100 ° C. dryer for 24 hours to obtain a catalyst powder.
촉매 파우더를 크기별(45-75㎛, 75-180㎛, 180-250㎛ 및 250-300㎛)로 선별하였다. 선별된 촉매 파우더에 첨가제를 사용하지 않고, 850℃에서 2*3 mm 촉매 펠렛을 10, 15, 또는 20kN의 압축 강도를 사용하여 압축 성형하였다. 850℃에서 공기 분위기에서 6시간 동안 소성하여 수증기 메탄 개질용 Ni계 촉매 펠렛을 제조하였다. Catalyst powders were selected by size (45-75 μm, 75-180 μm, 180-250 μm and 250-300 μm). 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.
실험예Experimental Example
1: 압축 1: compression
강도 별Strength stars
강도 평가 Strength rating
실시예 1에 따라 촉매 펠렛을 제조시 적용되는 압축 성형의 압축 강도에 따른 촉매 펠렛의 기계적 강도 평가를 수행하였다. 실시예 1의 촉매는 촉매 파우더를 각각 10, 15, 20 kN의 힘을 가하여 압축 성형하여 제조된 것을 사용하였으며, 제조된 촉매의 기계적 강도를 각각 측정하여 도 4(a)에 나타냈다. 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).
실험 결과 2*3mm 펠렛을 성형하기 위해 15kN을 가할 경우 촉매 펠렛의 기계적 강도가 1.8 kgf로 가장 우수한 것으로 나타났다.Experimental results showed that the mechanical strength of the catalyst pellets was the best at 1.8 kgf when 15 kN was added to form 2 * 3 mm pellets.
실험예Experimental Example
2: 촉매 파우더 2: catalyst powder
사이즈 별By size
강도 평가 Strength rating
실시예 1에 따라 촉매 펠렛을 제조시, 촉매 파우더의 크기에 따른 촉매 펠렛의 기계적 강도 평가를 수행하였다. 실시예 1의 촉매는 크기가 각각 45 내지 75 ㎛, 75 내지 180 ㎛, 180 내지 250㎛, 및 250 내지 300㎛인 촉매 파우더들을 15kN의 압축 강도로 압축성형하여 제조된 것을 사용하였으며, 제조된 촉매의 기계적 강도를 각각 측정하여 도 4(b)에 나타냈다. In preparing the catalyst pellets according to 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 μm, 75 to 180 μm, 180 to 250 μm, and 250 to 300 μm with a compressive strength of 15 kN, respectively. The mechanical strength of each was measured and shown in FIG. 4 (b).
그 결과, 45~75㎛ 사이즈의 촉매 파우더를 이용하여 성형한 촉매 펠렛의 기계적 강도가 가장 우수한 것으로 나타났다. 또한, 촉매의 사이즈가 45㎛ 이하일 경우 성형 모듈에 달라붙어 모듈 파손 원인이 됨을 확인하였다.As a result, the mechanical strength of the catalyst pellets formed using the catalyst powder of 45 ~ 75㎛ size was found to be the most excellent. In addition, when the size of the catalyst is 45㎛ or less, it was confirmed that the cause of module damage by sticking to the molding module.
비교예Comparative example
: 압출 성형을 통한 촉매의 제조 및 이의 강도 평가: Preparation of Catalysts by Extrusion and Evaluation of Their Strength
촉매 펠렛 제조시 압출 성형법을 이용한 것을 제외하고는 실시예 1과 동일하게 촉매 펠렛을 제조하였다. Catalyst pellets were prepared in the same manner as in Example 1 except that the extrusion pellets were used to prepare the catalyst pellets.
상기 촉매 펠렛과 실시예 1에 따라 제조된 촉매 펠렛의 기계적 강도를 각각 측정하여 도 3에 나타냈다. 이 때, 촉매 파우더는 모두 45~75㎛ 크기를 사용하였으며, 압축 성형시의 압축 강도는 15kN이었다.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㎛, the compression strength at the time of compression molding was 15kN.
실험예Experimental Example
3: 첨가제 평가 3: additive evaluation
촉매의 성형성을 향상시키기 위해 촉매의 압축 성형 시 첨가제로서 PVA, MC바인더, 탈크, 그라파이트를 사용할 수 있다. In order to improve the moldability of the catalyst, PVA, MC binder, talc, graphite may be used as an additive during compression molding of the catalyst.
45-75㎛의 촉매 파우더에 PVA, MC바인더, 탈크, 그라파이트를 각각 5wt%씩 첨가하여 15kN의 압축 강도로 압축성형하여 제조한 펠렛 촉매의 강도를 측정하여 그 결과를 도 5에 나타냈다. 5 wt% of PVA, MC binder, talc, and graphite were added to the catalyst powder of 45-75 μm, respectively, and the strength of the pellet catalyst prepared by compression molding at 15 kN compression strength was measured. The results are shown in FIG. 5.
