KR102073959B1 - Catalyst for synthesizing synthetic natural gas and manufacturing method for high calorific synthetic natural gas using the same - Google Patents
Catalyst for synthesizing synthetic natural gas and manufacturing method for high calorific synthetic natural gas using the same Download PDFInfo
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- KR102073959B1 KR102073959B1 KR1020170181241A KR20170181241A KR102073959B1 KR 102073959 B1 KR102073959 B1 KR 102073959B1 KR 1020170181241 A KR1020170181241 A KR 1020170181241A KR 20170181241 A KR20170181241 A KR 20170181241A KR 102073959 B1 KR102073959 B1 KR 102073959B1
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- South Korea
- Prior art keywords
- catalyst
- natural gas
- weight
- parts
- synthetic natural
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 28
- 238000002309 gasification Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 36
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 26
- 229910017052 cobalt Inorganic materials 0.000 claims description 25
- 239000010941 cobalt Substances 0.000 claims description 25
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 239000003345 natural gas Substances 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000003245 coal Substances 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 description 32
- 239000000203 mixture Substances 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 16
- -1 C 3 hydrocarbon Chemical class 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 description 7
- ZZCONUBOESKGOK-UHFFFAOYSA-N aluminum;trinitrate;hydrate Chemical compound O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZZCONUBOESKGOK-UHFFFAOYSA-N 0.000 description 6
- XZXAIFLKPKVPLO-UHFFFAOYSA-N cobalt(2+);dinitrate;hydrate Chemical compound O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XZXAIFLKPKVPLO-UHFFFAOYSA-N 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000003949 liquefied natural gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BTOGSPCPAIGMPH-UHFFFAOYSA-N O.[N+](=O)([O-])[O-].[Ru+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound O.[N+](=O)([O-])[O-].[Ru+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] BTOGSPCPAIGMPH-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- MTJZBBNYZUZBRX-UHFFFAOYSA-K aluminum;azanium;disulfate;hydrate Chemical compound [NH4+].O.[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MTJZBBNYZUZBRX-UHFFFAOYSA-K 0.000 description 1
- NMSGLFREHLNYDF-UHFFFAOYSA-K aluminum;triacetate;hydrate Chemical compound O.[Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O NMSGLFREHLNYDF-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- B01J35/0006—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1662—Conversion of synthesis gas to chemicals to methane (SNG)
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
본 발명은 합성천연가스 합성용 촉매 및 이를 이용한 합성천연가스의 제조방법에 관한 것으로서, 구체적으로, 석탄, 바이오 매스(mass), 폐기물 등과 같은 다양한 원료의 가스화를 통해 얻어진 합성가스(CO+H2)를 이용하여 합성천연가스(SNG)를 합성하는 공정에 사용되는 촉매 및 이를 이용한 합성천연가스의 제조방법에 관한 것이다.The present invention relates to a catalyst for synthesizing synthetic natural gas and a method for preparing a synthetic natural gas using the same, and specifically, a synthetic gas (CO + H 2) obtained through gasification of various raw materials such as coal, biomass, waste, and the like. The present invention relates to a catalyst used in a process for synthesizing synthetic natural gas (SNG) and a method for producing a synthetic natural gas using the same.
Description
본 발명은 합성천연가스 합성용 촉매 및 이를 이용한 합성천연가스의 제조방법에 관한 것으로서, 구체적으로, 석탄, 바이오 매스(mass), 폐기물 등과 같은 다양한 원료의 가스화를 통해 얻어진 합성가스(CO+H2)를 이용하여 합성천연가스(SNG)를 합성하는 공정에 사용되는 촉매 및 이를 이용한 합성천연가스의 제조방법에 관한 것이다.The present invention relates to a catalyst for synthesizing synthetic natural gas and a method for preparing a synthetic natural gas using the same, and specifically, a synthetic gas (CO + H 2) obtained through gasification of various raw materials such as coal, biomass, waste, and the like. The present invention relates to a catalyst used in a process for synthesizing synthetic natural gas (SNG) and a method for producing a synthetic natural gas using the same.
합성천연가스는 가정용 및 발전용으로 사용할 수 있는 차세대 에너지로서, 석탄을 합성천연가스(synthetic natural gas, SNG)로 전환하는 연구가 활발히 진행되고 있다. 그러나, 합성천연가스는 천연가스에 비해 상대적으로 발열량이 낮아, 천연가스를 사용하여 산화철의 환원을 통해 제철을 생산하는 방법인 직접환원법(direct reduction), 및 산업용 및 가정용의 천연가스 배관망에 연결하여 사용하기에는 문제가 있었다. 하기 표 1에서 보는 바와 같이, 합성천연가스(SNG)는 98% 이상이 메탄으로 구성되어, 액화천연가스(liquefied natural gas, LNG)나 파이프라인 천연가스(pipeline natural gas, PNG)에 비하여 다량의 메탄을 포함함에도 불구하고 10,000 kcal/㎥ 이하의 낮은 발열량을 가졌다.Synthetic natural gas is the next generation energy that can be used for home and power generation, and research into converting coal into synthetic natural gas (SNG) is being actively conducted. However, synthetic natural gas has a lower calorific value than natural gas, and is connected to the direct reduction method, which is a method of producing iron through reduction of iron oxide using natural gas, and to a natural gas pipeline network for industrial and home use. There was a problem to use. As shown in Table 1, synthetic natural gas (SNG) is composed of more than 98% methane, a large amount of liquefied natural gas (liquefied natural gas, LNG) or pipeline natural gas (PNG) Despite the inclusion of methane it had a low calorific value of less than 10,000 kcal / m 3.
이에 대한 대안으로, 합성천연가스의 발열량을 조절하기 위해, 합성천연가스에 액화석유가스(liquefied petroleum gas)와 같은 가스연료를 혼합하여 10,000 kcal/㎥ 이상으로 발열량을 높이고 있다. 그러나, 합성천연가스에 가스연료를 추가하여 사용하는 것은 경제적인 면에서 이점이 거의 없으므로, 고발열량의 합성천연가스를 합성할 수 있는 새로운 공정이 요구되고 있는 실정이다.As an alternative to this, in order to control the calorific value of the synthetic natural gas, by mixing a gas fuel such as liquefied petroleum gas (liquefied petroleum gas) to increase the calorific value to 10,000 kcal / ㎥ or more. However, since the use of gas fuel in addition to the synthetic natural gas has little economic advantage, there is a demand for a new process for synthesizing a synthetic gas having a high calorific value.
