KR20210053359A - Hollow fiber type LSCF oxygen removing catalyst coated with Pd, preparation method thereof, and method for removing oxygen in methane mixture gas by using the same - Google Patents
Hollow fiber type LSCF oxygen removing catalyst coated with Pd, preparation method thereof, and method for removing oxygen in methane mixture gas by using the same Download PDFInfo
- Publication number
- KR20210053359A KR20210053359A KR1020190136487A KR20190136487A KR20210053359A KR 20210053359 A KR20210053359 A KR 20210053359A KR 1020190136487 A KR1020190136487 A KR 1020190136487A KR 20190136487 A KR20190136487 A KR 20190136487A KR 20210053359 A KR20210053359 A KR 20210053359A
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- hollow fiber
- oxygen
- lscf
- coated
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 185
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 129
- 239000001301 oxygen Substances 0.000 title claims abstract description 124
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 123
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000007789 gas Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 192
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims description 72
- 239000011248 coating agent Substances 0.000 claims description 69
- 239000008188 pellet Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 238000007772 electroless plating Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 28
- 230000003647 oxidation Effects 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000000977 initiatory effect Effects 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 12
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000004697 Polyetherimide Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920001601 polyetherimide Polymers 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000000701 coagulant Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 206010000372 Accident at work Diseases 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000008570 general process Effects 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- -1 siloxanes Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229930188023 Magnone Natural products 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910018967 Pt—Rh Inorganic materials 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/06—
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/14841—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
- C07C7/1485—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds oxides; hydroxides; salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
- C07C9/04—Methane
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
- B01J2523/24—Strontium
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/37—Lanthanides
- B01J2523/3706—Lanthanum
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/845—Cobalt
-
- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
Abstract
Description
본 발명은 페롭스카이트 산소 제거 촉매제에 관한 것으로, 더욱 상세하게는 특정 농도의 팔라듐(Pd)로 코팅된 중공사형 LSCF 산소 제거 촉매제, 이의 제조방법 및 이를 이용한 메탄 혼합 가스의 산소 제거 방법에 관한 것이다.The present invention relates to a perovskite oxygen removal catalyst, and more particularly, to a hollow fiber LSCF oxygen removal catalyst coated with a specific concentration of palladium (Pd), a method for preparing the same, and a method for removing oxygen from a methane mixed gas using the same .
Municipal Solid Wastes (MSW) 에서 배출되는 매립지 가스(LFG)에는 온실가스(GHG) 배출량에 가장 중요한 원인 중 하나일 뿐만 아니라 재생 에너지원으로서 가치가 큰 메탄(CH4,45%-55%)이 포함되어 있다. 매립지 가스 내에는 이산화탄소(CO2, 35%-50%), 질소(N2, 0-20%), 산소(O2, 0-2%), 황화수소(H2S, 0. 005-2%), 기타 미량 화합물(실록산류(siloxanes), <0.02%)이 존재한다. Landfill gas (LFG) emitted from Municipal Solid Wastes (MSW) contains methane (CH 4 ,45%-55%), which is not only one of the most important sources of greenhouse gas (GHG) emissions, but also a valuable source of renewable energy. Has been. In the landfill gas, carbon dioxide (CO 2 , 35%-50%), nitrogen (N 2 , 0-20%), oxygen (O 2 , 0-2%), hydrogen sulfide (H 2 S, 0. 005-2%) ), and other trace compounds (siloxanes, <0.02%) are present.
최근 세계 각 국에서 기후변화 방지에 초점을 맞춰 매립지 가스의 활용은 광범위해졌으며, 다양한 연구가 수행 중에 있다. 매립지 가스를 자원으로 활용하기 위해 메탄의 순도를 높이기 위한 전처리 기술 개발이 필요하다. 특히, 산소는 파이프 관 부식, 폭발성의 위험 등의 이유 때문에 제거해야 한다. 하지만 매립지 가스 조성에서 산소의 농도가 낮기 때문에 귀금속 촉매를 사용하여 메탄의 완전 산화 반응을 유도하기는 매우 힘들다. Recently, the use of landfill gas has been extensively focused on the prevention of climate change in countries around the world, and various studies are being conducted. In order to utilize the landfill gas as a resource, it is necessary to develop a pretreatment technology to increase the purity of methane. In particular, oxygen must be removed for reasons such as corrosion of pipes, danger of explosion, etc. However, since the concentration of oxygen in the gas composition of the landfill is low, it is very difficult to induce a complete oxidation reaction of methane using a noble metal catalyst.
최근 LFG로부터 이산화탄소, 질소, 황화수소, 및 실록산 제거 연구가 많이 진행되고 있으나, LFG를 도시가스 관망에 연결하기 위한 수준까지 업그레이드 연구는 진행되지 않고 있다. 또한 한국 도시 가스 사업법 제26조(UGBA)에 따르면, 허용할 수 있는 산소의 상한선은 <0.03 mol%이기 때문에, 바이오 가스로부터 산소를 제거하는 기술은 도시가스 관망에 연결하는 가스의 고품질화를 위해 꼭 개발해야하는 기술이다.Recently, a lot of researches on removing carbon dioxide, nitrogen, hydrogen sulfide, and siloxane from LFG have been conducted, but research on upgrading to the level to connect LFG to the city gas pipe network has not been conducted. In addition, according to Article 26 (UGBA) of the Korean Urban Gas Business Act, the upper limit of allowable oxygen is <0.03 mol%, so the technology to remove oxygen from biogas is essential for the high quality of the gas connected to the city gas pipe network. It's a skill that needs to be developed.
산소를 제거할 수 있는 방법으로는 흡착, 흡수, 분리막, 촉매 반응 등이 있다. LFG 내의 산소는 미량이기 때문에 농도차를 구동력으로 하는 다른 분리방법에 비해 완전 산화 촉매 반응이 유리하다. 매립지 가스 내에는 산소의 농도가 낮기 때문에 일반적으로는 불완전 연소가 일어나지만, 촉매를 이용할 경우 완전 연소 반응을 시킬 수 있다. Methods that can remove oxygen include adsorption, absorption, separation membranes, and catalytic reactions. Since oxygen in LFG is in a very small amount, a complete oxidation catalytic reaction is more advantageous than other separation methods using the difference in concentration as a driving force. In general, incomplete combustion occurs because the concentration of oxygen in the landfill gas is low, but when a catalyst is used, a complete combustion reaction can be performed.
페롭스카이트는 미량의 산소 조건하에서 완전 연소가 가능한 촉매로 연구 된 바 있다[Marchetti, L. and Forni, L., Applied Catalysis B: Env., 15, 179-187 (1998)]. 페롭스카이트 금속 산화물은 ABO3의 구조를 갖는 세라믹인데, 이때, A는 주로 란타나이드 계열의 알칼리 토금속, B는 전이금속을 나타낸다. 페롭스카이트 내 A, B 양이온은 일반적으로 +3가의 전하를 띄고 -2가의 산소 음이온 3개와 결합하여 결과적으로 페롭스카이트 물질은 전기적으로 중성을 띈다. ABO3의 구조를 갖는 페롭스카이트에 도핑을 하면 다른 전하를 갖는 원자들이 부분적으로 치환하게 되면서 전이금속의 산화수가 변하게 되고 이에 따라 산소가 이탈하여 산소 빈자리(oxygen vacancy) 생성이 가능하다. 따라서 산소 빈자리를 통해 산소가 이동하거나 흡착될 수 있다. 이러한 특징뿐만 아니라 구조적, 열적으로 안정성을 지니고 있기 때문에 페롭스카이트 금속 산화물은 분리막 뿐만 아니라 산화 촉매로 사용될 수 있다.Perovskite has been studied as a catalyst capable of complete combustion under a trace amount of oxygen [Marchetti, L. and Forni, L., Applied Catalysis B: Env., 15, 179-187 (1998)]. The perovskite metal oxide is a ceramic having a structure of ABO 3 , in which A is mainly an alkaline earth metal of lanthanide series, and B is a transition metal. The A and B cations in the perovskite generally have a positive charge and are combined with three -divalent oxygen anions, and as a result, the perovskite material is electrically neutral. When doping the perovskite having the structure of ABO 3 , atoms with different charges are partially substituted, and the oxidation number of the transition metal is changed, and thus oxygen is released and oxygen vacancy can be generated. Thus, oxygen may move or be adsorbed through the oxygen vacancies. Because of these characteristics as well as structural and thermal stability, perovskite metal oxide can be used not only as a separator but also as an oxidation catalyst.
상기 페롭스카이트와 관련된 종래 기술로서, 본 발명자는 대한민국 특허등록 제10-1869461호를 통하여 La1 - xSrxCo1 - yFeyO3 -δ(이하 LSCF)를 포함하는 분말형 페롭스카이트 촉매제를 제시한 바가 있다. 그러나, 분말형태의 촉매는 실험실 규모로 적은 양을 사용할 시, 촉매 특성을 파악할 순 있으나, 많은 양을 사용할 시 압력강하가 증가하여 반응속도는 저하되기 때문에 실제 공정시스템에 적용하기가 쉽지 않다. As a prior art related to the perovskite, the inventors of the present invention disclosed a powdered perovskite containing La 1 - x Sr x Co 1 - y Fe y O 3 -δ (hereinafter, LSCF) through Korean Patent Registration No. 10-1869461. There has been a suggestion of a catalyst catalyst. However, when using a small amount of a catalyst in a laboratory scale, the characteristics of the catalyst can be grasped, but when a large amount is used, the pressure drop increases and the reaction rate decreases, so it is not easy to apply it to an actual process system.
따라서 실제 공정시스템에 적용하기 위하여는 압력강하를 최소화하기 위한 촉매 형태가 중요하고, 완전 산화 온도는 500℃ 이하, 바람직하게는 450℃인 것이 요구되고 있다. 왜냐하면 완전 산화 온도가 500℃를 초과하면 촉매의 2차 소결이 발생하여 산소를 흡착하는 기공이 줄어들어 촉매 활성이 저하되기 때문이다.Therefore, in order to be applied to an actual process system, a catalyst type for minimizing the pressure drop is important, and the complete oxidation temperature is required to be 500°C or less, preferably 450°C. This is because when the complete oxidation temperature exceeds 500°C, secondary sintering of the catalyst occurs, and the pores adsorbing oxygen are reduced, thereby reducing the catalytic activity.
이에, 본 발명자는 실제 공정시스템에 적용하기 위하여, LSCF 촉매를 분말형태가 아닌 중공사막 형태로 성형하였다[Korean Chem. Eng. Res., 56(3), 297-302 (2018)]. 중공사막은 가운데 구멍이 있는 얇은 관 형태의 분리막이다. 특히, 중공사막은 한 번의 프로세스를 통해 비대칭형의 기공을 형성할 수 있는 장점이 있다. 또한 외부 기공과 내부 기공이 동시에 존재하므로 비표면적은 상대적으로 넓다. 따라서 이를 촉매 성형에 적용하여 비표면적을 증가시키고 압력강하를 최소화할 수 있다.Accordingly, the present inventors molded the LSCF catalyst in the form of a hollow fiber membrane rather than a powder form in order to apply it to an actual process system [Korean Chem. Eng. Res., 56(3), 297-302 (2018)]. The hollow fiber membrane is a membrane in the form of a thin tube with a hole in the middle. In particular, the hollow fiber membrane has the advantage of being able to form asymmetric pores through a single process. In addition, since external pores and internal pores exist at the same time, the specific surface area is relatively large. Therefore, it is possible to increase the specific surface area and minimize the pressure drop by applying this to catalyst molding.
상기 LSCF 촉매 중, La0 . 1Sr0 . 9Co0 . 2Fe0 . 8O3 -δ (LSCF-1928) 촉매는 산소 흡착량 측정을 위한 온도 프로그래밍 환원(Temperature Programmed Reduction, TPR) 분석시, 도 1에 나타낸 바와 같이, 촉매 표면에 흡착 된 산소량을 나타내는 것으로 보이는 첫 번째 피크 α는 260 ℃에서 나타났으며, 촉매 격자 내 산소 공공(oxygen vacancy)에서 탈착된 산소량을 나타내는 두 번째 피크 β는 480 ℃에서 나타남으로써, 완전 산화 온도가 500 ℃ 이하로, 공정시스템에 적합한 특성을 나타내었다.In the LSCF catalyst, La 0 . 1 Sr 0 . 9 Co 0 . 2 Fe 0 . 8 O 3 -δ (LSCF-1928) catalyst is the first to show the amount of oxygen adsorbed on the catalyst surface as shown in FIG. 1 when temperature programmed reduction (TPR) analysis for measuring the amount of oxygen adsorption is measured. Peak α appeared at 260°C, and the second peak β, indicating the amount of oxygen desorbed from oxygen vacancy in the catalyst lattice, appeared at 480°C. The complete oxidation temperature was 500°C or less, which is suitable for the process system. Shown.