도 5에서 보는 바와 같이, PVA 또는 MC 바인더는 점도제 역할을 하여, 촉매의 성형성을 갖추게 할 수 있으나, 촉매 균열의 원인이 되어 강도를 하락시킬 수 있다. 또한, 탈크나 그라파이트는 윤활제로서 펠렛의 성형 시 모듈 틈 사이에 끼는 파우더를 최소화할 수 있으나, 촉매 강도를 매우 떨어뜨릴 수 있음을 알 수 있었다.As shown in FIG. 5, 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. In addition, 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.
실험예Experimental Example
4: 활성 평가 4: activity evaluation
실시예 1에서 제조한 2*3mm 펠렛 촉매에 대해 증기와 메탄의 비(S/C)=3, SV=10,000/h, 600℃ 조건 하에서 수증기 메탄개질 반응에 대한 활성을 평가하여 그 결과를 하기 표 1 및 도 6에 나타냈다. 실시예 1의 촉매는 45-75㎛의 촉매 파우더를 15kN의 압축 강도로 압축성형하여 제조된 것을 사용하였다. The 2 * 3mm pellet catalyst prepared in Example 1 was evaluated for the activity of steam methane reforming reaction under the ratio of steam to methane (S / C) = 3, SV = 10,000 / h, 600 ° C. It is shown in Table 1 and FIG. The catalyst of Example 1 was prepared by compression molding a catalyst powder of 45-75㎛ with a compressive strength of 15kN.
도 6에서 보는 바와 같이, 수증기 메탄개질 반응 결과 본 실시예에 따라 제조한 촉매 펠렛이 니켈 알루미나를 기반으로 한 상용촉매(바스프사의 MCFC용 연료개질 촉매)보다 높은 메탄전환율 및 평형전환율 대비 전환율을 나타낸 것을 확인할 수 있다.As shown in FIG. 6, 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.
표 1에서 두 촉매 모두 균열이 없는 표면 형상을 나타내고, 본 실시예의 촉매 펠렛은 상용촉매과 유사한 길이 및 직경을 갖는 것을 확인하였다. In Table 1, both catalysts showed a surface shape without cracking, and the catalyst pellets of this example were confirmed to have a length and diameter similar to those of the commercial catalyst.
또한, 반응전 상용촉매의 비표면적이 본 실시예의 촉매 펠렛에 비해 약 2배 정도 컸으나, 반응 후 비표면적이 1/3 수준으로 감소한 반면, 본 실시예의 펠렛 촉매는 비표면적이 반응 전 106m2/g, 반응 후 91m2/g로 소폭 감소하는 것으로 나타났다. 이는 촉매 성분의 차이에 기인한 것으로 사료된다(상용촉매: 니켈 60 중량%, 실시예 1에 따른 촉매(MgNi/Al2O3): 니켈 20 중량%). In addition, while the specific surface area of the commercial catalyst before the reaction was about twice as large as that of the catalyst pellet of the present embodiment, the specific surface area of the pellet catalyst of the present embodiment was reduced to 1/3 level after the reaction, whereas the specific surface area of the pellet catalyst of the present embodiment was 106 m 2 / g, after the reaction was found to slightly decrease to 91m 2 / g. It is believed that this is due to the difference in the catalyst components (commercial catalyst: 60 wt% nickel, catalyst according to Example 1 (MgNi / Al 2 O 3 ): 20 wt% nickel).
또한, 상기 표 1에서 보는 바와 같이, 본 발명의 펠렛 촉매는 상용촉매보다 기계적 강도가 훨씬 우수함을 알 수 있다.In addition, as shown in Table 1, it can be seen that the pellet catalyst of the present invention is much superior in mechanical strength than the commercial catalyst.
Claims (16)
- 보헤마이트(boehmite)에 니켈 전구체를 함침시켜 담지한 촉매 파우더를 압축성형하여 소성한 것인, 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.A Ni-based catalyst molded product for steam methane reforming (SMR), wherein the catalyst powder impregnated with boehmite is impregnated with a nickel precursor, followed by compression molding and baking.
- 제1항에 있어서, 평균 직경이 2 내지 3mm인 펠렛인 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the pellets have an average diameter of 2 to 3 mm.
- 제1항에 있어서, 상기 압축성형은 압축강도가 5 kN 내지 25 kN인 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the compression molding has a compressive strength of 5 kN to 25 kN.
- 제1항에 있어서, 기계적 강도가 8 내지 20kgf인 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the mechanical strength is 8 to 20 kgf.
- 제1항에 있어서, 압축성형 전 촉매 파우더의 사이즈는 45 내지 75㎛인 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체. The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the catalyst powder before compression molding has a size of 45 to 75 µm.
- 제1항에 있어서, 비표면적이 50 내지 200 m2/g이고, 평균 기공 직경이 5 내지 15 nm 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the specific surface area is 50 to 200 m 2 / g, and the average pore diameter is 5 to 15 nm.