이에 대한 대안으로 한국 등록특허 제10-1691817호는 수성가스전이 및 이산화탄소 제거와 함께 탄소질 물질의 가스화로부터 유도되는 합성 가스의 메탄화를 이용하여, (H2-CO2)/(CO+CO2)의 몰비가 3.00보다 큰 합성가스를 생성하는 합성천연가스(SNG)의 생성방법을 개시하고 있다. 상술한 바와 같이 제조된 합성천연가스(SNG)는 과량의 이산화탄소 및 수소 없이 일정한 고품질을 갖는다.As an alternative, Korean Patent No. 10-1691817 uses (H 2 -CO 2 ) / (CO + CO) by using methanation of synthesis gas derived from gasification of carbonaceous material with water gas transition and carbon dioxide removal. Disclosed is a method for producing a synthetic natural gas (SNG) which produces a syngas having a molar ratio of 2 ) greater than 3.00. Synthetic natural gas (SNG) prepared as described above has a constant high quality without excess carbon dioxide and hydrogen.
그러나, 상기 등록특허는 종래의 SNG에 비하여 발열량이 높은 SNG를 생산할 수 있으나, 이는 SNG 생성시 발생하는 이산화탄소의 비율을 감소시켜 발열량을 높인 것으로써 SNG의 발열 탄소원은 메탄 하나만 존재하므로 이로 인한 발열량 제한은 피할 수 없다는 문제점이 있었다.However, the registered patent may produce SNG having a higher calorific value than conventional SNG, but this is to reduce the ratio of carbon dioxide generated when SNG is generated, thereby increasing the calorific value, so that only one methane exothermic carbon source exists, thereby limiting calorific value. There was a problem that could not be avoided.
이에, 본 발명은 발열 탄소원으로 메탄 이외에 탄소수 2 이상의 탄화수소를 포함함으로써, 종래 메탄만 포함하는 SNG의 발열량의 한계를 극복하여 높은 발열량을 갖는 SNG를 제조할 수 있는 촉매, 및 이를 이용한 합성천연가스의 제조방법을 제공하고자 한다.Accordingly, the present invention includes a catalyst capable of producing SNG having a high calorific value by overcoming the limitation of the calorific value of conventional SNG containing only methane, by including hydrocarbons having 2 or more carbon atoms in addition to methane as the exothermic carbon source, and a synthetic natural gas using the same. It is intended to provide a manufacturing method.
본 발명은 산화알루미늄, 니켈 및 코발트를 포함하고,The present invention includes aluminum oxide, nickel and cobalt,
상기 산화알루미늄 100 중량부를 기준으로 11 중량부 이상의 상기 코발트를 포함하는 합성천연가스 합성용 촉매를 제공한다.It provides a catalyst for synthesizing natural gas comprising at least 11 parts by weight of the cobalt based on 100 parts by weight of the aluminum oxide.
나아가, 본 발명은 산화알루미늄, 니켈, 코발트 및 루테늄을 포함하고,Furthermore, the present invention includes aluminum oxide, nickel, cobalt and ruthenium,
상기 산화알루미늄 100 중량부를 기준으로 0.05 내지 7 중량부의 루테늄 및 1 내지 10 중량부의 상기 코발트를 포함하는, 합성천연가스 합성용 촉매를 제공한다. It provides a catalyst for synthesizing natural gas comprising 0.05 to 7 parts by weight of ruthenium and 1 to 10 parts by weight of the cobalt based on 100 parts by weight of the aluminum oxide.
또한, 본 발명은 연료의 가스화로 생성된 합성 가스를 수성가스전환 공정, 메탄화 공정, 탈황 및 이산화탄소 분리 공정을 거쳐 합성천연가스를 제조하는 방법에 있어서,In addition, the present invention is a method for producing a synthetic natural gas through a water gas conversion process, methanation process, desulfurization and carbon dioxide separation process of the synthesis gas generated by the gasification of the fuel,
상기 메탄화 공정이 상기 합성천연가스 합성용 촉매를 포함하여 수행하고,The methanation process is performed including the catalyst for synthesizing natural gas,
상기 메탄화 공정이 메탄화 반응 및 피셔-트롭쉬 반응이 동시에 진행되는, 합성천연가스의 제조방법을 제공한다.The methanation process provides a method for producing a synthetic natural gas in which a methanation reaction and a Fischer-Tropsch reaction are simultaneously performed.
본 발명에 따른 합성천연가스의 제조방법은 메탄과 함께 탄소수 2 이상의 탄화수소를 포함하여 고발열량의 합성천연가스를 제조할 수 있다.The method for producing a synthetic natural gas according to the present invention may include a hydrocarbon having 2 or more carbon atoms together with methane to produce a high calorific value synthetic natural gas.
본 발명은 산화알루미늄, 니켈 및 코발트를 포함하고,The present invention includes aluminum oxide, nickel and cobalt,
상기 산화알루미늄 100 중량부를 기준으로 11 중량부 이상의 상기 코발트를 포함하는, 합성천연가스 합성용 촉매를 제공한다.It provides a catalyst for synthesizing natural gas comprising at least 11 parts by weight of the cobalt based on 100 parts by weight of the aluminum oxide.
또한, 본 발명은 산화알루미늄, 니켈, 코발트 및 루테늄을 포함하고,In addition, the present invention includes aluminum oxide, nickel, cobalt and ruthenium,
상기 산화알루미늄 100 중량부를 기준으로 0.05 내지 7 중량부의 상기 루테늄 및 1 내지 10 중량부의 상기 코발트를 포함하는, 합성천연가스 합성용 촉매를 제공한다.It provides a catalyst for synthesizing natural gas comprising 0.05 to 7 parts by weight of the ruthenium and 1 to 10 parts by weight of the cobalt based on 100 parts by weight of the aluminum oxide.
상기 촉매는 코발트를 11 중량부 이상의 양으로 포함할 경우 루테늄을 포함하지 않고, 코발트를 1 내지 10 중량부의 양으로 포함할 경우 소량의 루테늄을 포함함으로써, 상기 촉매를 이용하여 제조된 합성천연가스는 탄소수 2 이상의 탄화수소를 포함하여 발열량이 우수하다.The catalyst does not include ruthenium when cobalt is included in an amount of 11 parts by weight or more, and when a cobalt is included in an amount of 1 to 10 parts by weight, a small amount of ruthenium is synthesized. It is excellent in calorific value including hydrocarbon having 2 or more carbon atoms.
상기 산화알루미늄은 산화알루미늄 전구체로부터 얻어질 수 있다. 상기 산화알루미늄 전구체로는, 예를 들어, 알루미늄 나이트레이트 수화물(Al(NO3)3·9H2O), 알루미늄 아세테이트 수화물(Al(CH3CO2)·H2O), 알루미늄 암모늄설페이트 수화물(AlNH4(SO4)2·12H2O) 및 알루미늄 클로라이드 수화물(AlCl3·6H2O) 등을 들 수 있다.The aluminum oxide can be obtained from an aluminum oxide precursor. To the aluminum oxide precursor, for example, aluminum nitrate hydrate (Al (NO 3) 3 · 9H 2 O), aluminum acetate hydrate (Al (CH 3 CO 2) · H 2 O), aluminum ammonium sulfate hydrate ( AlNH 4 (SO 4 ) 2 .12H 2 O) and aluminum chloride hydrate (AlCl 3 .6H 2 O).