그러나, 실제로 산소를 포함한 바이오가스 노출 전, 후 중공사형 LSCF-1928 촉매의 XRD 결과를 참고하면, 도 2에 나타낸 바와 같이, 바이오가스 노출 전에는 페로브스카이트의 XRD 피크와 일치함으로써 페로브스카이트 구조를 유지하였으나, 바이오가스 노출 후에는 페로브스카이트 피크 외에, 바이오가스 내의 CO2와 LSCF-1928 촉매의 Sr이 반응하여 SrCO3의 부산물 피크가 함께 나타남을 확인하였다. 이렇게 부산물로 생성된 SrCO3은 LSCF-1928 촉매의 기공을 막아 시간이 지날수록 LSCF-1928 촉매의 성능을 저하시키는 문제가 있다.However, referring to the XRD results of the hollow fiber LSCF-1928 catalyst before and after the biogas exposure including oxygen, as shown in FIG. 2, the XRD peak of the perovskite before the biogas exposure coincides with the perovskite. The structure was maintained, but after exposure to the biogas, it was confirmed that in addition to the perovskite peak, CO 2 in the biogas and Sr of the LSCF-1928 catalyst reacted, and a by-product peak of SrCO 3 appeared together. SrCO 3 produced as a by-product has a problem of deteriorating the performance of the LSCF-1928 catalyst as time passes by clogging the pores of the LSCF-1928 catalyst.
따라서, 이러한 LSCF 촉매의 성능 저하를 개선할 수 있는 새로운 방법이 필요한 실정이다.Therefore, there is a need for a new method capable of improving the performance degradation of the LSCF catalyst.
본 발명의 제1 목적은 LSCF 촉매의 성능이 개선된 산소 제거 촉매제를 제공하는 것이다.A first object of the present invention is to provide an oxygen removal catalyst with improved performance of an LSCF catalyst.
본 발명의 제2 목적은 상기 산소 제거 촉매제의 제조방법을 제공하는 것이다.A second object of the present invention is to provide a method for preparing the oxygen removal catalyst.
상기 제1 목적을 달성하기 위하여, 본 발명은 중공사형 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2) 펠렛; 및 상기 중공사형 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2) 펠렛의 표면상에 5.1 wt% 내지 22.5 wt%의 농도로 코팅된 팔라듐(Pd) 나노입자를 포함하는 산소 제거 촉매제를 제공한다.In order to achieve the above first object, the present invention is hollow fiber La (1-x) Sr x Co y Fe 1 - y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2 ) Pellets; And the hollow fiber type La (1-x) Sr x Co y Fe 1 - y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) 5.1 wt% to the surface of the pellets It provides an oxygen removal catalyst comprising palladium (Pd) nanoparticles coated at a concentration of 22.5 wt%.
더욱 바람직하게는, 상기 팔라듐(Pd) 나노입자는 중공사형 La(1-x)SrxCoyFe1 -yO3-δ (0<x<1, 0<y<1, 0≤δ<2) 펠렛의 표면상에 코팅되어, 100% 산소 제거 전화율이 나타나는 온도를 낮출 수 있다.More preferably, the palladium (Pd) nanoparticles are hollow fiber La( 1-x )Sr x Co y Fe 1 -y O 3-δ (0<x<1, 0<y<1, 0≤δ< 2) It is coated on the surface of the pellet, so that the temperature at which 100% oxygen removal conversion rate appears can be lowered.
더욱 바람직하게는, 상기 La(1-x)SrxCoyFe1 - yO3 -δ에서 x=0.9이고, y=0.2 이며, 0≤δ<2일 수 있다.More preferably, the La (1-x) Sr x Co y Fe 1 - x = 0.9 and y O 3 in -δ, and y = 0.2, it may be 0≤δ <2.
더욱 바람직하게는, 상기 La(1-x)SrxCoyFe1 - yO3 -δ에서 x=0.2이고, y=0.2이며, 0≤δ<2일 수 있다.More preferably, the La (1-x) Sr x Co y Fe 1 - x = 0.2 and y O 3 in -δ, and y = 0.2, it may be 0≤δ <2.
또한, 상기 제2 목적을 달성하기 위하여, 본 발명은 중공사형 La(1-x)SrxCoyFe1 -yO3-δ (0<x<1, 0<y<1, 0≤δ<2) 조성을 가진 펠렛을 제조하는 단계; 및 상기 펠렛 제조 단계에서 제조된 중공사형 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1) 조성을 가진 펠렛의 표면에 팔라듐(Pd) 나노입자를 5.1 wt% 내지 22.5 wt%의 농도로 코팅하는 단계를 포함하는 산소 제거 촉매제의 제조방법을 제공한다.In addition, in order to achieve the second object, the present invention is a hollow fiber type La( 1-x )Sr x Co y Fe 1 -y O 3-δ (0<x<1, 0<y<1, 0≤δ <2) preparing a pellet having a composition; And the pellet a hollow threaded La (1-x) prepared in step Sr x Co y Fe 1 - y O 3 -δ (0 <x <1, 0 <y <1) palladium on the surface of the pellet having a composition (Pd ) It provides a method for producing an oxygen removal catalyst comprising the step of coating the nanoparticles at a concentration of 5.1 wt% to 22.5 wt%.
더욱 바람직하게는, 상기 팔라듐(Pd) 나노입자를 코팅하는 단계는 무전해도금법을 사용할 수 있다.More preferably, the step of coating the palladium (Pd) nanoparticles may use an electroless plating method.
더욱 바람직하게는, 상기 La(1-x)SrxCoyFe1 - yO3 -δ에서 x=0.9이고, y=0.2 이며, 0≤δ<2일 수 있다.More preferably, the La (1-x) Sr x Co y Fe 1 - x = 0.9 and y O 3 in -δ, and y = 0.2, it may be 0≤δ <2.
더욱 바람직하게는, 상기 La(1-x)SrxCoyFe1 - yO3 -δ에서 x=0.2이고, y=0.2 이며, 0≤δ<2일 수 있다.More preferably, the La (1-x) Sr x Co y Fe 1 - x = 0.2 and y O 3 in -δ, and y = 0.2, it may be 0≤δ <2.
또한, 상기 제3 목적을 달성하기 위하여, 본 발명은 중공사형 La(1- x)SrxCoyFe1-yO3-δ (0<x<1, 0<y<1, 0≤δ<2) 펠렛; 및 상기 중공사형 La(1-x)SrxCoyFe1 -yO3-δ (0<x<1, 0<y<1, 0≤δ<2) 펠렛의 표면상에 5.1 wt% 내지 22.5 wt%의 농도로 코팅된 팔라듐(Pd) 나노입자를 포함하는 산소 제거 촉매제를 반응조 내에 제공하는 단계; 상기 반응조를 가열하는 단계; 및 상기 반응조가 가열된 상태에서, 상기 반응조 내로 메탄 혼합가스를 유입시키면, 상기 메탄 혼합가스의 메탄이 상기 촉매제에 의하여 완전 연소됨에 따라 상기 메탄 혼합 가스 내의 산소가 제거되는 단계를 포함하는, 산소 제거 촉매제를 이용한 메탄 혼합 가스의 산소 제거 방법을 제공한다.In addition, in order to achieve the third object, the present invention is a hollow fiber type La( 1- x )Sr x Co y Fe 1-y O 3-δ (0<x<1, 0<y<1, 0≤δ <2) pellets; And 5.1 wt% on the surface of the hollow fiber La( 1-x )Sr x Co y Fe 1 -y O 3-δ (0<x<1, 0<y<1, 0≤δ<2) pellet Providing an oxygen removal catalyst including palladium (Pd) nanoparticles coated at a concentration of 22.5 wt% in a reaction tank; Heating the reaction tank; And when the methane mixed gas is introduced into the reaction tank while the reaction tank is heated, oxygen in the methane mixed gas is removed as the methane of the methane mixed gas is completely burned by the catalyst. It provides a method for removing oxygen from a methane mixed gas using a catalyst.
더욱 바람직하게는, 상기 반응조를 가열하는 단계는 300~450℃로 가열하는 단계를 포함할 수 있다.More preferably, heating the reaction tank may include heating to 300 to 450°C.
본 발명에 따른 팔라듐(Pd) 나노입자로 코팅된 중공사형 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2)(LSCF) 촉매는 특정 농도의 팔라듐이 코팅되어, 종래 팔라듐 코팅되지 않은 일반 LSCF 촉매와 비교시 현저히 촉매 성능 개시 온도 및 메탄 완전 산화 온도(100% 산소 제거 전화율을 나타내는 온도)를 50 ℃이상 현저하게 낮추어, 공정 조건에 부합되는 약 350~400℃의 온도에서 100% 산소 제거 전화율을 나타내고, 장시간 경과 후에도 촉매 성능이 유지됨으로써, 높은 안정성과 향상된 촉매 성능을 나타내므로, 기존 촉매를 대체하여 산소 제거 촉매제로 유용하게 사용될 수 있다. 이에 따라, 매립지 가스와 같은 미량의 산소를 포함하는 메탄 혼합가스에서 산소만을 빠르게 제거하여 매립 가스 정제 장치의 동작 시 산소로 인한 산업 재해의 위험성을 낮출 수 있다.Palladium (Pd), a hollow fiber type La (1-x) nanoparticles coated with Sr x Co y Fe 1 according to the invention - y O 3 -δ (0 < x <1, 0 <y <1, 0≤δ < 2) The (LSCF) catalyst is coated with a specific concentration of palladium, and compared with the conventional LSCF catalyst without palladium coating, the catalyst performance initiation temperature and the complete oxidation temperature of methane (the temperature representing 100% oxygen removal conversion rate) are significantly higher than 50 ℃. Remarkably lowered, it shows 100% oxygen removal conversion rate at a temperature of about 350 to 400℃ that meets the process conditions, and the catalytic performance is maintained even after a long period of time, resulting in high stability and improved catalytic performance. It can be usefully used as a catalyst for removal. Accordingly, it is possible to reduce the risk of industrial accidents caused by oxygen when the landfill gas purification apparatus is operated by rapidly removing only oxygen from the methane mixed gas containing a trace amount of oxygen, such as a landfill gas.
다만, 본 발명의 효과들은 이상에서 언급한 효과로 제한되지 않으며, 언급되지 않은 또 다른 효과들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.
도 1은 종래 중공사형 LSCF-1928 촉매의 온도에 따른 환원특성(Temperature programmed reduction, TPR) 분석 결과이다.
도 2는 종래 중공사형 LSCF-1928 촉매의 바이오가스 노출 전 후의 XRD 그래프를 나타낸다.
도 3은 본 발명의 일 실시예에 따른 중공사형 LSCF 촉매의 제조과정을 나타내는 개략도이다.
도 4는 본 발명의 일 실시예에 따른 무전해도금법에 따라 중공사형 LSCF 촉매 상에 Pd를 코팅하는 과정을 나타내는 모식도이다.
도 5는 본 발명의 일 비교예에 따라 제조된, Pd 코팅이 없는 중공사형 LSCF-1928 촉매의 (a) 횡단면 사진, (b) 횡단면의 확대도, (c) 표면 이미지, 및 (d) 표면 이미지의 확대도이다.
도 6은 본 발명의 제조예 1에 따라 제조된, Pd 코팅된(Pd의 표면 코팅농도 5.1wt%) 중공사형 LSCF-1928 촉매의 (a) 횡단면 사진, (b) 횡단면의 확대도, (c) 표면 이미지, 및 (d) 표면 이미지의 확대도이다.
도 7은 본 발명의 제조예 2에 따라 제조된, Pd 코팅된(Pd의 표면 코팅농도 15.8wt%) 중공사형 LSCF-1928 촉매의 (a) 횡단면 사진, (b) 횡단면의 확대도, (c) 표면 이미지, 및 (d) 표면 이미지의 확대도이다.
도 8은 본 발명의 제조예 3에 따라 제조된, Pd 코팅된(Pd의 표면 코팅농도 20.3wt%) 중공사형 LSCF-1928 촉매의 (a) 횡단면 사진, (b) 횡단면의 확대도, (c) 표면 이미지, 및 (d) 표면 이미지의 확대도이다.
도 9는 본 발명의 제조예 5에 따라 제조된, Pd로 코팅된 중공사형 LSCF-8228 촉매의 (a) 전체 사진, (b) 단면의 SEM 이미지(35x), (c) 단면의 SEM 이미지(200x), (d)SEM 현미경으로 본 상부 이미지(1000x), 및 (e) Pd 입자의 EDS 맵핑 사진을 나타낸다.
도 10은 본 발명의 일 실험예에 따른 중공사형 LSCF 촉매를 이용한 메탄 완전 산화 실험의 개략도이다.
도 11은 본 발명의 일 실험예에 따른, Pd 코팅된 중공사형 LSCF-1928 촉매의 Pd의 표면 코팅농도에 따른 메탄 완전 산화 실험 결과를 나타내는 그래프이다.
도 12는 본 발명의 일 실험예에 따른, Pd 코팅이 없는 중공사형 LSCF-8228 촉매의 일반 모사 매립지 가스 환경과 고농도 황화수소(20 ppm)의 극한 환경에서의 산소 제거 전화율을 나타내는 그래프이다.
도 13은 본 발명의 일 실험예에 따른, Pd 코팅된 중공사형 LSCF-8228 촉매의 일반 모사 매립지 가스 환경과 고농도 황화수소(20 ppm)의 극한 환경에서의 산소 제거 전화율을 나타내는 그래프이다.
도 14는 본 발명의 일 실험예에 따른, Pd 코팅 유무에 따른 중공사형 LSCF-8228 촉매의 시간에 따른 산소 제거 전화율의 변화를 나타내는 그래프이다.1 is a temperature-dependent reduction characteristic (Temperature programmed reduction, TPR) analysis result of a conventional hollow fiber LSCF-1928 catalyst.
