KR100989598B1 - 합성가스 제조용 Ni/MgO/Al2O3 촉매 및 그 제조방법 및 합성가스 제조방법 - Google Patents
합성가스 제조용 Ni/MgO/Al2O3 촉매 및 그 제조방법 및 합성가스 제조방법 Download PDFInfo
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- KR100989598B1 KR100989598B1 KR1020080134071A KR20080134071A KR100989598B1 KR 100989598 B1 KR100989598 B1 KR 100989598B1 KR 1020080134071 A KR1020080134071 A KR 1020080134071A KR 20080134071 A KR20080134071 A KR 20080134071A KR 100989598 B1 KR100989598 B1 KR 100989598B1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 129
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 63
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 55
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010304 firing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 8
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical group O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011363 dried mixture Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 23
- 238000003786 synthesis reaction Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000011777 magnesium Substances 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract 6
- 238000002407 reforming Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005038 synthesis gas manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 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
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/16—Reducing
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
Claims (9)
- Al(OH)3, 니켈 전구체 및 마그네시아 전구체(MgO)를 물(H2O)의 첨가없이 혼합하여 건조, 소성시켜 제조된 알루미나(Al2O3)를 담체로 하고, 상기 담체에 담지된 니켈(Ni)과 마그네시아(MgO)로 이루어지는 것을 특징으로 하는 합성가스 제조용 Ni/MgO/Al2O3 촉매.
- 제1항에 있어서,,상기 니켈 전구체는 니켈 수화물인 것을 특징으로 하는 합성가스 제조용 Ni/MgO/Al2O3 촉매.
- 제1항에 있어서,상기 마그네시아(MgO) 전구체는 마그네슘 수화물인 것을 특징으로 하는 합성가스 제조용 Ni/MgO/Al2O3 촉매.
- 제1항 내지 제3항 중 어느 한 항에 있어서,상기 알루미나(Al2O3) 담체는 그 표면적이 50 ~ 200 ㎡/g 인 것을 특징으로 하는 합성가스 제조용 Ni/MgO/Al2O3 촉매.
- Al(OH)3, 니켈 전구체 및 마그네시아(MgO) 전구체를 물(H2O)의 첨가없이 실온에서 30분이상 혼합시키는 혼합 단계와;상기 혼합물을 100 ~ 300 ℃ 의 온도에서 건조시키는 건조 단계와;상기 건조된 혼합물을 600 ~ 1000 ℃의 온도에서 소성시켜 알루미나(Al2O3) 담체에 니켈과 마그네시아를 담지시키는 소성 단계를 포함하여 구성되는 것을 특징으로 하는 합성가스 제조용 Ni/MgO/Al2O3 촉매의 제조방법.
- 제5항에 있어서,상기 니켈 전구체는 니켈 수화물인 것을 특징으로 하는 합성가스 제조용 Ni/MgO/Al2O3 촉매의 제조방법.
- 제5항에 있어서,상기 마그네시아(MgO) 전구체는 마그네슘 수화물인 것을 특징으로 하는 합성가스 제조용 Ni/MgO/Al2O3 촉매의 제조방법.
- 제5항에 있어서,상기 알루미나(Al2O3) 담체는 그 표면적이 50 ~ 200 ㎡/g 인 것을 특징으로 하는 합성가스 제조용 Ni/MgO/Al2O3 촉매의 제조방법.
- 제5항 내지 제8항 중 어느 한 항의 제조방법에 의해 제조된 Ni/MgO/Al2O3 촉매를 수소분위기하에 700 ℃ 이상에서 환원시키는 단계와, 공간속도가 100 ~ 500,000 hr-1이고, 반응온도가 500 ~ 1000 ℃의 조건으로 반응기에서 반응시키는 단계로 구성되는 것을 특징으로 하는 합성가스 제조방법.
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