상기 니켈은 니켈 전구체로부터 얻어질 수 있다. 상기 니켈 전구체로는, 예를 들어, 니켈 나이트레이트 수화물(Ni(NO3)2·4H2O), 니켈 아세테이트(Ni(CO2CH3)2·4H2O), 니켈 옥살레이트(NiC2O4), 니켈 아세테이트(Ni(CH3COO)2) 및 니켈 클로라이드(NiCl2·6H2O) 등을 들 수 있다.The nickel can be obtained from a nickel precursor. In the nickel precursor, e.g., nickel nitrate hydrate (Ni (NO 3) 2 · 4H 2 O), nickel acetate (Ni (CO 2 CH 3) 2 · 4H 2 O), nickel oxalate (NiC 2 O 4 ), nickel acetate (Ni (CH 3 COO) 2 ), nickel chloride (NiCl 2 · 6H 2 O), and the like.
상기 코발트는 코발트 전구체로부터 얻어질 수 있다. 상기 코발트 전구체로는, 예를 들어, 코발트 나이트레이트 수화물(Co(NO3)2·6H2O), 코발트 아세테이트 수화물(Co(CO2CH3)2·4H2O), 코발트 아세테이트(Co(CH3COO)2) 및 코발트 클로라이드(CoCl2) 등을 들 수 있다.The cobalt can be obtained from cobalt precursors. Examples of the cobalt precursor include cobalt nitrate hydrate (Co (NO 3 ) 2 .6H 2 O), cobalt acetate hydrate (Co (CO 2 CH 3 ) 2 .4H 2 O), cobalt acetate (Co ( CH 3 COO) 2 ), cobalt chloride (CoCl 2 ), and the like.
상기 루테늄은 루테늄 전구체로부터 얻어질 수 있다. 상기 루테늄 전구체로는, 예를 들어, 루테늄 나이트레이트 수화물(Ru(NO)3·xH2O), 루테늄 클로라이드 수화물 (RuCl3·xH2O) 및 루테늄 니트로실 나이트레이트 (Ru(NO)(NO3)x(OH)y) 등을 들 수 있다.The ruthenium may be obtained from a ruthenium precursor. To the ruthenium precursor, e.g., ruthenium nitrate hydrate (Ru (NO) 3 · xH 2 O), ruthenium chloride hydrate (RuCl 3 · xH 2 O), and ruthenium nitrosyl nitrate (Ru (NO) (NO 3 ) x (OH) y ) etc. are mentioned.
상기 촉매는 상기 산화알루미늄 100 중량부를 기준으로 11 중량부 이상의 상기 코발트를 포함한다. 구체적으로, 상기 촉매는 상기 산화알루미늄 100 중량부를 기준으로 11 내지 30 중량부, 12 내지 25 중량부, 또는 12 내지 20 중량부의 상기 코발트를 포함할 수 있다.The catalyst comprises at least 11 parts by weight of the cobalt based on 100 parts by weight of the aluminum oxide. Specifically, the catalyst may include 11 to 30 parts by weight, 12 to 25 parts by weight, or 12 to 20 parts by weight of the cobalt based on 100 parts by weight of the aluminum oxide.
상기 촉매는 상기 산화알루미늄 100 중량부를 기준으로 0.05 내지 7 중량부의 상기 루테늄 및 1 내지 10 중량부의 상기 코발트를 포함한다. 구체적으로, 상기 촉매는 상기 산화알루미늄 100 중량부를 기준으로 0.05 내지 6 중량부, 0.05 내지 5 중량부, 또는 0.1 내지 5 중량부의 상기 루테늄, 및 1 내지 10 중량부, 3 내지 10 중량부, 또는 3 내지 8 중량부의 상기 코발트를 포함할 수 있다.The catalyst comprises 0.05 to 7 parts by weight of the ruthenium and 1 to 10 parts by weight of the cobalt based on 100 parts by weight of the aluminum oxide. Specifically, the catalyst is 0.05 to 6 parts by weight, 0.05 to 5 parts by weight, or 0.1 to 5 parts by weight of the ruthenium, and 1 to 10 parts by weight, 3 to 10 parts by weight, or 3 based on 100 parts by weight of the aluminum oxide To 8 parts by weight of the cobalt.
상기 촉매는 지르코늄(Zr), 세륨(Ce), 백금(Pt), 로듐(Rh), 팔라듐(Pd) 및 갈륨(Ga)으로 이루어진 군으로부터 선택된 1종 이상의 조촉매를 더 포함할 수 있다.The catalyst may further include one or more cocatalysts selected from the group consisting of zirconium (Zr), cerium (Ce), platinum (Pt), rhodium (Rh), palladium (Pd), and gallium (Ga).
상기 촉매는 다공성 지지체를 더 포함할 수 있다.The catalyst may further comprise a porous support.
상기 다공성 지지체는 제올라이트, 알루미나 및 실리카로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 구체적으로, 상기 다공성 지지체는 제올라이트일 수 있다.The porous support may include one or more selected from the group consisting of zeolite, alumina and silica. Specifically, the porous support may be zeolite.
상기 촉매는 산화알루미늄 100 중량부를 기준으로 30 내지 60 중량부의 다공성 지지체를 포함할 수 있다. 구체적으로, 상기 촉매는 산화알루미늄 100 중량부를 기준으로 30 내지 55 중량부, 35 내지 50 중량부, 또는 40 내지 50 중량부의 다공성 지지체를 포함할 수 있다.The catalyst may include 30 to 60 parts by weight of the porous support based on 100 parts by weight of aluminum oxide. Specifically, the catalyst may include 30 to 55 parts by weight, 35 to 50 parts by weight, or 40 to 50 parts by weight of the porous support based on 100 parts by weight of aluminum oxide.
260 ℃ 및 20 kg/㎠의 반응기에 수소(H2)와 일산화탄소(CO)를 3:1의 몰비로 공급하면서 메탄화 반응을 수행했을 때, 상기 촉매의 일산화탄소 전환율은 90 내지 100 %일 수 있다. 구체적으로, 상술한 바와 같은 메탄화 반응시, 상기 촉매의 일산화탄소 전환율은 91 내지 100 %, 또는 92 내지 100 %일 수 있다.When the methanation reaction is performed while supplying hydrogen (H 2 ) and carbon monoxide (CO) at a molar ratio of 3: 1 to a reactor at 260 ° C. and 20 kg / cm 2 , the carbon monoxide conversion of the catalyst may be 90 to 100%. . Specifically, in the methanation reaction as described above, the carbon monoxide conversion of the catalyst may be 91 to 100%, or 92 to 100%.