2 shows an XRD graph of a conventional hollow fiber LSCF-1928 catalyst before and after exposure to biogas.
3 is a schematic diagram showing a manufacturing process of a hollow fiber type LSCF catalyst according to an embodiment of the present invention.
4 is a schematic diagram showing a process of coating Pd on a hollow fiber LSCF catalyst according to an electroless plating method according to an embodiment of the present invention.
5 is a (a) cross-sectional photograph of a hollow fiber LSCF-1928 catalyst without a Pd coating, (b) an enlarged view of the cross-section, (c) a surface image, and (d) a surface of a hollow fiber-type LSCF-1928 catalyst prepared according to a comparative example of the present invention. This is an enlarged view of the image.
6 is a Pd-coated (Pd surface coating concentration of 5.1wt%) hollow fiber LSCF-1928 catalyst prepared according to Preparation Example 1 of the present invention (a) a cross-sectional photograph, (b) an enlarged view of the cross-section, (c) ) A surface image, and (d) an enlarged view of the surface image.
7 is a Pd-coated (Pd surface coating concentration of 15.8 wt%) hollow fiber LSCF-1928 catalyst prepared according to Preparation Example 2 of the present invention (a) a cross-sectional photograph, (b) an enlarged view of the cross-section, (c ) A surface image, and (d) an enlarged view of the surface image.
8 is a Pd-coated (Pd surface coating concentration of 20.3 wt%) hollow fiber LSCF-1928 catalyst prepared according to Preparation Example 3 of the present invention (a) a cross-sectional photograph, (b) an enlarged view of the cross-section, (c ) A surface image, and (d) an enlarged view of the surface image.
9 is a (a) overall photograph, (b) a cross-sectional SEM image (35x), (c) a cross-sectional SEM image of the hollow fiber LSCF-8228 catalyst coated with Pd prepared according to Preparation Example 5 of the present invention ( 200x), (d) an upper image (1000x) seen under a SEM microscope, and (e) an EDS mapping picture of Pd particles.
10 is a schematic diagram of an experiment for complete oxidation of methane using a hollow fiber LSCF catalyst according to an experimental example of the present invention.
11 is a graph showing the results of a complete methane oxidation experiment according to the surface coating concentration of Pd of the Pd-coated hollow fiber LSCF-1928 catalyst according to an experimental example of the present invention.
12 is a graph showing the oxygen removal conversion rate in an extreme environment of a general simulated landfill gas environment and a high concentration hydrogen sulfide (20 ppm) of a hollow fiber LSCF-8228 catalyst without a Pd coating according to an experimental example of the present invention.
13 is a graph showing the oxygen removal conversion rate in an extreme environment of a general simulated landfill gas environment and a high concentration hydrogen sulfide (20 ppm) of a Pd-coated hollow fiber LSCF-8228 catalyst according to an experimental example of the present invention.
14 is a graph showing a change in oxygen removal conversion rate over time of a hollow fiber LSCF-8228 catalyst with or without Pd coating according to an experimental example of the present invention.
본 발명이 여러 가지 수정 및 변형을 허용하면서도, 그 특정 실시예들이 도면들로 예시되어 나타내어지며, 이하에서 상세히 설명될 것이다. 그러나 본 발명을 개시된 특별한 형태로 한정하려는 의도는 아니며, 오히려 본 발명은 청구항들에 의해 정의된 본 발명의 사상과 합치되는 모든 수정, 균등 및 대용을 포함한다.While the present invention allows various modifications and variations, specific embodiments thereof are illustrated and shown in the drawings, and will be described in detail below. However, it is not intended to limit the present invention to the particular form disclosed, but rather the present invention includes all modifications, equivalents, and substitutions consistent with the spirit of the present invention as defined by the claims.
층, 영역 또는 기판과 같은 요소가 다른 구성 요소 "상(on)"에 존재하는 것으로 언급될 때, 이것은 직접적으로 다른 요소 상에 존재하거나 또는 그 사이에 중간 요소가 존재할 수도 있다는 것을 이해할 수 있을 것이다.When an element such as a layer, region or substrate is referred to as being “on” another component, it will be understood that it may exist directly on the other element or there may be intermediate elements between them. .
[Pd 코팅된 중공사형 [Pd coated hollow fiber type LSCFLSCF 촉매제] Catalyst]
본 발명은 LSCF 조성의 산소 제거 촉매제를 제공한다.The present invention provides an oxygen removal catalyst of LSCF composition.
본 발명자들은 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2)(LSCF) 조성의 종래의 촉매가 바이오가스 노출시 SrCO3 부산물을 생성하여, 촉매 활성이 저하되는 문제를 해결하고, 촉매 성능 및 안정성을 향상시키고자 예의 연구한 결과, 상기 LSCF 조성의 촉매를 중공사형의 펠렛으로 제조하고, 그 표면을 특정 함량의 팔라듐(Pd) 나노입자로 코팅한 결과, 산소 흡착 성능이 현저히 향상되어 100% 산소 제거 전화율을 나타내는 온도가 현저히 낮아지고, 장시간 운전시에도 촉매 성능이 유지되어 높은 안정성을 나타냄을 발견하였다.The present inventors have found that La (1-x) Sr x Co y Fe 1 - y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) (LSCF) is a conventional catalyst of the following composition Bio When exposed to gas, SrCO3 by-product is generated, thereby solving the problem of deteriorating catalyst activity, and as a result of intensive research to improve catalyst performance and stability, the LSCF composition catalyst was prepared into hollow fiber pellets, and the surface was specified. As a result of coating with an amount of palladium (Pd) nanoparticles, it was found that the oxygen adsorption performance was remarkably improved, the temperature indicating 100% oxygen removal conversion rate was significantly lowered, and the catalytic performance was maintained even during long-time operation, indicating high stability.
구체적으로, 본 발명자들은 종래 LSCF 촉매의 성분 중 Sr이 CO2와 반응하여 부산물인 SrCO3를 생성하고, 상기 SrCO3는 산소 흡착 사이트를 막아 촉매 성능을 저하시키므로, 상기 SrCO3의 생성을 방지하기 위한 코팅물질 중, CO2와 반응성이 없고, 촉매 활성을 높여줄 수 있는 물질로서 팔라듐(Pd)을 발견하였다. 이에, Pd의 표면 코팅농도를 다양하게 변화시키면서 다수의 반복실험을 통하여 Pd 코팅 전/후의 중공사형 LSCF 촉매에 대한 메탄 완전 산화 실험을 수행하였으며, 이 중 의미있는 데이터만을 선별하여 도 11에 나타내었다.Specifically, the inventors of the present invention to prevent the generation of SrCO 3 because Sr among the components of the conventional LSCF catalyst reacts with CO 2 to generate SrCO 3 as a by-product, and the SrCO 3 blocks the oxygen adsorption site to reduce catalyst performance. Among the coating materials for, we discovered palladium (Pd) as a material that is not reactive with CO 2 and can increase catalytic activity. Accordingly, a complete methane oxidation experiment was performed on the hollow fiber LSCF catalyst before/after Pd coating through a number of repeated experiments while varying the surface coating concentration of Pd, and only meaningful data among them were selected and shown in FIG. .
도 11에 나타낸 바와 같이, Pd 코팅 전의 중공사형 LSCF 촉매는 100% 산소 제거 전화율을 나타내는 완전 산화 온도가 475 ℃었으나, Pd 코팅 후 중공사형 LSCF 촉매의 완전 산화 온도는 낮아짐으로써, Pd 코팅 후 중공사형 LSCF 촉매의 성능이 향상된 것을 확인하였다. 이는 표면의 Pd 코팅 층으로부터 전달된 산소가 LSCF 산소 빈자리 및 표면에 흡착되고 이후 메탄과 반응하여 완전 산화되는 것으로 사료된다.As shown in FIG. 11, the hollow fiber LSCF catalyst before Pd coating had a complete oxidation temperature of 475° C. showing 100% oxygen removal conversion rate, but the complete oxidation temperature of the hollow fiber LSCF catalyst after Pd coating was lowered. It was confirmed that the performance of the LSCF catalyst was improved. It is believed that oxygen transferred from the Pd coating layer on the surface is adsorbed to the LSCF oxygen vacancies and the surface, and then reacted with methane to be completely oxidized.
그러나, 본 발명에 따른 Pd 코팅된 중공사형 LSCF 촉매는 Pd의 표면 코팅농도가 증가할수록 100% 산소 제거 전화율을 나타내는 완전 산화 온도가 낮아지면서 성능이 향상되다가 일정 한계에 도달하면 떨어지는 경향을 나타내었다. However, the Pd-coated hollow fiber LSCF catalyst according to the present invention exhibited a tendency to decrease when the surface coating concentration of Pd was increased, as the complete oxidation temperature, indicating 100% oxygen removal conversion rate, decreased and the performance was improved and then reached a certain limit.
구체적으로, Pd의 표면 코팅농도가 5.1 wt%보다 작을 경우에는 너무 적은 양의 Pd가 코팅되어 팔라듐 코팅에 따른 성능 개선 효과가 없고, 촉매의 최대 성능은 Pd의 표면 코팅농도가 20.3 wt%인 경우에서 나타났으며, 이때, 완전 산화 온도는 약 400 ℃였다. 그러나, Pd의 표면 코팅농도가 22.5 wt%로 증가하는 경우, 오히려 Pd가 촉매의 산소 흡착 표면을 막기 때문에 도 1의 α 혹은 β 흡착종이 기능하지 못하면서 전체적으로 성능이 감소하면서 완전 산화 온도가 450℃로 다시 증가하는 것으로 나타났다. 이에, Pd의 표면 코팅농도가 22.5 wt%를 초과하면 완전 산화 온도가 더욱 증가하여 공정 조건에 부합되지 않을 수 있다.Specifically, when the surface coating concentration of Pd is less than 5.1 wt%, there is no effect of improving the performance due to the palladium coating because too little Pd is coated, and the maximum performance of the catalyst is when the surface coating concentration of Pd is 20.3 wt%. At this time, the complete oxidation temperature was about 400 °C. However, when the surface coating concentration of Pd is increased to 22.5 wt%, since Pd blocks the oxygen adsorption surface of the catalyst, the α or β adsorbed species in Fig. 1 do not function, and the overall performance decreases and the complete oxidation temperature reaches 450°C. It turns out to increase again. Accordingly, when the surface coating concentration of Pd exceeds 22.5 wt%, the complete oxidation temperature further increases, and the process conditions may not be met.
따라서, 본 발명에 따른 중공사형 LSCF 촉매는 Pd의 표면 코팅농도가 5.1 wt% 내지 22.5 wt%일 때 산소 제거 성능이 향상되어, 일반적인 공정 조건에서 요구되는 450℃ 이하의 온도에서 완전 산화가 수행될 수 있으므로, 본 발명의 특징은 중공사형 LSCF 펠렛의 표면상에 팔라듐(Pd) 나노입자가 5.1 wt% 내지 22.5 wt% 농도로 코팅된 산소 제거 촉매제를 제공함에 있다.Therefore, in the hollow fiber LSCF catalyst according to the present invention, when the surface coating concentration of Pd is 5.1 wt% to 22.5 wt%, oxygen removal performance is improved, so that complete oxidation can be performed at a temperature of 450°C or less required in general process conditions. Therefore, a feature of the present invention is to provide an oxygen removal catalyst in which palladium (Pd) nanoparticles are coated at a concentration of 5.1 wt% to 22.5 wt% on the surface of a hollow fiber LSCF pellet.
본 발명의 LSCF 산소 제거 촉매제에 있어서, 일 실시예에서, 상기 La(1-x)SrxCoyFe1 -yO3-δ에서 x=0.9이고, y=0.2이며, 0≤δ<2일 수 있다. 다른 실시예에서, 상기 La(1-x)SrxCoyFe1-yO3-δ에서 x=0.2이고, y=0.2이며, 0≤δ<2일 수 있다.In the LSCF oxygen removal catalyst of the present invention, in one embodiment, in the La( 1-x )Sr x Co y Fe 1 -y O 3-δ , x=0.9, y=0.2, and 0≤δ<2 Can be In another embodiment, in the La( 1-x )Sr x Co y Fe 1-y O 3-δ , x=0.2, y=0.2, and 0≤δ<2.
본 발명의 LSCF 산소 제거 촉매제는 중공사형(중공사막 형태)인 것이 바람직하다. 중공사막은 가운데 구멍이 있는 얇은 관 형태의 분리막으로, 외부 기공과 내부 기공이 동시에 존재하고, 비대칭형의 기공이 형성되므로 비표면적은 상대적으로 넓다. 따라서 이를 촉매 성형에 적용하면 비표면적이 증가하고, 압력강하를 최소화할 수 있어, 산소 흡착에 용이하다. 또한 타 성형 촉매에 비해 대규모 공정에 적용하기 매우 유리하므로, 대량의 촉매 성형이 가능한 장점이 있다.The LSCF oxygen removal catalyst of the present invention is preferably a hollow fiber type (hollow fiber membrane type). The hollow fiber membrane is a membrane in the form of a thin tube with a hole in the middle. Since external and internal pores exist at the same time, and asymmetric pores are formed, the specific surface area is relatively large. Therefore, when this is applied to catalyst molding, the specific surface area is increased and the pressure drop can be minimized, so that it is easy for oxygen adsorption. In addition, since it is very advantageous to apply to a large-scale process compared to other molding catalysts, there is an advantage that a large amount of catalyst molding is possible.