- 제1항에 있어서, 500~900 ℃에서의 수증기 메탄 개질 공정(SMR)에서 메탄전환율이 평형전환율 대비 80%이상인 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.The Ni-based catalyst molded product for steam methane reforming (SMR) according to claim 1, wherein the methane conversion in the steam methane reforming process (SMR) at 500 to 900 ° C. is 80% or more of the equilibrium conversion.
- 제1항에 있어서, 수증기 메탄 개질 반응 전 촉매는 Ni종 결정(結晶)을 포함하는 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the catalyst before the steam methane reforming reaction comprises Ni species crystals.
- 제8항에 있어서, 상기 Ni종 결정은 NiAl2O3인 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 8, wherein the Ni crystal is NiAl 2 O 3 .
- 제1항에 있어서, 상기 소성은 500 내지 1000 ℃에서 수행되는 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.The Ni-based catalyst compact for steam methane reforming (SMR) according to claim 1, wherein the firing is performed at 500 to 1000 ° C.
- 제1항에 있어서, La, Mg 및 Pd로 구성된 군에서 1종 이상 선택된 조촉매를 더 포함하는 것이 특징인 수증기 메탄 개질(SMR)용 Ni계 촉매 성형체.The Ni-based catalyst molded product for steam methane reforming (SMR) according to claim 1, further comprising a cocatalyst selected from the group consisting of La, Mg, and Pd.
- 1) 니켈 전구체 용액을 준비하는 단계; 1) preparing a nickel precursor solution;2) 단계 1)의 용액에 보헤마이트를 침지하여 보헤마이트에 니켈 전구체를 함침시키는 단계; 2) impregnating boehmite into the solution of step 1) to impregnate the boehmite with a nickel precursor;3) 보헤마이트에 나켈 전구체가 담지된 촉매 파우더를 수득하는 단계; 및 3) obtaining a catalyst powder having a nickel precursor supported on boehmite; And4) 단계 3)의 분말을 압축 성형하고 소성하는 단계;를 포함하는 수증기 메탄 개질용 Ni계 촉매 성형체의 제조방법.4) compressing the powder of step 3) and firing the powder; a method of manufacturing a Ni-based catalyst molded body for reforming steam methane, including.
- 수증기 메탄 개질 공정(SMR) 및 수소분리 공정을 동시에 수행하는 반응기로서, SMR 용 촉매로 제1항 내지 제11항 중 어느 한 항에 기재된 Ni계 촉매 성형체를 사용하는 것이 특징인 반응기.A reactor for simultaneously performing a steam methane reforming process (SMR) and a hydrogen separation process, wherein the reactor is characterized by using the Ni-based catalyst molded body according to any one of claims 1 to 11 as a catalyst for SMR.
- 제13항에 있어서, 수성가스 전환반응용 촉매를 더 포함하는 것이 특징인 반응기.The reactor according to claim 13, further comprising a catalyst for water gas shift reaction.
- 하나의 반응기에서 수증기 메탄 개질 공정(SMR) 및 수소분리 공정을 수행하여 천연가스로부터 합성가스 또는 수소가스를 제조하는 방법에 있어서,In a method for producing syngas or hydrogen gas from natural gas by performing steam methane reforming process (SMR) and hydrogen separation process in one reactor,제1항 내지 제11항 중 어느 한 항에 기재된 Ni계 촉매 성형체 하 SMR 공정을 수행하는 것이 특징인 합성가스 또는 수소가스 제조방법.A method for producing a syngas or hydrogen gas, characterized by performing an SMR process under the Ni-based catalyst molded body according to any one of claims 1 to 11.
- 제15항에 있어서, 상기 반응기에서 수소분리 공정 이후 수성가스 전환반응도 수행되는 것이 특징인 합성가스 또는 수소가스 제조방법.The method of claim 15, wherein a water gas shift reaction is also performed after the hydrogen separation process in the reactor.
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| KR102616015B1 (en) * | 2021-12-28 | 2023-12-20 | 한국화학연구원 | Catalyst for Methane Chlorination Reaction in Which a Graphtic Carbon Based Material is Highly Dispersed in an Inorganic Matrix |
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| KR20140106793A (en) * | 2013-02-27 | 2014-09-04 | 한국화학연구원 | Method for the preparation of molded article of nickel-containing catalyst for mixed modification reaction of methane and the molded catalyst article thus obtained |
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| US7108804B2 (en) * | 2002-06-12 | 2006-09-19 | National University Of Singapore | Supported nickel catalyst for synthesis gas preparation |
| KR20070076439A (en) * | 2006-01-16 | 2007-07-24 | 도다 고교 가부시끼가이샤 | Porous carrier for steam-reforming catalysts, steam-reforming catalyst and process for producing reactive mixed gas |
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