상기 메탄화 반응의 생성물은 총 카본몰%를 기준으로 20 내지 40 카본몰%의 탄소수 2 이상의 탄화수소가스를 포함할 수 있다. 구체적으로, 상기 메탄화 반응의 생성물이 총 카본몰%를 기준으로 25 내지 40 카본몰%의 탄소수 2 이상의 탄화수소가스를 포함할 수 있다.The product of the methanation reaction may include a hydrocarbon gas of 20 to 40 carbon mol% or more carbon atoms based on the total carbon mol%. Specifically, the product of the methanation reaction may include a hydrocarbon gas of 25 to 40 carbon mol% 2 or more carbon atoms based on the total carbon mol%.
상기 탄소수 2 이상의 탄화수소가스는, 예를 들어, 에탄, 프로판, 부탄, 펜탄 등을 들 수 있다.Examples of the hydrocarbon gas having 2 or more carbon atoms include ethane, propane, butane, pentane and the like.
상기 촉매는 소결, 코크스화 또는 오염 등에 의한 비활성화를 방지하기 위해, 칼슘 아세테이트, 마그네슘 아세테이트, 나이트레이트 및 클로라이드 계열의 전구체로 이루어진 군으로부터 선택된 1종 이상의 촉매 활성 성분에 포함할 수 있다. 또한, 상기 전구체는 촉매 100 중량부에 대하여 1 내지 5 중량부의 양으로 포함될 수 있다.The catalyst may be included in at least one catalytically active ingredient selected from the group consisting of calcium acetate, magnesium acetate, nitrate and chloride series precursors to prevent deactivation by sintering, coking or contamination. In addition, the precursor may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the catalyst.
예를 들어, 상기 촉매는 산화알루미늄 전구체, 니켈 전구체 및 코발트 전구체를 포함하는 전구체 혼합물, 또는 산화알루미늄 전구체, 니켈 전구체, 코발트 전구체 및 루테늄 전구체를 포함하는 전구체 혼합물과 침전제를 혼합하여 공침함으로써 제조될 수 있다. 또한, 상기 촉매는 상기 전구체 혼합물 및 침전제를 다공성 지지체에 첨가하여 함침시킴으로써 제조될 수 있다.For example, the catalyst can be prepared by mixing and coprecipitating a precursor mixture comprising an aluminum oxide precursor, a nickel precursor and a cobalt precursor, or a precursor mixture comprising an aluminum oxide precursor, a nickel precursor, a cobalt precursor, and a ruthenium precursor and a precipitant. have. In addition, the catalyst may be prepared by impregnating the precursor mixture and the precipitant by adding the porous support.
상술한 바와 같이 제조된 촉매는 (a) 100 내지 200 ℃에서 12 내지 30 시간 동안 건조하는 단계; (b) 건조된 촉매를 300 내지 700 ℃, 또는 400 내지 600 ℃에서 소성하는 단계; 및 (c) 소성된 촉매를 280 내지 700 ℃, 수소 존재 및 상압 하에서 환원하는 단계를 통해 건조, 소성 및 환원될 수 있다.The catalyst prepared as described above is (a) drying for 12 to 30 hours at 100 to 200 ℃; (b) calcining the dried catalyst at 300 to 700 ° C., or 400 to 600 ° C .; And (c) reducing the calcined catalyst at 280 to 700 ° C. under hydrogen presence and atmospheric pressure.
상기 공침이란 2종 이상의 이온들을 수용액 혹은 비수용액에서 동시에 침전시키는 것으로, 상기 전구체 혼합물에 포함된 전구체들을 동시에 침전시키는 것을 의미한다.The coprecipitation is to simultaneously precipitate two or more ions in an aqueous solution or a non-aqueous solution, and means to simultaneously precipitate precursors included in the precursor mixture.
상기 함침이란 금속에 다른 금속이나 기타 물질을 완전히 밀착시키는 것으로, 상기 전구체 혼합물을 다공성 지지체의 기공에 담지시키는 것을 의미한다.The impregnation means to completely adhere other metals or other materials to the metal, and to impregnate the precursor mixture in the pores of the porous support.
합성천연가스의Synthetic natural gas 제조방법 Manufacturing method
본 발명은 연료의 가스화로 생성된 합성 가스를 수성가스전환 공정, 메탄화 공정, 탈황 및 이산화탄소 분리 공정을 거쳐 합성천연가스를 제조하는 방법에 있어서,The present invention is a method for producing a synthetic natural gas through the synthesis gas generated by the gasification of the fuel through a water gas conversion process, methanation process, desulfurization and carbon dioxide separation process,
상기 메탄화 공정이 상술한 바와 같은 합성천연가스 합성용 촉매를 포함하여 수행하고,The methanation process is carried out including the catalyst for synthesizing natural gas as described above,
상기 메탄화 공정이 메탄화 반응 및 피셔-트롭쉬 반응(fishcher tropsch process)이 동시에 진행되는, 합성천연가스의 제조방법을 제공한다.The methanation process provides a method for producing a synthetic natural gas, in which a methanation reaction and a Fisher-Tropsch reaction are simultaneously performed.
상기 연료는 탄화수소계열의 원료로, 예를 들면, 석탄이나 저급 연료일 수 있다. 구체적으로, 상기 연료는 석탄, 바이오매스, 폐기물, 중질잔사유 등일 수 있다.The fuel is a hydrocarbon-based raw material, and may be, for example, coal or lower fuel. Specifically, the fuel may be coal, biomass, waste, heavy residue oil, or the like.
상기 메탄화 공정에서 메탄화 반응 및 피셔-트롭쉬 반응이 동시에 진행되면 하기 화학식 1 내지 5와 같은 양론비로 탄화수소와 물이 생성된다. 이와 같은 탄화수소가 생성되면, 물을 제외한 상태에서 메탄화 반응만을 고려할 때, 반응 후 생성물은 부피가 25%로 감소하지만, 피셔-트롭쉬 반응으로 인해 탄소수 2 이상의 탄화수소가 생성되면, 반응 후 생성물은 부피가 14.3%(C2의 탄화수소), 10%(C3의 탄화수소), 7.7%(C4의 탄화수소), 6.3%(C5의 탄화수소) 등으로 감소한다. 따라서, 메탄화 공정에서 메탄화 반응 및 피셔-트롭쉬 반응이 동시에 진행되어 탄소수 2 이상의 탄화수소가 생성되면, 상기 메탄화 공정 이후에 위치한 반응기의 용량을 줄일 수 있다.When the methanation reaction and the Fischer-Tropsch reaction proceeds simultaneously in the methanation process, hydrocarbons and water are produced at a stoichiometric ratio such as the following Chemical Formulas 1 to 5. When such hydrocarbons are produced, considering only the methanation reaction in the absence of water, the product after the reaction is reduced to 25% by volume, but if the hydrocarbon-Tropsch reaction generates hydrocarbons having 2 or more carbon atoms, the product after the reaction The volume is reduced to 14.3% (C 2 hydrocarbon), 10% (C 3 hydrocarbon), 7.7% (C 4 hydrocarbon), 6.3% (C 5 hydrocarbon). Accordingly, when the methanation reaction and the Fischer-Tropsch reaction are simultaneously performed in the methanation process to produce hydrocarbons having 2 or more carbon atoms, the capacity of the reactor located after the methanation process can be reduced.