[Pd 코팅된 중공사형 [Pd coated hollow fiber type LSCFLSCF 촉매제의 제조방법] Method for producing catalyst]
또한, 본 발명은 Pd 코팅된 중공사형 LSCF 촉매제의 제조방법을 제공한다.In addition, the present invention provides a method for preparing a Pd-coated hollow fiber LSCF catalyst.
본 발명에 따른 Pd 코팅된 중공사형 LSCF 촉매제의 제조방법은 The method for preparing a Pd-coated hollow fiber LSCF catalyst according to the present invention is
(a) La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2) 조성을 가진 중공사형 펠렛을 제조하는 단계; 및 (a) La (1-x ) Sr x Co y Fe 1 - to prepare a y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) hollow fiber pellets having a composition; And
(b) 상기 펠렛 제조 단계에서 제조된 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2) 조성을 가진 중공사형 펠렛의 표면에 팔라듐(Pd) 나노입자를 코팅하는 단계를 포함한다.hollow with y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) composition - (b) the La (1-x) Sr x
이하, 본 발명에 따른 Pd 코팅된 중공사형 LSCF 촉매제의 제조방법을 단계별로 설명한다.Hereinafter, a method of preparing a Pd-coated hollow fiber LSCF catalyst according to the present invention will be described step by step.
상기 단계 (a)는 LSCF 중공사형 펠렛을 제조하는 단계이다.The step (a) is a step of preparing an LSCF hollow fiber pellet.
상기 LSCF 중공사형 펠렛의 제조는 Preparation of the LSCF hollow fiber pellets
(1) 고분자 바인더 및 유기용매를 혼합하여 고분자 용액을 제조하는 단계;(1) preparing a polymer solution by mixing a polymer binder and an organic solvent;
(2) 상기 고분자 용액에 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2) 분말 및 가소제를 첨가하여 방사액을 제조하는 단계; (2) La (1-x ) Sr x
(3) 상기 방사액을 내부응고제와 함께 방사노즐로 공급 및 토출하여 중공사막 선구물질을 형성하는 단계; 및(3) forming a hollow fiber membrane precursor material by supplying and discharging the spinning solution together with an internal coagulant to a spinning nozzle; And
(4) 상기 중공사막 선구물질을 상전이, 세정, 건조 및 소결시켜 LSCF 중공사형 펠렛을 얻는 단계를 포함하는 방법으로 수행될 수 있다.(4) The hollow fiber membrane precursor may be phase-transferred, washed, dried, and sintered to obtain LSCF hollow fiber pellets.
적절한 원하는 조성의 LSCF 분말, 고분자 바인더, 유기용매 및 가소제는 시중에서 구입할 수 있으며, 당업자라면 적절한 것을 선택할 수 있다. LSCF powders, polymer binders, organic solvents, and plasticizers having appropriate desired compositions are commercially available, and those skilled in the art can select appropriate ones.
상기 고분자 바인더는 폴리술폰, 폴리에테르술폰, 폴리에테르이미드, 폴리아미드 및 폴리아크릴로니트릴로 이루어진 군에서 선택된 1종 이상일 수 있다.The polymeric binder may be at least one selected from the group consisting of polysulfone, polyethersulfone, polyetherimide, polyamide, and polyacrylonitrile.
상기 유기용매는 N-메틸피롤리돈(NMP), 디메틸 포름아미드(DMF), 디메틸아세트아미드(DMAc), 트리에틸포스페이트(TEP) 및 디메틸술폭시드(DMSO)로 이루어진 군에서 선택된 1종 이상일 수 있다.The organic solvent may be at least one selected from the group consisting of N-methylpyrrolidone (NMP), dimethyl formamide (DMF), dimethylacetamide (DMAc), triethyl phosphate (TEP), and dimethyl sulfoxide (DMSO). have.
상기 LSCF 분말은 x=0.2 또는 0.9이고, y=0.2이고, 50~69 중량%로 첨가될 수 있다.The LSCF powder is x=0.2 or 0.9, y=0.2, and may be added in an amount of 50 to 69% by weight.
상기 가소제는 폴리비닐피롤리돈, 폴리비닐알코올 및 폴리에틸렌글리콜 30-디폴리하이드록시스테아레이트로 이루어진 군에서 선택된 1종 이상일 수 있다.The plasticizer may be one or more selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, and polyethylene glycol 30-dipolyhydroxystearate.
다음으로, 제조된 방사액을 내부응고제와 함께 방사노즐로 공급 및 토출하여 중공사막 선구물질을 형성할 수 있으며, 이때 상기 내부응고제로는 물을 사용할 수 있으나, 이에 제한되는 것은 아니다.Next, the prepared spinning solution may be supplied and discharged to a spinning nozzle together with an internal coagulant to form a precursor material for a hollow fiber membrane. In this case, water may be used as the internal coagulant, but is not limited thereto.
방사된 중공사막 선구물질을 물에서 24시간 정도 침지시킴으로써 추가적으로 상전이 과정을 거칠 수 있으며, 상전이된 중공사막 선구물질은 세척 후에 100 내지 150 ℃ 온도에서 건조시킬 수 있고, 건조 후에는 700 내지 1200 ℃의 온도에서 소결시킴으로써 중공사형 LSCF 펠렛을 제조할 수 있다.The spun hollow fiber membrane precursor can be additionally subjected to a phase transition process by immersing the spun hollow fiber membrane precursor material in water for about 24 hours, and the phase-transferred hollow fiber membrane precursor material can be dried at a temperature of 100 to 150 °C after washing, and after drying, a temperature of 700 to 1200 °C. Hollow fiber LSCF pellets can be prepared by sintering at temperature.
다음으로, 단계 (b)는 LSCF 중공사형 펠렛의 표면에 팔라듐(Pd) 나노입자를 코팅하는 단계이다.Next, step (b) is a step of coating palladium (Pd) nanoparticles on the surface of the LSCF hollow fiber pellets.
코팅하는 방법은 공지된 것으로 당업자라면 적절한 것을 선택할 수 있을 것이나, 무전해도금법을 이용하여 코팅하는 것이 바람직하다.The coating method is known, and those skilled in the art will be able to select an appropriate one, but it is preferable to coat using an electroless plating method.
일례로, 팔라듐 코팅을 위한 팔라듐 전구체(PdCl2), Na2EDTA, 암모니아, 하이드라진 수화물(hydrazine hydrate)가 혼합되어 있는 도금용액에 LSCF 중공사형 펠렛을 넣어 코팅할 수 있으나, 이에 제한되는 것은 아니다.As an example, a palladium precursor for palladium coating (PdCl 2 ), Na 2 EDTA, ammonia, and hydrazine hydrate may be coated by putting LSCF hollow fiber pellets in a plating solution mixed, but is not limited thereto.
이때, 팔라듐(Pd) 나노입자의 표면 코팅량은 5.1 wt% 내지 22.5 wt%인 것이 바람직하다. 만일, 상기 코팅 농도가 5.1 wt% 미만이면, 너무 적은 양의 Pd가 코팅되어 촉매 성능 향상에 미치는 영향이 미미하며, 22.5 wt%를 초과하면 Pd가 산소의 흡착 표면을 막기 때문에 오히려 촉매 성능이 저하되는 문제가 있다. 본 발명의 LSCF 산소 제거 촉매제는 표면에 Pd 나노입자가 적절한 비율로 코팅될 때 촉매 성능이 증가할 수 있다.At this time, it is preferable that the surface coating amount of the palladium (Pd) nanoparticles is 5.1 wt% to 22.5 wt%. If the coating concentration is less than 5.1 wt%, too little Pd is coated and the effect on catalyst performance improvement is insignificant. If it exceeds 22.5 wt%, the catalyst performance is rather degraded because Pd blocks the adsorption surface of oxygen. There is a problem. The LSCF oxygen removal catalyst of the present invention may increase catalytic performance when Pd nanoparticles are coated on the surface in an appropriate ratio.
이러한 방법으로 제조된, 팔라듐(Pd) 나노입자로 코팅된 LSCF 중공사형 펠렛은, 종래 팔라듐 코팅되지 않은 일반 LSCF 펠렛과 비교시 현저히 촉매 성능 개시 온도 및 메탄 완전 산화 온도(100% 산소 제거 전화율을 나타내는 온도)를 50 ℃이상 현저하게 낮추어, 공정 조건에 부합되는 약 350~400℃의 온도에서 100% 산소 제거 전화율을 나타내고(도 11 내지 13 참조), 장시간 경과 후에도 촉매 성능이 유지됨(도 14 참조)으로써, 높은 안정성과 향상된 촉매 성능을 나타내므로, 기존 촉매를 대체하여 산소 제거 촉매제로 유용하게 사용될 수 있다.The LSCF hollow fiber pellets coated with palladium (Pd) nanoparticles prepared in this way show remarkably catalytic performance initiation temperature and methane complete oxidation temperature (100% oxygen removal conversion rate compared to conventional LSCF pellets not coated with palladium). Temperature) was significantly lowered by 50° C. or more, showing a 100% oxygen removal conversion rate at a temperature of about 350 to 400° C. meeting the process conditions (see Figs. 11 to 13), and catalytic performance is maintained even after a long period of time (see Fig. 14). As a result, it exhibits high stability and improved catalytic performance, and thus can be usefully used as an oxygen removal catalyst by replacing the existing catalyst.
이에 따라, 매립지 가스와 같은 미량의 산소를 포함하는 메탄 혼합가스에서 산소만을 빠르게 제거하여 매립 가스 정제 장치의 동작 시 산소로 인한 산업 재해의 위험성을 낮출 수 있다.Accordingly, it is possible to reduce the risk of industrial accidents caused by oxygen when the landfill gas purification apparatus is operated by rapidly removing only oxygen from the methane mixed gas containing a trace amount of oxygen, such as a landfill gas.
[Pd 코팅된 중공사형 [Pd coated hollow fiber type LSCFLSCF 촉매제를 이용한 메탄 혼합 가스의 산소 제거 방법] Method for removing oxygen from methane mixed gas using catalyst]
또한, 본 발명은 상기 Pd 코팅된 중공사형 LSCF 촉매제를 이용한 메탄 혼합 가스의 산소 제거 방법을 제공한다.In addition, the present invention provides a method for removing oxygen from a methane mixed gas using the Pd-coated hollow fiber LSCF catalyst.
본 발명에 다른 메탄 혼합 가스의 산소 제거 방법은A method for removing oxygen from a methane mixed gas according to the present invention is
산소 제거 촉매제를 반응조 내에 제공하는 단계; Providing an oxygen removal catalyst in the reaction tank;
상기 반응조를 가열하는 단계; 및 Heating the reaction tank; And
상기 반응조가 가열된 상태에서, 상기 반응조 내로 메탄 혼합가스를 유입시키면, 상기 메탄 혼합가스의 메탄이 상기 촉매제에 의하여 완전 연소됨에 따라 상기 메탄 혼합 가스 내의 산소가 제거되는 단계를 포함한다.And when the methane mixed gas is introduced into the reaction tank while the reaction tank is heated, oxygen in the methane mixed gas is removed as methane of the methane mixed gas is completely burned by the catalyst.
우선, 반응조 내에 산소 제거 촉매제를 제공한다.First, an oxygen removal catalyst is provided in the reaction tank.
이때, 상기 산소 제거 촉매제로는 본 발명에 따른 Pd 코팅된 중공사형 LSCF 촉매제를 사용한다.At this time, the Pd-coated hollow fiber LSCF catalyst according to the present invention is used as the oxygen removal catalyst.
여기서, 반응조는 산소 제거 장치 내의 반응조일 수 있다.Here, the reaction tank may be a reaction tank in the oxygen removal device.
다음으로, 상기 반응조는 가열된다.Next, the reaction tank is heated.
즉, 상술한 바와 같이, 상기 Pd 코팅된 중공사형 LSCF 촉매제가 메탄 혼합 가스내의 산소를 포집하면서, 300~450℃로 가열됨에 따라, 촉매제에서는 메탄과 산소의 완전 연소 반응이 일어나게 된다. 즉, 상기 반응조가 가열된 상태에서, 상기 반응조 내로 메탄 혼합가스를 유입시키면, 상기 메탄 혼합가스의 메탄이 상기 페롭스카이트 촉매제에 포집된 산소와 완전 연소됨에 따라 상기 메탄 혼합 가스 내의 산소가 제거된다. That is, as described above, as the Pd-coated hollow fiber LSCF catalyst is heated to 300 to 450° C. while collecting oxygen in the methane mixed gas, a complete combustion reaction of methane and oxygen occurs in the catalyst. That is, when the methane mixed gas is introduced into the reaction tank while the reaction tank is heated, oxygen in the methane mixed gas is removed as the methane of the methane mixed gas is completely combusted with the oxygen collected in the perovskite catalyst. .
즉, 다음의 반응식 1과 같은 반응에 의해 산소가 제거된다.That is, oxygen is removed by a reaction as shown in
[반응식 1][Scheme 1]
CH4 + 2O2 → C02 + 2H2OCH 4 + 2O 2 → C0 2 + 2H 2 O
즉, 메탄 1몰을 이용하여 2몰의 산소가 제거된다. That is, 2 moles of oxygen are removed using 1 mole of methane.