[화학식 1][Formula 1]
CO + 3H2 → CH4 + H2OCO + 3H 2 → CH 4 + H 2 O
[화학식 2][Formula 2]
2CO + 5H2 → C2H6 + 2H2O2CO + 5H 2 → C 2 H 6 + 2H 2 O
[화학식 3][Formula 3]
3CO + 7H2 → C3H8 + 3H2O3CO + 7H 2 → C 3 H 8 + 3H 2 O
[화학식 4][Formula 4]
4CO + 9H2 → C4H10 + 4H2O4CO + 9H 2 → C 4 H 10 + 4H 2 O
[화학식 5][Formula 5]
5CO + 11H2 → C5H12 + 5H2O5CO + 11H 2 → C 5 H 12 + 5H 2 O
상기 화학식 1 내지 5에서 보는 바와 같이, 메탄화 반응에는 수성가스 전환공정을 통하여 수소(H2)와 일산화탄소(CO)의 몰비가 3.0 : 1인 합성가스를 공급해야 한다. 그러나, 본 발명의 제조방법은 메탄화 반응과 피셔-트롭쉬 반응이 동시에 진행되므로 수소와 일산화탄소의 몰비가 3.0 : 1 보다 낮은 조건에서도 운전이 가능하다. 이로 인해, 본 발명의 제조방법은 수성가스 전환공정에서 이산화탄소로 전환되는 일산화탄소의 양을 줄일 수 있고, 기존의 공정에 비해 탄소(C)의 전환율이 우수하다.As shown in Chemical Formulas 1 to 5, the methanation reaction must be supplied with a synthesis gas having a molar ratio of hydrogen (H 2 ) and carbon monoxide (CO) of 3.0: 1 through a water gas conversion process. However, in the production method of the present invention, since the methanation reaction and the Fischer-Tropsch reaction proceed simultaneously, the molar ratio of hydrogen and carbon monoxide is lower than 3.0: 1, and thus it can be operated. Therefore, the production method of the present invention can reduce the amount of carbon monoxide converted to carbon dioxide in the water gas conversion process, it is excellent in the conversion rate of carbon (C) compared to the existing process.
구체적으로, 상기 메탄화 공정에 공급되는 합성가스는 수소(H2)와 일산화탄소(CO)의 몰비가 2 내지 3 : 1일 수 있다. 보다 구체적으로, 상기 메탄화 공정에 공급되는 합성가스는 수소(H2)와 일산화탄소(CO)의 몰비가 2.5 내지 3 : 1일 수 있다.Specifically, the syngas supplied to the methanation process may have a molar ratio of hydrogen (H 2 ) and carbon monoxide (CO) of 2 to 3: 1. More specifically, the syngas supplied to the methanation process may have a molar ratio of hydrogen (H 2 ) and carbon monoxide (CO) of 2.5 to 3: 1.
상기 메탄화 공정은 250 내지 650 ℃ 및 15 내지 30 kg/㎠의 조건에서 500 내지 20,000 L/kgcathr의 공간속도로 수행될 수 있다. 구체적으로, 상기 메탄화 공정은 250 내지 500 ℃ 및 15 내지 25 kg/㎠의 조건에서 1,000 내지 10,000 L/kgcathr의 공간속도로 수행될 수 있다.The methanation process may be performed at a space velocity of 500 to 20,000 L / kg cat hr under conditions of 250 to 650 ° C. and 15 to 30 kg / cm 2. Specifically, the methanation process may be performed at a space velocity of 1,000 to 10,000 L / kg cat hr under the conditions of 250 to 500 ℃ and 15 to 25 kg / ㎠.
상기 내용을 하기 실시예에 의하여 더욱 상세하게 설명한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 실시예의 범위가 이들만으로 한정되는 것은 아니다.The above content is described in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited thereto.
[[ 실시예Example ]]
제조예Production Example 1. 니켈-코발트-알루미늄/제올라이트 촉매의 제조 1. Preparation of nickel-cobalt-aluminum / zeolite catalysts
ZSM-5 지지체 1.25 g을 400 ㎖의 3차 증류수에 넣고 교반하면서 60℃로 유지시켜 다공성 지지체 용액을 제조하였다. 한편, 니켈 나이트레이트 수화물(Ni(NO3)2·6H2O) 1.053g, 코발트 나이트레이트 수화물(Co(NO3)2·6H2O) 1.839g 및 알루미늄 나이트레이트 수화물(Al(NO3)3·9H2O) 12.514g을 200 ㎖의 3차 증류수에 첨가하여 전구체 혼합물을 제조하였다. 이후, 탄산나트륨(Na2CO3) 6.2862g을 200 ㎖의 3차 증류수에 녹여 침전제 용액을 제조하였다. 상기 다공성 지지체 용액에 상기 전구체 혼합물 및 침전체 용액을 첨가하여 5g의 촉매를 제조하였다.1.25 g of a ZSM-5 support was placed in 400 ml of tertiary distilled water and maintained at 60 ° C. while stirring to prepare a porous support solution. Meanwhile, 1.053 g of nickel nitrate hydrate (Ni (NO 3 ) 2 .6H 2 O), 1.839 g of cobalt nitrate hydrate (Co (NO 3 ) 2 · 6H 2 O) and aluminum nitrate hydrate (Al (NO 3 )). 12.514 g 3 · 9H 2 O) was added to 200 mL of tertiary distilled water to prepare a precursor mixture. Thereafter, 6.2862 g of sodium carbonate (Na 2 CO 3 ) was dissolved in 200 ml of tertiary distilled water to prepare a precipitant solution. 5 g of the catalyst was prepared by adding the precursor mixture and the precipitate solution to the porous support solution.
이후, 제조된 촉매를 60 ℃에서 3시간 동안 교반하여 물을 제거하고, 105 ℃에서 20시간 동안 건조하였다. 이후 건조된 촉매를 400 ℃의 공기 분위기에서 5시간 동안 소성 처리하여 니켈-코발트-알루미늄/제올라이트 촉매를 제조하였다. 이때, 상기 촉매의 조성은 금속기준 5 중량부 Ni-15 중량부 Co-100 중량부 Al2O3/ZSM-5이었다.Thereafter, the prepared catalyst was stirred at 60 ° C. for 3 hours to remove water, and dried at 105 ° C. for 20 hours. Thereafter, the dried catalyst was calcined in an air atmosphere at 400 ° C. for 5 hours to prepare a nickel-cobalt-aluminum / zeolite catalyst. In this case, the composition of the catalyst was 5 parts by weight of Ni-15 parts by weight of Co-100 parts by weight of Al 2 O 3 / ZSM-5.