메탄 혼합 가스에는 2% 미만의 산소가 있으며, 메탄은 적어도 35%이 포함되게 된다. 이와 같은 메탄 혼합 가스 내에서 상기의 화학식과 같은 반응이 페롭스카이트 촉매제에서 발생됨에 따라, 메탄 성분비에는 크게 영향을 미치지 않으면서도 미량의 산소를 제거하여 천연가스 내에서의 산소 성분비 이하로 메탄 혼합가스 내의 산소를 제거하게 된다. 다시말해, 본 발명에 따른 페롭스카이트 산소 제거 촉매제를 이용하는 경우 300~400 ℃의 저온에서, 메탄가스와 산소의 완전 연소 반응을 촉진시킬 수 있게 되고 이에 따라, 매립지 가스와 같은 미량의 산소를 포함하는 메탄 혼합가스에서 산소만을 빠르게 제거하여 매립 가스 정제 장치의 동작시 산소로 인한 산업 재해의 위험성을 낮출 수 있게 된다.The methane gas mixture contains less than 2% oxygen and at least 35% methane. In such a methane mixed gas, as the reaction of the above formula occurs in the perovskite catalyst, a small amount of oxygen is removed without significantly affecting the methane component ratio, so that the methane mixture gas is less than the oxygen component ratio in the natural gas. It will remove oxygen inside. In other words, when the perovskite oxygen removal catalyst according to the present invention is used, it is possible to accelerate the complete combustion reaction of methane gas and oxygen at a low temperature of 300 to 400° C., and thus, a trace amount of oxygen such as a landfill gas is included. It is possible to reduce the risk of industrial accidents caused by oxygen when the landfill gas purification device is operated by rapidly removing only oxygen from the mixed methane gas.
이하, 본 발명의 이해를 돕기 위해서 제조예 및 실험예(example)를 제시한다. 그러나 하기의 제조예 및 실험예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 본 발명이 하기의 제조예 및 실험예에 한정되는 것은 아니다.Hereinafter, a manufacturing example and an experimental example (example) are presented to aid the understanding of the present invention. However, the following Preparation Examples and Experimental Examples are provided for easier understanding of the present invention, and the present invention is not limited to the following Preparation Examples and Experimental Examples.
<< 제조예Manufacturing example 1 : Pd가 코팅된 중공사형 1: Pd coated hollow fiber type LaLa 00 .. 1One SrSr 00 .. 99 CoCo 00 .. 22 FeFe 00 .. 88 OO 33 -δ-δ ( ( LSCFLSCF -1928) 촉매의 제조>-1928) Preparation of catalyst>
(1) (One) LSCFLSCF -1928 분말 촉매 제조-1928 powder catalyst manufacturing
구연산법으로 LSCF-1928 분말을 제조하였다. LSCF-1928 powder was prepared by the citric acid method.
구체적으로, La(NO3)3·6H2O(순도 99.99%, Aldrich, USA), Sr(NO3)2(순도 99%, Aldrich, USA), Co(NO3)·6H2O(순도 98%, Aldrich, USA), Fe(NO3)3·9H2O(순도 99%, Aldrich USA)을 화학양론에 맞게 질량을 측정한 후, 증류수에 녹여 총 0.1 M의 용액을 제조하였다. 이 용액을 자력교반기를 이용하여 교반시켜 고르게 분산시킨 후, 시트르산(citric acid)(순도 99.5%, SAMCHUN, Korea)을 첨가하였다. 상기 시트르산은 용액 내 금속 이온 몰수의 1.2배에 해당하는 양만큼 첨가하였다. Specifically, La(NO 3 ) 3 ·6H 2 O (purity 99.99%, Aldrich, USA), Sr(NO 3 ) 2 (purity 99%, Aldrich, USA), Co(NO 3 )·6H 2 O (purity 98%, Aldrich, USA), Fe(NO 3 ) 3 ·9H 2 O (purity 99%, Aldrich USA) was measured in accordance with the stoichiometry, and then dissolved in distilled water to prepare a total solution of 0.1 M. After the solution was stirred using a magnetic stirrer and evenly dispersed, citric acid (purity 99.5%, SAMCHUN, Korea) was added. The citric acid was added in an amount corresponding to 1.2 times the number of moles of metal ions in the solution.
이후, 혼합용액을 90 ℃의 온도에서 약 3~4시간 동안 반응시켰다, 반응 후, 황색의 기체가 발생할 때까지 건조시켜 갈색의 겔을 얻었다. 얻은 겔 시료를 110 ℃의 오븐에서 24시간 건조한 후, 유발에서 분쇄하여 선구분말을 얻었다. 그 결과로 얻은 선구분말을 800 ℃에서 2시간 하소한 후, 1,300 ℃에서 5시간 동안 소결하여 최종 분말을 얻었다.Thereafter, the mixed solution was reacted at a temperature of 90° C. for about 3 to 4 hours. After the reaction, it was dried until a yellow gas was generated to obtain a brown gel. The obtained gel sample was dried in an oven at 110° C. for 24 hours, and then pulverized in a mortar to obtain a precursor powder. The resulting precursor powder was calcined at 800° C. for 2 hours and then sintered at 1,300° C. for 5 hours to obtain a final powder.
(2) 중공사형 (2) Hollow fiber type LSCFLSCF -1928 촉매 제조-1928 catalyst production
상기 (1)에서 얻은 LSCF-1928 분말에 대하여 상전지 방적법을 이용하여 중공사형 촉매를 제조하였다.With respect to the LSCF-1928 powder obtained in (1) above, a hollow fiber catalyst was prepared using a phase cell spinning method.
구체적으로, 7.78wt% 폴리에테르이미드(polyetherimide, PEI, Sigma Aldrich, USA)와 31.12wt% 1-메틸-2-피롤리돈(1-Methyl-2-pyrrolidone, NMP, 99.5%, Samchun Pure Chemical CO., LTD, Korea), 0.58wt% 폴리비닐피롤리돈(Polyvinylpyrrolidone, PVP, Sigma Aldrich, USA)을 48시간 동안 혼합하여 도프용액을 제조하였다. 이후, 상기 도프용액에 진공을 걸어 기포를 탈기하였다. Specifically, 7.78wt% polyetherimide (polyetherimide, PEI, Sigma Aldrich, USA) and 31.12wt% 1-methyl-2-pyrrolidone (1-Methyl-2-pyrrolidone, NMP, 99.5%, Samchun Pure Chemical CO ., LTD, Korea), 0.58wt% polyvinylpyrrolidone (PVP, Sigma Aldrich, USA) was mixed for 48 hours to prepare a dope solution. Thereafter, a vacuum was applied to the dope solution to degas the air bubbles.
중공사막 방사를 위해 이중 노즐(외경 3.0 mm, 내경 1.2 mm)을 이용하였고, 5 bar의 질소의 압력을 가해 중공사막 노즐의 외부에 도프용액을 공급하였다. 시린지 펌프(syringe pump, Fusion 100, chemyx, USA)를 이용해 내부 응고제를 5 ml/min의 유량으로 노즐의 내부로 공급하였으며, 내부 응고제 및 외부 응고제로서 증류수를 사용하였다. 방사된 중공사막은 2 cm의 에어갭(air gap)을 갖는 외부 응고조로 들어가 약 24시간 동안 상전이 과정을 통해 용매 교환이 일어나도록 하였다. 이후, 중공사막을 3회 세척하였고, 120 ℃의 오븐에서 약 24시간 건조한 후, 박스로(box furnace)를 이용하여 800 ℃에서 하소 및 소결하여 검은색의 중공사형 LSCF-1928 촉매를 제조하였다. A double nozzle (outer diameter 3.0 mm, inner diameter 1.2 mm) was used for spinning the hollow fiber membrane, and a dope solution was supplied to the outside of the hollow fiber membrane nozzle by applying nitrogen pressure of 5 bar. An internal coagulant was supplied to the inside of the nozzle at a flow rate of 5 ml/min using a syringe pump (
(3) 중공사형 촉매 표면에 팔라듐(Pd) 코팅(3) Palladium (Pd) coating on the surface of the hollow fiber catalyst
팔라듐(Pd) 코팅은 무전해도금법을 이용하여 수행하였으며, PdCl2(순도99%, SigmaAldrich, USA) 0.45 g/L, Na2EDTA(순도>99%, SigmaAldrich, USA) 8.5 g/L, 암모니아(ammonia)(순도28%, Junsei, Japan) 80 ml/L, 하이드라진 수화물(hydrazine hydrate)(순도50-60%, SigmaAldrich, USA) 0.07168 ml/L이 혼합되어 있는 도금용액에, 상기 (2)에서 제조된 중공사형 LSCF-1928 촉매를 넣어 50 ℃에서 코팅하였다.Palladium (Pd) coating was performed using the electroless plating method, PdCl 2 (purity 99%, SigmaAldrich, USA) 0.45 g/L, Na 2 EDTA (purity>99%, SigmaAldrich, USA) 8.5 g/L, ammonia (ammonia) (purity 28%, Junsei, Japan) 80 ml/L, hydrazine hydrate (purity 50-60%, SigmaAldrich, USA) 0.07168 ml/L is mixed in the plating solution, the above (2) The hollow fiber type LSCF-1928 catalyst prepared in was put and coated at 50°C.
코팅과정에서 Pd가 가라 앉아 불균일하게 코팅되는 것을 방지하기 위해, 마그네틱 바를 이용하여 교반을 진행해주며 수행하였다. 이를 통해 Pd 코팅 된 갈색의 중공사형 LSCF-1928 촉매를 얻었다.In order to prevent Pd from sinking and non-uniform coating during the coating process, stirring was performed using a magnetic bar. Through this, a Pd-coated brown hollow fiber LSCF-1928 catalyst was obtained.
<< 제조예Manufacturing example 2-4> 2-4>
Pd의 코팅량을 변화시키기 위해 도금용액의 조성량을 변화시킨 것을 제외하고는 제조예 1과 동일한 방법으로 수행하여 Pd 코팅 된 중공사형 LSCF-1928 촉매를 얻었다.A Pd-coated hollow fiber LSCF-1928 catalyst was obtained by performing the same method as in Preparation Example 1, except that the composition amount of the plating solution was changed to change the coating amount of Pd.
무전해도금 용액 조성은 하기 표 1에 나타내었다.The composition of the electroless plating solution is shown in Table 1 below.
NH 4 OH (28%) (ml/L)
<< 제조예Manufacturing example 5 : Pd가 코팅된 중공사형 5: Pd coated hollow fiber type LaLa 00 .. 88 SrSr 00 .. 22 CoCo 00 .. 22 FeFe 00 .. 88 OO 33 -δ-δ ( ( LSCFLSCF -8228) 촉매의 제조>-8228) Preparation of catalyst>
도프 용액으로서 상업용 La0 . 8Sr0 . 2Co0 . 2Fe0 . 8O3 -δ (Kceracell,한국) 분말과 33wt% N,N-디메틸아세트아미드(N,N-dimethylacetamide, DMAc, Samchun Pure Chemical Co., Ltd., Korea), 6.2wt% 폴리에테르이미드(polyetherimide, PEI, Sigma Aldrich, U.S.A.), 0.8wt% 폴리비닐 피롤리돈(polyvinyl pyrrolidone, PVP, Sigma Aldrich, U.S.A.)을 혼합하여 제조하였다. 얻어진 현탁액을 10 cm의 에어갭(air gap)을 가진 물의 응고조로 압출하여 중공사형 LSCF-8228 촉매를 제조하였다. 이후, 건조과정을 거쳐 건조된 중공사형 LSCF-8228 촉매를 약 5 mm의 길이로 절단한 다음, 1000℃에서 3시간 동안 소결시켰다. Commercial La 0 as a dope solution . 8 Sr 0 . 2 Co 0 . 2 Fe 0 . 8 O 3 -δ (Kceracell, Korea) powder and 33wt% N,N-dimethylacetamide (N,N-dimethylacetamide, DMAc, Samchun Pure Chemical Co., Ltd., Korea), 6.2wt% polyetherimide (polyetherimide) , PEI, Sigma Aldrich, USA), 0.8wt% polyvinyl pyrrolidone (polyvinyl pyrrolidone, PVP, Sigma Aldrich, USA) was prepared by mixing. The obtained suspension was extruded into a water coagulation bath having an air gap of 10 cm to prepare a hollow fiber LSCF-8228 catalyst. Thereafter, the hollow fiber LSCF-8228 catalyst dried through a drying process was cut into a length of about 5 mm, and then sintered at 1000° C. for 3 hours.
팔라듐(Pd) 코팅은 무전해도금법을 이용하여 수행하였으며, PdCl2(순도99%, SigmaAldrich, USA) 1.8 g/L, Na2EDTA(순도>99%, SigmaAldrich, USA) 34 g/L, 암모니아(ammonia)(순도28%, Junsei, Japan) 320 ml/L, 하이드라진 수화물(hydrazine hydrate)(순도50-60%, SigmaAldrich, USA) 0.2867 ml/L이 혼합되어 있는 도금용액에, 제조된 중공사형 LSCF-8228 촉매를 넣어 50 ℃에서 코팅하였다.Palladium (Pd) coating was performed using the electroless plating method, PdCl 2 (purity 99%, SigmaAldrich, USA) 1.8 g/L, Na 2 EDTA (purity >99%, SigmaAldrich, USA) 34 g/L, ammonia (ammonia) (purity 28%, Junsei, Japan) 320 ml/L, hydrazine hydrate (purity 50-60%, SigmaAldrich, USA) 0.2867 ml/L in a mixed plating solution, manufactured hollow fiber type The LSCF-8228 catalyst was added and coated at 50°C.