제조예Production Example 2. 니켈-코발트-루테늄-알루미늄/제올라이트 촉매의 제조 2. Preparation of nickel-cobalt-ruthenium-aluminum / zeolite catalysts
전구체 혼합물로 니켈 나이트레이트 수화물(Ni(NO3)2·6H2O) 3.160g, 코발트 나이트레이트 수화물(Co(NO3)2·6H2O) 0.613g, 알루미늄 나이트레이트 수화물(Al(NO3)3·9H2O) 12.514g, 및 루테늄 나이트레이트 수화물(Ru(NO)(NO3)3) 0.0105g을 200 ㎖의 3차 증류수에 첨가하여 제조하고, 침전제 용액으로 탄산나트륨(Na2CO3) 6.6088g을 첨가하여 제조한 것을 제외하고는, 제조예 1과 동일한 방법으로 촉매를 제조하였다.3.160 g of nickel nitrate hydrate (Ni (NO 3 ) 2 · 6H 2 O) as precursor mixture, 0.613 g of cobalt nitrate hydrate (Co (NO 3 ) 2 · 6H 2 O), aluminum nitrate hydrate (Al (NO 3) ) 3 · 9H 2 O) 12.514g , and ruthenium nitrate hydrate (Ru (NO) (NO 3 ) 3) a prepared by adding to deionized water of 200 ㎖ 0.0105g, and a precipitant solution of sodium carbonate (Na 2 CO 3 A catalyst was prepared in the same manner as in Preparation Example 1, except that 6.6088 g was added thereto.
제조된 촉매는 니켈-코발트-알루미늄/제올라이트 촉매이었고, 상기 촉매의 조성은 금속기준 15 중량부 Ni-5 중량부 Co-0.1 중량부 Ru-100 중량부 Al2O3/ZSM-5이었다.The prepared catalyst was a nickel-cobalt-aluminum / zeolite catalyst, and the composition of the catalyst was 15 parts by weight of Ni-5 parts by weight of Co-0.1 parts by weight of Ru-100 parts by weight of Al 2 O 3 / ZSM-5.
제조예Production Example 3. 니켈-코발트-루테늄-알루미늄 촉매의 제조 3. Preparation of Nickel-Cobalt-Ruthenium-Aluminum Catalyst
니켈 나이트레이트 수화물(Ni(NO3)2·6H2O) 3.160g, 코발트 나이트레이트 수화물(Co(NO3)2·6H2O) 0.613g, 알루미늄 나이트레이트 수화물(Al(NO3)3·9H2O) 12.514g, 및 루테늄 나이트레이트 수화물(Ru(NO)(NO3)3) 0.5229g을 200 ㎖의 3차 증류수에 첨가하여 전구체 혼합물을 제조하였다. 한편, 탄산나트륨(Na2CO3) 6.6088g을 200 ㎖의 3차 증류수에 첨가하여 침전제 용액을 제조하였다. 이후, 400 ㎖의 3차 증류수에 상기 전구체 혼합물 및 상기 침전제 용액을 넣고 교반하면서 60℃로 유지하며 공침하여 5g의 촉매를 제조하였다.Nickel nitrate hydrate (Ni (NO 3 ) 2 · 6H 2 O) 3.160 g, cobalt nitrate hydrate (Co (NO 3 ) 2 · 6H 2 O) 0.613 g, aluminum nitrate hydrate (Al (NO 3 ) 3 A precursor mixture was prepared by adding 12.514 g of 9H 2 O) and 0.5229 g of ruthenium nitrate hydrate (Ru (NO) (NO 3 ) 3 ) to 200 mL of tertiary distilled water. Meanwhile, 6.6088 g of sodium carbonate (Na 2 CO 3 ) was added to 200 ml of tertiary distilled water to prepare a precipitant solution. Thereafter, the precursor mixture and the precipitant solution were added to 400 ml of tertiary distilled water and co-precipitated while maintaining at 60 ° C. while stirring to prepare 5 g of a catalyst.
제조된 촉매는 니켈-코발트-루테늄-알루미늄 촉매이었고, 상기 촉매의 조성은 금속기준 15 중량부 Ni-5 중량부 Co-5 중량부 Ru-100 중량부 Al2O3이었다.The prepared catalyst was a nickel-cobalt-ruthenium-aluminum catalyst, and the composition of the catalyst was 15 parts by weight of Ni-5 parts by weight of Co-5 parts by weight of Ru-100 parts by weight of Al 2 O 3 .
비교예Comparative example 1. 니켈/알루미늄 금속산화물 촉매 1. Nickel / Aluminum Metal Oxide Catalysts
니켈 전구체인 니켈 나이트레이트 수화물(Ni(NO3)2·6H2O) 3.06g을 60 ㎖의 3차 증류수에 녹인 후, 알루미늄 금속산화물 지지체(제조사: 삼전화학, 제품명: 알루미늄 파우더) 3g과 혼합하고 60 ℃에서 6시간 동안 교반하고 감압증류장치를 이용하여 물을 제거하였다. 이후, 105 ℃에서 20시간 동안 건조한 후 500 ℃의 공기 분위기에서 5시간 동안 소성 처리하여 니켈/알루미늄 금속산화물 촉매를 제조하였다. 이때, 상기 촉매의 조성은 금속기준 20 중량부 Ni/Al2O3이었으며, 촉매의 비표면적은 207.9 ㎡/g이었다.3.06 g of nickel nitrate hydrate (Ni (NO 3 ) 2 .6H 2 O), a nickel precursor, was dissolved in 60 ml of tertiary distilled water and mixed with 3 g of an aluminum metal oxide support (manufacturer: Samjeon Chemical, product name: aluminum powder). And stirred at 60 ℃ for 6 hours and water was removed using a vacuum distillation apparatus. Thereafter, the resultant was dried at 105 ° C. for 20 hours and calcined at 500 ° C. for 5 hours to prepare a nickel / aluminum metal oxide catalyst. In this case, the composition of the catalyst was 20 parts by weight of Ni / Al 2 O 3 based on the metal, the specific surface area of the catalyst was 207.9 m 2 / g.
비교예Comparative example 2. 니켈-알루미늄/제올라이트 촉매의 제조 2. Preparation of Nickel-Aluminum / zeolite Catalysts
전구체 혼합물로 니켈 나이트레이트 수화물(Ni(NO3)2·6H2O) 4.213g 및 알루미늄 나이트레이트 수화물(Al(NO3)3·9H2O) 12.514g을 200 ㎖의 3차 증류수에 첨가하여 제조하고, 침전제 용액으로 200 ㎖의 3차 증류수 및 탄산나트륨(Na2CO3) 6.7701g을 혼합하여 제조한 것을 제외하고는, 제조예 1과 동일한 방법으로 촉매를 제조하였다. As a precursor mixture, 4.213 g of nickel nitrate hydrate (Ni (NO 3 ) 2 .6H 2 O) and 12.514 g of aluminum nitrate hydrate (Al (NO 3 ) 3 .9H 2 O) were added to 200 ml of tertiary distilled water. A catalyst was prepared in the same manner as in Preparation Example 1, except that 200 ml of tertiary distilled water and 6.7701 g of sodium carbonate (Na 2 CO 3 ) were mixed with the precipitant solution.
제조된 촉매는 니켈-알루미늄 촉매이었으며, 상기 촉매의 조성은 금속기준 5 중량부 Ni-100 중량부 Al2O3/ZSM-5이었다.The prepared catalyst was a nickel-aluminum catalyst, and the composition of the catalyst was 5 parts by weight of Ni-100 parts by weight of Al 2 O 3 / ZSM-5 based on metal.
비교예Comparative example 3. 니켈-코발트-알루미늄/제올라이트 촉매의 제조 3. Preparation of Nickel-Cobalt-Aluminum / zeolite Catalysts
전구체 혼합물에 루테늄 전구체를 혼합하지 않은 것을 제외하고는, 제조예 2와 동일한 방법으로 촉매를 제조하였으며, 제조된 촉매는 니켈-코발트-알루미늄/제올라이트 촉매를 제조하였다. 이때, 상기 촉매의 조성은 금속기준 15 중량부 Ni-5 중량부 Co-100 중량부 Al2O3/ZSM-5이었다.A catalyst was prepared in the same manner as in Preparation Example 2, except that the ruthenium precursor was not mixed with the precursor mixture, and the prepared catalyst prepared a nickel-cobalt-aluminum / zeolite catalyst. In this case, the composition of the catalyst was 15 parts by weight of Ni-5 parts by weight of Co-100 parts by weight of Al 2 O 3 / ZSM-5.
비교예Comparative example 4. 니켈-코발트-알루미늄/제올라이트 촉매의 제조 4. Preparation of nickel-cobalt-aluminum / zeolite catalysts
전구체 혼합물로 니켈 나이트레이트 수화물(Ni(NO3)2·6H2O) 2.107g, 코발트 나이트레이트 수화물(Co(NO3)2·6H2O) 1.226g 및 알루미늄 나이트레이트 수화물 (Al(NO3)3·9H2O) 12.514g을 200 ㎖의 3차 증류수에 첨가하여 제조하고, 침전제 용액으로 200 ㎖의 3차 증류수 및 탄산나트륨(Na2CO3) 6.4475g을 혼합하여 제조한 것을 제외하고는, 제조예 1과 동일한 방법으로 촉매를 제조하였다.2.107 g of nickel nitrate hydrate (Ni (NO 3 ) 2 · 6H 2 O), 1.226 g of cobalt nitrate hydrate (Co (NO 3 ) 2 · 6H 2 O) and aluminum nitrate hydrate (Al (NO 3) 12.514 g) 3 .9H 2 O) was added to 200 ml of tertiary distilled water, except that 200 ml of tertiary distilled water and 6.4475 g of sodium carbonate (Na 2 CO 3 ) were mixed with a precipitant solution. , The catalyst was prepared in the same manner as in Preparation Example 1.
제조된 촉매는 니켈-코발트-알루미늄/제올라이트 촉매이었고, 상기 촉매의 조성은 금속기준 15 중량부 Ni-5 중량부 Co-100 중량부 Al2O3/ZSM-5이었다.The prepared catalyst was a nickel-cobalt-aluminum / zeolite catalyst, and the composition of the catalyst was 15 parts by weight of Ni-5 parts by weight of Co-100 parts by weight of Al 2 O 3 / ZSM-5.
시험예Test Example 1. One. 메탄화Methanation 공정 fair
메탄화 공정을 시작하기 전에 1/2인치 스테인레스 고정층 반응기에 0.3 g의 제조예 1 내지 3 및 비교예 2 내지 4의 촉매를 장입하였다. 이후, 300 ℃의 수소(8 부피% H2/He) 분위기하에서 4시간 동안 촉매를 환원 처리하였다. 이후, 반응기를 260 ℃, 20 kg/㎠, 및 4,000 L/kgcat·hr의 공간속도으로 4 부피%의 아르곤을 포함하는 일산화탄소와 수소를 포함하는 합성 가스(일산화탄소 : 수소의 몰비= 1 : 3)를 반응기에 주입하여 피셔-트롭쉬 반응과 메탄화 반응을 수행하였다. 상기 반응으로 생성된 생성물의 분석 결과는 촉매의 활성이 안정화되어 유지되는 반응 시작 10시간 후에 2 시간 동안 생성된 생성물의 선택도 및 전환율의 평균값을 계산하여 하기 표 2에 나타냈다.0.3 g of catalysts of Preparation Examples 1-3 and Comparative Examples 2-4 were charged to a 1/2 inch stainless fixed bed reactor before starting the methanation process. Thereafter, the catalyst was reduced for 4 hours under hydrogen (8 vol% H 2 / He) atmosphere at 300 ° C. Subsequently, the reactor was subjected to synthesis gas containing carbon monoxide and hydrogen containing 4% by volume of argon at a space velocity of 260 ° C., 20 kg / cm 2, and 4,000 L / kg cat.hr. ) Was injected into the reactor to carry out the Fischer-Tropsch reaction and the methanation reaction. The analysis result of the product produced by the reaction is shown in Table 2 by calculating the average value of the selectivity and conversion of the product produced for 2 hours after the start of the reaction 10 hours after the activity of the catalyst is maintained stabilized.
반면, 비교예 1의 촉매는 450 ℃의 수소(8 부피% H2/He) 분위기하에서 6시간 동안 환원 처리하고, 350 ℃, 20 kg/㎠, 및 3,000 L/kgcat·hr의 공간속도로 반응을 수행한 것을 제외하고는, 상술한 바와 같이 동일한 방법으로 메탄화 공정을 수행하였으며, 생성물의 선택도 및 전환율의 평균값을 하기 표 2에 나타냈다.On the other hand, the catalyst of Comparative Example 1 was reduced for 6 hours in an atmosphere of hydrogen (8 vol% H 2 / He) at 450 ° C., and at a space velocity of 350 ° C., 20 kg / cm 2, and 3,000 L / kg cat.hr. Except that the reaction was carried out, the methanation process was carried out in the same manner as described above, the average value of the selectivity and conversion of the product is shown in Table 2 below.