코팅과정에서 Pd가 가라 앉아 불균일하게 코팅되는 것을 방지하기 위해, 마그네틱 바를 이용하여 교반을 진행해주며 수행하였다. 이를 통해 Pd 코팅 된 중공사형 LSCF-8228 촉매를 얻었다.In order to prevent Pd from sinking and non-uniform coating during the coating process, stirring was performed using a magnetic bar. Through this, a Pd-coated hollow fiber LSCF-8228 catalyst was obtained.
<< 비교예Comparative example 1 : Pd가 코팅되지 않은 중공사형 1: Hollow fiber type without Pd coating LaLa 00 .. 1One SrSr 00 .. 99 CoCo 00 .. 22 FeFe 00 .. 88 OO 33 -δ-δ ( ( LSCFLSCF -1928) 촉매의 제조>-1928) Preparation of catalyst>
팔라듐 코팅 단계를 진행하지 않고, 제조예 1과 동일한 방법으로 중공사형 LSCF-1928 촉매를 제조하였다.A hollow fiber LSCF-1928 catalyst was prepared in the same manner as in Preparation Example 1 without performing the palladium coating step.
<< 비교예Comparative example 2 : Pd가 코팅되지 않은 중공사형 2: Hollow fiber type without Pd coating LaLa 00 .. 88 SrSr 00 .. 22 CoCo 00 .. 22 FeFe 00 .. 88 OO 33 -δ-δ ( ( LSCFLSCF -8228) 촉매의 제조>-8228) Preparation of catalyst>
팔라듐 코팅 단계를 진행하지 않고, 제조예 5와 동일한 방법으로 중공사형 LSCF-8228 촉매를 제조하였다.Without performing the palladium coating step, a hollow fiber LSCF-8228 catalyst was prepared in the same manner as in Preparation Example 5.
<< 실험예Experimental example 1 : 주사전자현미경(Scanning Electron Microscope, 1: Scanning Electron Microscope (Scanning Electron Microscope, SEMSEM ) 분석>) Analysis>
비교예 및 제조예에서 제조된, Pd 코팅이 없거나 Pd 코팅된 LSCF-1928 촉매 및 LSCF-8228 촉매의 기공 구조를 분석하기 위해, 단면을 깨끗하게 절단한 시편을 준비하고, 전자주사현미경(FE-SEM, S-4800, Hitachi, Japan)을 이용하여 중공사막의 단면 및 표면을 촬영하여 도 5 내지 도 9에 나타내었다.In order to analyze the pore structure of the LSCF-1928 catalyst and LSCF-8228 catalyst without Pd coating or Pd coating prepared in Comparative Examples and Preparation Examples, a cleanly cut specimen was prepared, and an electron scanning microscope (FE-SEM , S-4800, Hitachi, Japan) was shown in FIGS. 5 to 9 by photographing the cross-section and the surface of the hollow fiber membrane.
도 5는 본 발명의 일 비교예에 따라 제조된, Pd 코팅이 없는 중공사형 LSCF-1928 촉매의 (a) 횡단면 사진, (b) 횡단면의 확대도, (c) 표면 이미지, 및 (d) 표면 이미지의 확대도이다.5 is a (a) cross-sectional photograph of a hollow fiber LSCF-1928 catalyst without a Pd coating, (b) an enlarged view of the cross-section, (c) a surface image, and (d) a surface of a hollow fiber-type LSCF-1928 catalyst prepared according to a comparative example of the present invention. This is an enlarged view of the image.
도 6은 본 발명의 제조예 1에 따라 제조된, Pd 코팅된(Pd의 표면 코팅농도 5.1wt%) 중공사형 LSCF-1928 촉매의 (a) 횡단면 사진, (b) 횡단면의 확대도, (c) 표면 이미지, 및 (d) 표면 이미지의 확대도이다.6 is a Pd-coated (Pd surface coating concentration of 5.1wt%) hollow fiber LSCF-1928 catalyst prepared according to Preparation Example 1 of the present invention (a) a cross-sectional photograph, (b) an enlarged view of the cross-section, (c) ) A surface image, and (d) an enlarged view of the surface image.
도 7은 본 발명의 제조예 2에 따라 제조된, Pd 코팅된(Pd의 표면 코팅농도 15.8wt%) 중공사형 LSCF-1928 촉매의 (a) 횡단면 사진, (b) 횡단면의 확대도, (c) 표면 이미지, 및 (d) 표면 이미지의 확대도이다.7 is a Pd-coated (Pd surface coating concentration of 15.8 wt%) hollow fiber LSCF-1928 catalyst prepared according to Preparation Example 2 of the present invention (a) a cross-sectional photograph, (b) an enlarged view of the cross-section, (c ) A surface image, and (d) an enlarged view of the surface image.
도 8은 본 발명의 제조예 3에 따라 제조된, Pd 코팅된(Pd의 표면 코팅농도 20.3wt%) 중공사형 LSCF-1928 촉매의 (a) 횡단면 사진, (b) 횡단면의 확대도, (c) 표면 이미지, 및 (d) 표면 이미지의 확대도이다.8 is a Pd-coated (Pd surface coating concentration of 20.3 wt%) hollow fiber LSCF-1928 catalyst prepared according to Preparation Example 3 of the present invention (a) a cross-sectional photograph, (b) an enlarged view of the cross-section, (c ) A surface image, and (d) an enlarged view of the surface image.
도 9는 본 발명의 일 실시예에 따라 제조된, Pd로 코팅된 중공사형 LSCF-8228 촉매의 (a) 전체 사진, (b) 단면의 SEM 이미지(35x), (c) 단면의 SEM 이미지(200x), (d)SEM 현미경으로 본 상부 이미지(1000x), 및 (e) Pd 입자의 EDS 맵핑 사진을 나타낸다.9 is a (a) overall photograph, (b) a cross-sectional SEM image (35x), (c) a cross-sectional SEM image of the hollow fiber LSCF-8228 catalyst coated with Pd prepared according to an embodiment of the present invention ( 200x), (d) an upper image (1000x) seen under a SEM microscope, and (e) an EDS mapping picture of Pd particles.
도 5 내지 도 9에 나타낸 바와 같이, 본 발명에 따른 LSCF 촉매는 기공을 갖는 중공사막의 형태인 것을 확인하였으며, Pd 코팅이 이루어지지 않은 도 5의 (d)를 참조하면, 중공사막 표면이 미세한 입자로 치밀하게 이루어져 있으나, Pd 코팅 후, 도 6 내지 도 8의 (d)에 나타낸 바와 같이, Pd 결정 입자들이 부착되어 있는 것을 확인할 수 있으며, 도 9의 (e)에 나타낸 바와 같이, Pd 입자의 EDS 맵핑 결과, Pd 입자가 붉은 색으로 나타났다.5 to 9, it was confirmed that the LSCF catalyst according to the present invention was in the form of a hollow fiber membrane having pores, and referring to FIG. 5(d) without Pd coating, the surface of the hollow fiber membrane was fine. It is made of particles densely, but after Pd coating, as shown in Figs. 6 to 8 (d), it can be seen that Pd crystal particles are attached, and as shown in Fig. 9 (e), Pd particles As a result of EDS mapping, Pd particles appeared in red.
이를 통해 본 발명에 따른 LSCF 촉매는 중공사막 상에 Pd 입자가 성공적으로 코팅됨을 확인하였다.Through this, it was confirmed that the LSCF catalyst according to the present invention was successfully coated with Pd particles on the hollow fiber membrane.
<< 실험예Experimental example 2 : 촉매의 산소 제거 성능 측정> 2: Measurement of the oxygen removal performance of the catalyst>
본 발명의 따른 Pd 코팅된 중공사형 LSCF 촉매의 산소 제거 성능을 측정하기 위하여, 도 10의 메탄 완전 산화 실험 장치를 구성하였다.In order to measure the oxygen removal performance of the Pd-coated hollow fiber LSCF catalyst according to the present invention, the methane complete oxidation experiment apparatus of FIG. 10 was constructed.
구체적으로, 모사 매립지 가스로 메탄, 헬륨, 이산화탄소, 질소, 산소를 봄베와 질량 유량 제어기(MFC)를 이용하여 메탄 50 mol%, 이산화탄소 40 mol%, 질소 8 mol%, 및 산소 2 mol%의 조성으로 혼합하여 내경 20 mm의 석영 재질의 반응기에 50 ml/min의 유량으로 공급하였다. Specifically, the composition of 50 mol% of methane, 40 mol% of carbon dioxide, 8 mol% of nitrogen, and 2 mol% of oxygen using a bomb and mass flow controller (MFC) as the simulated landfill gas And supplied to a reactor made of quartz with an inner diameter of 20 mm at a flow rate of 50 ml/min.
실험 전 촉매에 붙어있을 수 있는 산소 및 불순물을 제거하기 위하여 헬륨으로 퍼지(purge)하였고, 또한 반응기 공급 라인 내에 남아있을 수 있는 불순물 및 가스를 제거하기 위해 진공펌프를 이용하여 감압한 후 모사 매립지 가스를 공급하였다. Before the experiment, it was purged with helium to remove oxygen and impurities that may be attached to the catalyst, and after reducing pressure using a vacuum pump to remove impurities and gases that may remain in the reactor supply line, the simulated landfill gas Was supplied.
이후, 본 발명에 따른 중공사형 LSCF 촉매를 4 g 로딩하였으며, 도 10과 같이 촉매 층의 고정을 위하여 석영솜(Quartz wool)과 석영봉(Quartz stick)을 사용하여 고정하였다. 전기로를 이용하여 반응기의 온도를 조절하였고, 촉매의 전화율을 확인하기 위하여 반응 후 가스 조성 및 함량을 가스 크로마토그래피(GC)로 분석하였다. 실험 결과는 산소 전화율로 나타냈다.Thereafter, 4 g of the hollow fiber LSCF catalyst according to the present invention was loaded, and as shown in FIG. 10, a quartz wool and a quartz stick were used to fix the catalyst layer. The temperature of the reactor was controlled using an electric furnace, and the gas composition and content after the reaction were analyzed by gas chromatography (GC) in order to check the conversion rate of the catalyst. The experimental results were expressed by the oxygen conversion rate.
도 11은 Pd 코팅 전/후의 중공사형 LSCF-1928 촉매의 메탄 완전 산화 실험 결과이다.11 is a result of methane complete oxidation of a hollow fiber LSCF-1928 catalyst before/after Pd coating.
도 11에 나타낸 바와 같이, Pd 코팅 전의 중공사형 LSCF-1928 촉매의 완전 산화 온도는 475 ℃었으나, Pd 코팅 후 중공사형 LSCF-1928 촉매의 완전 산화는 이보다 낮은 온도에서 일어남을 확인하였다. 이로부터, Pd 코팅 후 중공사형 LSCF 촉매의 성능이 향상된 것을 알 수 있다.As shown in FIG. 11, it was confirmed that the complete oxidation temperature of the hollow fiber LSCF-1928 catalyst before Pd coating was 475° C., but the complete oxidation of the hollow fiber LSCF-1928 catalyst after Pd coating occurred at a lower temperature. From this, it can be seen that the performance of the hollow fiber LSCF catalyst is improved after Pd coating.
다음으로, Pd의 표면 코팅농도에 따른 촉매 성능을 관찰하였다.Next, the catalyst performance according to the surface coating concentration of Pd was observed.
구체적으로 Pd의 표면 코팅농도를 다양하게 변화시키면서 다수의 반복실험을 수행하였으며, 이 중 의미있는 데이터만을 선별하여 도 11에 나타내었다.Specifically, a number of replicate experiments were performed while varying the surface coating concentration of Pd, and only meaningful data among them were selected and shown in FIG. 11.
도 11에 나타낸 바와 같이, 본 발명에 따른 Pd 코팅된 중공사형 LSCF-1928 촉매는 Pd의 표면 코팅농도가 증가할수록 완전 산화 온도가 낮아지면서 성능이 향상되다가 일정 한계에 도달하면 떨어지는 경향을 나타내었다. As shown in FIG. 11, the Pd-coated hollow fiber LSCF-1928 catalyst according to the present invention exhibited a tendency to decrease when the total oxidation temperature decreases as the surface coating concentration of Pd increases, improving performance, and then reaching a certain limit.