(카본몰%)CO conversion rate
(Carbon Mall%)
탄화수소가스C 2 or more
Hydrocarbon gas
표 2에서 보는 바와 같이, 제조예 1 내지 3의 촉매는 메탄 및 C2 이상의 탄화수소가스를 포함하는 생성물이 생성되었다. 본 발명의 촉매는 C2 이상의 탄화수소가스를 포함하는 고발열량의 합성천연가스를 생산함을 확인할 수 있었다.As shown in Table 2, the catalyst of Preparation Examples 1 to 3 produced a product containing methane and C 2 or more hydrocarbon gas. The catalyst of the present invention was confirmed to produce a high calorific value synthetic natural gas containing a hydrocarbon gas of C 2 or more.
반면, 종래 메탄화 반응 촉매인 비교예 1의 촉매는 생성물에 C2 이상의 탄화수소가스가 포함하지 않으며, 코발트의 함량이 낮으면서 루테늄을 포함하지 않는 비교예 2 내지 4의 촉매는 생성물에 C2 이상의 탄화수소가스가 소량 포함되어 발열량이 낮았다. 특히, 비교예 2 및 3의 촉매는 일산화탄소의 전환율이 매우 낮았다.On the other hand, the catalyst of Comparative Example 1, which is a conventional methanation reaction catalyst, does not contain C 2 or more hydrocarbon gas in the product, and the catalysts of Comparative Examples 2 to 4 that do not contain ruthenium with low cobalt content have C 2 or more in the product. The calorific value was low due to the small amount of hydrocarbon gas included. In particular, the catalysts of Comparative Examples 2 and 3 had very low conversion of carbon monoxide.
시험예Test Example 2. 2.
일산화탄소와 수소의 몰비가 4:6, 5:5 또는 6:4로 조절한 합성 가스를 사용한 것을 제외하고는, 메탄화 공정을 수행하면서, 합성천연가스의 발열량을 측정하였으며, 그 결과를 표 3에 나타냈다.Except for using the synthesis gas in which the molar ratio of carbon monoxide and hydrogen was adjusted to 4: 6, 5: 5 or 6: 4, the calorific value of the synthetic natural gas was measured while performing the methanation process. Indicated.
표 3에서 보는 바와 같이, 종래 합성천연가스와 시험예 1의 합성천연가스를 5:5의 부피비로 분기하였을 때, 합성천연가스의 발열량이 10,400 kcal/N㎥로 나타나 발열량이 우수하였다.As shown in Table 3, when the conventional natural gas and the synthetic natural gas of Test Example 1 branched at a volume ratio of 5: 5, the calorific value of the synthetic natural gas was 10,400 kcal / Nm 3, indicating that the calorific value was excellent.
Claims (11)
다공성 지지체로서 제올라이트를 포함하고,
상기 산화알루미늄 100 중량부를 기준으로 11 중량부 이상의 상기 코발트를 포함하는, 합성천연가스 합성용 촉매.
Aluminum oxide, nickel and cobalt; And
Zeolite as a porous support,
A catalyst for synthesizing natural gas comprising 11 parts by weight or more of the cobalt based on 100 parts by weight of the aluminum oxide.
다공성 지지체로서 제올라이트를 포함하고,
상기 산화알루미늄 100 중량부를 기준으로 0.05 내지 7 중량부의 상기 루테늄 및 1 내지 10 중량부의 상기 코발트를 포함하는, 합성천연가스 합성용 촉매.
Aluminum oxide, nickel, cobalt and ruthenium (Ru); And
Zeolite as a porous support,
A catalyst for synthesizing natural gas comprising 0.05 to 7 parts by weight of the ruthenium and 1 to 10 parts by weight of the cobalt based on 100 parts by weight of the aluminum oxide.
상기 촉매가 지르코늄(Zr), 세륨(Ce), 백금(Pt), 로듐(Rh), 팔라듐(Pd) 및 갈륨(Ga)으로 이루어진 군으로부터 선택된 1종 이상의 조촉매를 더 포함하는, 합성천연가스 합성용 촉매.
The method according to claim 1 or 2,
Synthetic natural gas further comprises at least one promoter selected from the group consisting of zirconium (Zr), cerium (Ce), platinum (Pt), rhodium (Rh), palladium (Pd) and gallium (Ga) Catalyst for synthesis.
상기 촉매가 산화알루미늄 100 중량부를 기준으로 12 내지 20 중량부의 코발트를 포함하는, 합성천연가스 합성용 촉매.
The method of claim 1,
The catalyst for synthesizing natural gas comprising 12 to 20 parts by weight of cobalt based on 100 parts by weight of aluminum oxide.
상기 촉매가 산화알루미늄 100 중량부를 기준으로 30 내지 60 중량부의 다공성 지지체를 포함하는, 합성천연가스 합성용 촉매.
The method of claim 1,
Catalyst for synthesizing natural gas, the catalyst comprises 30 to 60 parts by weight of a porous support based on 100 parts by weight of aluminum oxide.
260 ℃ 및 20 kg/㎠의 반응기에 수소(H2)와 일산화탄소(CO)를 3:1의 몰비로 공급하면서 메탄화 반응을 수행했을 때, 상기 촉매의 일산화탄소 전환율이 90 내지 100 %인, 합성천연가스 합성용 촉매.
The method according to claim 1 or 2,
When the methanation reaction was carried out while supplying hydrogen (H 2 ) and carbon monoxide (CO) at a molar ratio of 3: 1 to a reactor at 260 ° C. and 20 kg / cm 2 , the carbon monoxide conversion of the catalyst was 90 to 100%. Catalyst for natural gas synthesis.
상기 메탄화 반응의 생성물이 총 카본몰%를 기준으로 20 내지 40 카본몰%의 탄소수 2 이상의 탄화수소가스를 포함하는, 합성천연가스 합성용 촉매.
The method of claim 8,
The product of the methanation reaction comprises a hydrocarbon gas of 20 to 40 carbon mol% or more carbon atoms of 2 or more based on the total carbon mol%, synthetic natural gas synthesis catalyst.
상기 메탄화 공정이 제1항 또는 제2항의 합성천연가스 합성용 촉매를 포함하여 수행하고,
상기 메탄화 공정이 메탄화 반응 및 피셔-트롭쉬 반응이 동시에 진행되는, 합성천연가스의 제조방법.
In the method for producing a synthetic natural gas through the synthesis gas produced by the gasification of the fuel through a water gas conversion process, methanation process, desulfurization and carbon dioxide separation process,
The methanation process is carried out including the catalyst for synthesizing the natural gas of claim 1 or 2,
The methanation process is a methanation reaction and Fischer-Tropsch reaction proceeds simultaneously, the method for producing a synthetic natural gas.
상기 메탄화 공정에 공급되는 합성가스는 수소(H2)와 일산화탄소(CO)의 몰비가 2 내지 3 : 1인, 합성천연가스의 제조방법.
The method of claim 10,
Synthesis gas supplied to the methanation process has a molar ratio of hydrogen (H 2 ) and carbon monoxide (CO) 2 to 3: 1, the method for producing a synthetic natural gas.
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