촉매의 최대 성능은 Pd의 표면 코팅농도가 20.3 wt%인 경우에서 나타났으며, 이때, 완전 산화 온도는 약 400 ℃였다. 그러나, Pd의 표면 코팅농도가 22.5 wt%로 증가한 경우, 완전 산화 온도는 450 ℃로서 촉매 활성이 감소하였음을 알 수 있다. 이로부터 Pd가 일정수준 이상으로 LSCF 촉매의 표면을 덮으면, 도 1의 α 혹은 β 흡착종이 기능하지 못하면서 전체적으로 성능이 감소하는 것을 알 수 있다. 즉, Pd의 표면 코팅농도가 5.1 wt%보다 작을 경우에는 너무 적은 양의 Pd가 코팅되어 성능이 안나오고, 22.5 wt%보다 클 경우에는 산소의 흡착 표면을 막기 때문에 성능이 떨어지는 것을 알 수 있다. 따라서 본 발명에 따른 중공사형 LSCF 촉매의 Pd의 표면 코팅농도는 5.1 wt% 내지 22.5 wt%인 것이 바람직하다.The maximum performance of the catalyst was found when the surface coating concentration of Pd was 20.3 wt%, and at this time, the complete oxidation temperature was about 400°C. However, when the surface coating concentration of Pd was increased to 22.5 wt%, the complete oxidation temperature was 450°C, indicating that the catalytic activity was decreased. From this, it can be seen that when the Pd covers the surface of the LSCF catalyst above a certain level, the α or β adsorbed species of FIG. 1 do not function, and the overall performance decreases. That is, it can be seen that when the surface coating concentration of Pd is less than 5.1 wt%, too little Pd is coated, resulting in poor performance, and when it is greater than 22.5 wt%, it blocks the adsorption surface of oxygen. Therefore, it is preferable that the surface coating concentration of Pd of the hollow fiber LSCF catalyst according to the present invention is 5.1 wt% to 22.5 wt%.
<< 실험예Experimental example 3 : 고농도의 황화수소를 포함하는 극한 환경에서의 촉매 성능 측정> 3: Measurement of catalyst performance in extreme environments containing high concentration of hydrogen sulfide>
본 발명의 따른 Pd 코팅된 중공사형 LSCF 촉매의 극한 환경에서의 촉매 성능을 알아보기 위하여 다음과 같은 실험을 수행하였다.In order to investigate the catalyst performance of the Pd-coated hollow fiber LSCF catalyst according to the present invention in an extreme environment, the following experiment was performed.
일반 모사 매립지 가스(LFG)로 메탄, 헬륨, 이산화탄소, 질소, 산소를 봄베와 질량 유량 제어기(MFC)를 이용하여 메탄 50 mol%, 이산화탄소 40 mol%, 질소 8 mol%, 및 산소 2 mol%의 조성으로 혼합하여 내경 20 mm의 석영 재질의 반응기에 50 ml/min의 유량으로 공급하였다. Methane, helium, carbon dioxide, nitrogen, and oxygen as general simulation landfill gas (LFG) were mixed with 50 mol% of methane, 40 mol% of carbon dioxide, 8 mol% of nitrogen, and 2 mol% of oxygen using a cylinder and mass flow controller (MFC). The composition was mixed and supplied to a reactor made of quartz with an inner diameter of 20 mm at a flow rate of 50 ml/min.
한편, 극한 환경을 조성하기 위하여, 일반 모사 매립지 가스(LFG)에 독성이 있는 황화수소를 20 ppm의 고농도로 첨가하였다.Meanwhile, in order to create an extreme environment, hydrogen sulfide, which is toxic to general simulated landfill gas (LFG), was added at a high concentration of 20 ppm.
두 경우에 대하여 비교예 2 및 제조예 5에서 제조된, Pd 코팅 전/후의 중공사형 LSCF-8228 촉매를 고정시키고 산소 전화율을 측정하여, 100% 산소가 제거되는 완전 산화 온도를 측정하였다.For both cases, the hollow fiber LSCF-8228 catalyst prepared in Comparative Example 2 and Preparation Example 5, before/after Pd coating, was fixed and the oxygen conversion rate was measured, and the complete oxidation temperature at which 100% oxygen was removed was measured.
실험 결과는 도 12 및 도 13에 나타내었다.The experimental results are shown in FIGS. 12 and 13.
도 12는 Pd 코팅이 없는 중공사형 LSCF-8228 촉매의 일반 모사 매립지 가스 환경과 고농도 황화수소(20 ppm)의 극한 환경에서의 산소 제거 전화율을 나타내는 그래프이다. 12 is a graph showing the oxygen removal conversion rate of a hollow fiber LSCF-8228 catalyst without a Pd coating in an extreme environment of a general simulated landfill gas environment and high concentration hydrogen sulfide (20 ppm).
도 13은 Pd 코팅된 중공사형 LSCF-8228 촉매의 일반 모사 매립지 가스 환경과 고농도 황화수소(20 ppm)의 극한 환경에서의 산소 제거 전화율을 나타내는 그래프이다. 13 is a graph showing the oxygen removal conversion rate of a Pd-coated hollow fiber LSCF-8228 catalyst in an extreme environment of a general simulated landfill gas environment and high concentration hydrogen sulfide (20 ppm).
도 12 및 도 13에 나타낸 바와 같이, 중공사형 LSCF-8228 촉매는 일반 모사 매립지 가스 환경에서는 약 480 ℃의 온도에서 100%의 산소 제거 전화율이 나타났으나, Pd 코팅 후, 320 ℃의 저온에서도 100%의 산소 제거 전화율이 나타나면서 촉매활성이 향상된 것으로 나타났다.12 and 13, the hollow fiber LSCF-8228 catalyst showed 100% oxygen removal conversion rate at a temperature of about 480° C. in a general simulated landfill gas environment, but after Pd coating, even at a low temperature of 320° C. It was found that the catalytic activity was improved as the oxygen removal conversion rate of% appeared.
또한, 10% 전화율이 일어나는 촉매 성능 개시 온도(LO10%)에 있어서, 본 발명에 따른 중공사형 LSCF-8228 촉매는 Pd 코팅 전에 약 330 ℃에서 촉매 성능을 개시하였으나, Pd 코팅 후에 약 225 ℃까지 촉매 성능 개시 온도가 낮아짐으로써, 하기 표 2에 나타낸 바와 같이, 종래 문헌에 개시된 산소 제거 촉매들의 촉매 성능 개시 온도와 비교할 때, 가장 낮은 개시온도를 보임으로써 촉매 성능이 우수함을 나타내었다.In addition, in the catalyst performance initiation temperature (LO 10% ) at which 10% conversion occurs, the hollow fiber LSCF-8228 catalyst according to the present invention initiated catalytic performance at about 330° C. before Pd coating, but up to about 225° C. after Pd coating. As the catalytic performance initiation temperature was lowered, as shown in Table 2 below, compared to the catalytic performance initiation temperature of the oxygen removal catalysts disclosed in the conventional literature, the lowest initiation temperature was shown, indicating excellent catalytic performance.
(℃)Catalyst activation initiation temperature
(℃)
(LFG 조성 환경)Catalyst material
(LFG composition environment)
(CH4 60%, CO2 30%, N2 8%, O2 2%) La 0 coated with Pd . 8 Sr 0 . 2 Co 0 . 2 Fe 0 . 8 O 3 -δ catalyst
(
(CH4 50.1-55.6%, CO2 32.6-38.5%, N2 4.8-8.7%,
O2 0.8-1.5%, H2S 462-856 ppm)Pt/α-Al 2 O 3 coated on a metal substrate
(CH 4 50.1-55.6%, CO 2 32.6-38.5%, N 2 4.8-8.7%,
O 2 0.8-1.5%, H 2 S 462-856 ppm)
(CH4 55.0%, CO2 44.0%, O2 1.0%)Α-Al 2 O 3 catalyst doped with Pt
(CH 4 55.0%, CO 2 44.0%, O 2 1.0%)
(50% CH4,40% CO2,8% N2,2% O2)La 0 . 8 Sr 0 . 2 Co 0 . 2 Fe 0 . 8 O 3 -δ
(50% CH 4 ,40% CO 2 ,8% N 2 ,2% O 2 )
(CH4 50%, CO2 40%, N2 9%, O2 1%)La 0 . 9 Sr 0 . 1 Co 0 . 2 Fe 0 . 8 O 3 -δ catalyst
(
(CH4 52.4%, CO2 33.6%, O2 2.3%)Pt-Rh/Al 2 O 3 coated on a metal substrate
(CH 4 52.4%, CO 2 33.6%, O 2 2.3%)
(b) Yang, Z., Chen, Z., Gong, H., Wu, W., Wang, X., Chen, L., Yang X. (2019). Fuel, 249, 161-168.
(c) Magnone, E., Kim, J.R., Kim, E.J., Park, J.H. (2016).Fuel, 183, 34-38.
(d) Kim, M. K., Pak, S.-H., Shin, M. C., Park, C., Magnone, E., Park, J. H. (2019). Korean Journal of Chemical Engineering, 36(7), 1201-1207.
(e) Gong, H., Chen, Z., Wang, M., Wu, W., Wang W. (2014)., Fuel, 120, 179-185.(a) Gong, H., Chen, Z., Zhang, M., Wu, W., Wang, W., Wang, W. (2015)., Fuel, 144, 43-49,
(b) Yang, Z., Chen, Z., Gong, H., Wu, W., Wang, X., Chen, L., Yang X. (2019). Fuel, 249, 161-168.
(c) Magnone, E., Kim, JR, Kim, EJ, Park, JH (2016). Fuel, 183, 34-38.
(d) Kim, MK, Pak, S.-H., Shin, MC, Park, C., Magnone, E., Park, JH (2019). Korean Journal of Chemical Engineering, 36(7), 1201-1207.
(e) Gong, H., Chen, Z., Wang, M., Wu, W., Wang W. (2014)., Fuel, 120, 179-185.
또한, 고농도 황화수소(20 ppm)의 극한 환경에서 중공사형 LSCF-8228 촉매는 580 ℃의 고온에서 100%의 산소 제거 전화율이 나타났으나, Pd 코팅 후, 100%의 산소 제거 전화율이 나타나는 온도는 약 400 ℃로서, 일반 공정에서 요구되는 450 ℃ 이하의 온도로 나타났다. 따라서, 본 발명에 따른 Pd 코팅된 중공사형 LSCF 촉매는 독성있는 고농도 황화수소를 포함하는 극한 환경에서도 일반 공정에서 요구되는 450 ℃ 이하의 온도에서 100% 산소 제거 전화율을 나타냄으로써, Pd 코팅 전과 비교시 산소 제거 촉매 활성이 현저히 향상됨을 알 수 있다.In addition, in the extreme environment of high concentration hydrogen sulfide (20 ppm), the hollow fiber LSCF-8228 catalyst showed 100% oxygen removal conversion rate at a high temperature of 580 ℃, but after Pd coating, the temperature at which the oxygen removal conversion rate of 100% appeared was about As 400° C., it was found to be a temperature of 450° C. or less required in a general process. Therefore, the Pd-coated hollow fiber LSCF catalyst according to the present invention exhibits a 100% oxygen removal conversion rate at a temperature of 450° C. or less required in a general process even in an extreme environment containing toxic high concentration hydrogen sulfide. It can be seen that the removal catalytic activity is remarkably improved.
<< 실험예Experimental example 4 : 촉매의 안정성 평가> 4: Evaluation of the stability of the catalyst>
본 발명의 따른 Pd 코팅된 중공사형 LSCF 촉매의 안정성을 알아보기 위하여 다음과 같은 실험을 수행하였다.In order to find out the stability of the Pd-coated hollow fiber LSCF catalyst according to the present invention, the following experiment was performed.
본 발명에 따른 Pd으로 코팅 된 중공사형 LSCF-8228 촉매와, 비교예의 Pd 코팅되지 않은 중공사형 LSCF-8228 촉매에 있어서, 황화수소가 0.5ppm 이하로 포함된 매립지 가스 환경에서, 각각 O2 전환율이 100%인 온도에서 시간에 따른 촉매 성능을 측정하여, 그 결과를 도 14에 나타내었다.In the hollow fiber LSCF-8228 catalyst coated with Pd according to the present invention and the hollow fiber LSCF-8228 catalyst without Pd coating of Comparative Example, in a landfill gas environment containing less than 0.5 ppm hydrogen sulfide, each O 2 conversion rate was 100 The catalyst performance was measured over time at a temperature of %, and the results are shown in FIG. 14.
도 14는 Pd 코팅 유무에 따른 중공사형 LSCF-8228 촉매의 시간에 따른 산소 제거 전화율의 변화를 나타내는 그래프이다. 14 is a graph showing a change in oxygen removal conversion rate over time of a hollow fiber LSCF-8228 catalyst with or without Pd coating.
도 14에 나타낸 바와 같이, 중공사형 LSCF-8228 촉매는 Pd 코팅 유무에 따라 시간에 따른 성능은 현저히 차이가 나는 것을 확인할 수 있다.As shown in FIG. 14, it can be seen that the performance of the hollow fiber LSCF-8228 catalyst significantly differs over time depending on the presence or absence of Pd coating.
구체적으로, Pd 코팅되지 않은 중공사형 LSCF-8228 촉매를 사용하는 경우, 초기에는 O2 전환율이 100 %에서 시간이 지날수록 점차 감소해서 4일 후에는 촉매 성능이 약 80 %이하가 되었다. 그러나, 본 발명에 따라 Pd 코팅된 LSCF-8228 촉매는 4일 후에도 100%에 가까운 전환율을 유지했다. Specifically, in the case of using a hollow fiber LSCF-8228 catalyst not coated with Pd, the O 2 conversion rate initially decreased from 100% to gradually over time, and the catalyst performance became less than about 80% after 4 days. However, the Pd-coated LSCF-8228 catalyst according to the present invention maintained a conversion rate close to 100% even after 4 days.
즉, 본 발명에 따른 Pd 코팅된 중공사형 LSCF-8228 촉매는 산소를 흡착시킬 수 있는 LSCF와 활성을 높이는 Pd의 시너지 효과에 의해 황화수소 분위기에서도 높은 활성을 나타내고, 안정한 내구성을 가짐을 보여주었다. That is, the Pd-coated hollow fiber LSCF-8228 catalyst according to the present invention exhibits high activity even in a hydrogen sulfide atmosphere due to the synergistic effect of LSCF that can adsorb oxygen and Pd that increases the activity, and has stable durability.
따라서, 본 발명에 따른 Pd 코팅된 중공사형 LSCF 촉매는 장기 안정성 및 고성능 산소제거 성능을 유지할 수 있으므로 산소 제거 촉매제로서 유용하게 사용될 수 있다.Therefore, the Pd-coated hollow fiber LSCF catalyst according to the present invention can maintain long-term stability and high-performance oxygen removal performance, and thus can be usefully used as an oxygen removal catalyst.
이상 본 발명을 바람직한 실시예를 참조하여 설명하였지만, 본 발명은 상기 실시예에 제한되지 않는다는 것을 이해하여야 한다. 본 발명은 후술하는 특허청구범위 내에서 상기 실시예를 다양하게 변형 및 수정할 수 있으며, 이들은 모두 본 발명의 범위 내에 속하는 것이다. 따라서, 본 발명은 특허청구범위 및 그 균등물에 의해서만 제한된다.Although the present invention has been described above with reference to preferred embodiments, it should be understood that the present invention is not limited to the above embodiments. The present invention can be variously modified and modified within the scope of the claims to be described later, all of which fall within the scope of the present invention. Accordingly, the present invention is limited only by the claims and their equivalents.
Claims (10)
상기 중공사형 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2) 펠렛의 표면상에 5.1 wt% 내지 22.5 wt%의 농도로 코팅된 팔라듐(Pd) 나노입자를 포함하는 산소 제거 촉매제.Hollow fiber La (1-x) Sr x Co y Fe 1 - y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) the pellets; And
The hollow fiber type La (1-x) Sr x Co y Fe 1 - y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) on the surface of the pellet 5.1 wt% to about 22.5 Oxygen removal catalyst comprising palladium (Pd) nanoparticles coated at a concentration of wt%.
상기 팔라듐(Pd) 나노입자는 중공사형 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1, 0≤δ<2) 펠렛의 표면상에 코팅되어, 100% 산소 제거 전화율이 나타나는 온도를 낮추는 것을 특징으로 하는 산소 제거 촉매제.The method of claim 1,
The surface of y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) Pellets - The palladium (Pd) nanoparticles are hollow fiber type La (1-x) Sr x Co y Fe 1 It is coated on the oxygen removal catalyst, characterized in that lowering the temperature at which 100% oxygen removal conversion rate appears.
상기 La(1-x)SrxCoyFe1 - yO3 -δ에서 x=0.9이고, y=0.2 이며, 0≤δ<2인 것을 특징으로 하는 산소 제거 촉매제.The method of claim 1,
The La (1-x) Sr x Co y Fe 1 - y O and 3 -δ x = 0.9 in, and y = 0.2, 0≤δ <2 a catalyst, characterized in that the oxygen removal.
상기 La(1-x)SrxCoyFe1 - yO3 -δ에서 x=0.2이고, y=0.2 이며, 0≤δ<2인 것을 특징으로 하는 산소 제거 촉매제.The method of claim 1,
The La (1-x) Sr x Co y Fe 1 - y O and 3 -δ x = 0.2 in, and y = 0.2, 0≤δ <2 a catalyst, characterized in that the oxygen removal.
상기 펠렛 제조 단계에서 제조된 중공사형 La(1-x)SrxCoyFe1 - yO3 -δ (0<x<1, 0<y<1) 조성을 가진 펠렛의 표면에 팔라듐(Pd) 나노입자를 5.1 wt% 내지 22.5 wt%의 농도로 코팅하는 단계를 포함하는 산소 제거 촉매제의 제조방법.Preparing a pellet with y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) composition - hollow fiber La (1-x) Sr x Co y Fe 1; And
The pellet a hollow fiber type La (1-x) Sr x Co y Fe 1 manufactured in the manufacturing step - palladium on the surface of the pellet with y O 3 -δ (0 <x <1, 0 <y <1) a composition (Pd) A method for producing an oxygen removal catalyst comprising the step of coating the nanoparticles at a concentration of 5.1 wt% to 22.5 wt%.
상기 팔라듐(Pd) 나노입자를 코팅하는 단계는 무전해도금법을 사용하는 것을 특징으로 하는 산소 제거 촉매제의 제조방법.The method of claim 5,
The step of coating the palladium (Pd) nanoparticles is a method of producing an oxygen removal catalyst, characterized in that using an electroless plating method.
상기 La(1-x)SrxCoyFe1 - yO3 -δ에서 x=0.9이고, y=0.2 이며, 0≤δ<2인 것을 특징으로 하는 산소 제거 촉매제의 제조방법.The method of claim 5,
The La (1-x) Sr x Co y Fe 1 - x = 0.9 and y O 3 in -δ, and y = 0.2, 0≤δ <2 A method for producing a catalyst for oxygen removal, characterized in that.
상기 La(1-x)SrxCoyFe1 - yO3 -δ에서 x=0.2이고, y=0.2 이며, 0≤δ<2인 것을 특징으로 하는 산소 제거 촉매제의 제조방법.The method of claim 5,
The La (1-x) Sr x Co y Fe 1 - x = 0.2 and y O 3 in -δ, and y = 0.2, 0≤δ <2 A method for producing a catalyst for oxygen removal, characterized in that.
상기 반응조를 가열하는 단계; 및
상기 반응조가 가열된 상태에서, 상기 반응조 내로 메탄 혼합가스를 유입시키면, 상기 메탄 혼합가스의 메탄이 상기 촉매제에 의하여 완전 연소됨에 따라 상기 메탄 혼합 가스 내의 산소가 제거되는 단계를 포함하는, 산소 제거 촉매제를 이용한 메탄 혼합 가스의 산소 제거 방법.Hollow fiber La (1-x) Sr x Co y Fe 1 - y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) the pellets; And the hollow fiber type La (1-x) Sr x Co y Fe 1 - y O 3 -δ (0 <x <1, 0 <y <1, 0≤δ <2) 5.1 wt% to the surface of the pellets Providing an oxygen removal catalyst including palladium (Pd) nanoparticles coated at a concentration of 22.5 wt% in a reaction tank;
Heating the reaction tank; And
When the methane mixed gas is introduced into the reaction tank while the reaction tank is heated, oxygen in the methane mixed gas is removed as the methane of the methane mixed gas is completely burned by the catalyst. Method for removing oxygen from methane mixed gas using.
상기 반응조를 가열하는 단계는 300~450℃로 가열하는 단계를 포함하는, 산소 제거 촉매제를 이용한 메탄 혼합 가스의 산소 제거 방법.The method of claim 9,
Heating the reaction tank comprises heating to 300 ~ 450 ℃, oxygen removal method of the methane mixed gas using an oxygen removal catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020190136487A KR102255220B1 (en) | 2019-10-30 | 2019-10-30 | Hollow fiber type LSCF oxygen removing catalyst coated with Pd, preparation method thereof, and method for removing oxygen in methane mixture gas by using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020190136487A KR102255220B1 (en) | 2019-10-30 | 2019-10-30 | Hollow fiber type LSCF oxygen removing catalyst coated with Pd, preparation method thereof, and method for removing oxygen in methane mixture gas by using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20210053359A true KR20210053359A (en) | 2021-05-12 |
| KR102255220B1 KR102255220B1 (en) | 2021-05-25 |
Family
ID=75918695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020190136487A KR102255220B1 (en) | 2019-10-30 | 2019-10-30 | Hollow fiber type LSCF oxygen removing catalyst coated with Pd, preparation method thereof, and method for removing oxygen in methane mixture gas by using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102255220B1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005087941A (en) * | 2003-09-19 | 2005-04-07 | Inst Of Research & Innovation | Oxygen adsorbent and oxygen/nitrogen separating method using the same |
| JP2008012439A (en) * | 2006-07-06 | 2008-01-24 | Kyuchaku Gijutsu Kogyo Kk | Oxygen producing method and apparatus by pressure swing method using high temperature oxygen adsorbent |
| KR20150094071A (en) * | 2014-02-10 | 2015-08-19 | 동국대학교 산학협력단 | Ceramic adsorbent for removal of oxygen |
| KR20170068801A (en) * | 2015-12-10 | 2017-06-20 | 동국대학교 산학협력단 | Method for removing oxygen in methane mixture gas by using oxygen catalyst, perovskite type oxygen removing catalyst used in the same, and land fill gas refine device applying land fill gas mathane direct converting technology using the same |
-
2019
- 2019-10-30 KR KR1020190136487A patent/KR102255220B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005087941A (en) * | 2003-09-19 | 2005-04-07 | Inst Of Research & Innovation | Oxygen adsorbent and oxygen/nitrogen separating method using the same |
| JP2008012439A (en) * | 2006-07-06 | 2008-01-24 | Kyuchaku Gijutsu Kogyo Kk | Oxygen producing method and apparatus by pressure swing method using high temperature oxygen adsorbent |
| KR20150094071A (en) * | 2014-02-10 | 2015-08-19 | 동국대학교 산학협력단 | Ceramic adsorbent for removal of oxygen |
| KR20170068801A (en) * | 2015-12-10 | 2017-06-20 | 동국대학교 산학협력단 | Method for removing oxygen in methane mixture gas by using oxygen catalyst, perovskite type oxygen removing catalyst used in the same, and land fill gas refine device applying land fill gas mathane direct converting technology using the same |
| KR101869461B1 (en) | 2015-12-10 | 2018-06-20 | 동국대학교 산학협력단 | Method for removing oxygen in methane mixture gas by using oxygen catalyst, perovskite type oxygen removing catalyst used in the same, and land fill gas refine device applying land fill gas mathane direct converting technology using the same |
Non-Patent Citations (3)
| Title |
|---|
| 1. Marchetti, L. and Forni, L., Applied Catalysis B: Env., 15, 179-187 (1998). |
| 2. Korean Chem. Eng. Res., 56(3), 297-302 (2018). |
| Journal of Membrane Science * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102255220B1 (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin | Inorganic membranes for process intensification: Challenges and perspective | |
| Lie et al. | Carbon membranes from cellulose and metal loaded cellulose | |
| KR102275948B1 (en) | Structured MOF fiber sorbent for capturing carbon dioxide and method of manufacturing the same | |
| KR101178457B1 (en) | A BSCF-5582 membrane coated with LSTF-6437 for oxygen separation and the menufacturing method thereof | |
| CN101279205B (en) | Ceramic hollow fiber oxygen permeable membrane with catalyst supported on surface and manufacture method thereof | |
| JP2013503027A (en) | Catalyst coating of membrane material | |
| Nian et al. | Preparation of a pure ZIF-67 membrane by self-conversion of cobalt carbonate hydroxide nanowires for H 2 separation | |
| Fasolin et al. | Single-step process to produce alumina supported hydroxy-sodalite zeolite membranes | |
| CN113600138B (en) | Nitrogen, oxygen and sulfur co-doped biomass charcoal material, and preparation method and application thereof | |
| KR102255220B1 (en) | Hollow fiber type LSCF oxygen removing catalyst coated with Pd, preparation method thereof, and method for removing oxygen in methane mixture gas by using the same | |
| DE102005034071B4 (en) | Method for reversible oxygen storage | |
| KR20130026639A (en) | Bscf tubular membrane coated with lstf oxide for oxygen separation and fabricating method thereof | |
| Jiang et al. | A novel porous‐dense dual‐layer composite membrane reactor with long‐term stability | |
| CN107970786B (en) | Mixed matrix membrane and preparation method thereof | |
| CN116283359A (en) | Preparation method and application of nano transition metal oxide modified flat ceramic membrane | |
| US11401213B2 (en) | Method for preparing composite metal oxide hollow fibre | |
| Ren et al. | A rational asymmetric hollow fiber membrane for oxygen permeation | |
| DE19826496B4 (en) | Oxygen ion and electron-conducting ceramic membrane, process for their preparation and their use | |
| KR102033239B1 (en) | BSCF separation membrane coated with oxide containing Ce, Sm and Sr, and preparation method thereof | |
| Othman et al. | In-situ catalytic surface modification of micro-structured La0. 6Sr0. 4Co0. 2Fe0. 8O3-δ (LSCF) oxygen permeable membrane using vacuum-assisted technique | |
| CN114381829A (en) | Microporous carbon fiber material prepared from polyacrylonitrile and used for separating multiple micromolecular gases in high selectivity manner, and preparation method and application thereof | |
| KR101460986B1 (en) | BSCF tubular Membrane coated with Barium-Chrome Based Oxide for oxygen separation and fabricating method thereof | |
| KR20140045136A (en) | Method of manufacturing pervaporation using metal ion complex | |
| Ilham et al. | Morphological and Physical Study of La0. 7Sr0. 3Co0. 2Fe0. 8O3-δ(LSCF 7328) Flat Membranes Modified by Polyethylene Glycol (PEG) | |
| Chae et al. | Oxygen permeation properties of Sm/Sr co-doped ceria decorated Ba0. 5Sr0. 5Co0. 8Fe0. 2O3-δ hollow fiber membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |