KR101661412B1 - Synthesis and applications of metal impregnated carbon catalyst from gases containing carbon dioxide - Google Patents
Synthesis and applications of metal impregnated carbon catalyst from gases containing carbon dioxide Download PDFInfo
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- KR101661412B1 KR101661412B1 KR1020150009870A KR20150009870A KR101661412B1 KR 101661412 B1 KR101661412 B1 KR 101661412B1 KR 1020150009870 A KR1020150009870 A KR 1020150009870A KR 20150009870 A KR20150009870 A KR 20150009870A KR 101661412 B1 KR101661412 B1 KR 101661412B1
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- Prior art keywords
- catalyst
- carbon
- metal
- carbon dioxide
- reaction
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 87
- 239000002184 metal Substances 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 75
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000007789 gas Substances 0.000 title claims abstract description 44
- 230000015572 biosynthetic process Effects 0.000 title claims description 9
- 238000003786 synthesis reaction Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 62
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 38
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 8
- 238000000197 pyrolysis Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910010277 boron hydride Inorganic materials 0.000 claims description 15
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- NFLRFBAIICNFNU-UHFFFAOYSA-N B.[Ca] Chemical compound B.[Ca] NFLRFBAIICNFNU-UHFFFAOYSA-N 0.000 claims description 2
- TZZUZBBNLWHWPH-UHFFFAOYSA-N B.[Mg] Chemical compound B.[Mg] TZZUZBBNLWHWPH-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZPLBDNLAPHXWKG-UHFFFAOYSA-N [Sr].B Chemical compound [Sr].B ZPLBDNLAPHXWKG-UHFFFAOYSA-N 0.000 claims description 2
- XLKNMWIXNFVJRR-UHFFFAOYSA-N boron potassium Chemical compound [B].[K] XLKNMWIXNFVJRR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000006057 reforming reaction Methods 0.000 abstract description 7
- 239000000567 combustion gas Substances 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 57
- 239000000203 mixture Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 9
- 238000007039 two-step reaction Methods 0.000 description 9
- 239000002803 fossil fuel Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- -1 alkaline earth metal boron hydride Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BEMTYRFDNZGZQX-UHFFFAOYSA-N [Zn].[Cs] Chemical compound [Zn].[Cs] BEMTYRFDNZGZQX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- RRMGGYGDQCMPKP-UHFFFAOYSA-N gold lithium Chemical compound [Li].[Au] RRMGGYGDQCMPKP-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- B01J37/088—Decomposition of a metal salt
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Abstract
본 발명은 이산화탄소가 포함된 배기 및 연소 가스를 환원제 및 금속전구체와 고온에서 반응시켜 금속 담지 탄소촉매를 얻거나 이산화탄소가 포함된 상기가스와 환원제의 반응으로부터 얻어진 탄소소재에 금속전구체를 담지시켜 금속 담지 탄소촉매를 얻을 수 있는 방법에 관한 것이다.
본 발명으로부터 얻어진 금속 담지 탄소촉매는 비교적 온건한 조건(상압)에서 이산화탄소로부터 합성되어 친환경적일 뿐만 아니라, 탄화수소 열분해를 통한 수소 생산시 탄화수소 개질반응의 촉매로 활용 될 수 있다.
탄화수소 열분해를 통해 높은 순도의 수소를 생산할 수 있을 뿐만 아니라 촉매재생 시 이산화탄소를 사용할 경우 이산화탄소로부터 부가가치가 높은 일산화탄소를 합성할 수 있다.The present invention relates to a process for producing a metal-supported carbon catalyst by reacting exhaust gas and combustion gas containing carbon dioxide at a high temperature with a reducing agent and a metal precursor or by carrying a metal precursor on a carbon material obtained from the reaction of the gas containing carbon dioxide with a reducing agent, And a method for obtaining a carbon catalyst.
The metal-supported carbon catalyst obtained from the present invention is synthesized from carbon dioxide under relatively moderate conditions (atmospheric pressure) and is environmentally friendly, and can be utilized as a catalyst for hydrocarbon reforming reaction during hydrogen production through thermal decomposition of hydrocarbons.
Hydrocarbon pyrolysis can produce hydrogen of high purity. In addition, when carbon dioxide is used for catalyst regeneration, carbon monoxide having a high added value can be synthesized from carbon dioxide.
Description
본 발명은 이산화탄소가 함유되어 있는 배기가스 및 생산공정 폐가스등으로부터 금속이 담지 된 탄소소재 촉매를 제조하고 이를 활용하는 방법에 관한 것으로서, 보다 상세하게는 이산화탄소로가 함유되어 있는 가스를 금속 전구체 및 환원제와 고온에서 반응시켜 탄소소재에 금속이 담지 된 탄소소재 촉매를 얻고 이를 탄화수소분해를 통한 수소 생산 또는 탄화수소 개질 반응에 활용하는 것이다. More particularly, the present invention relates to a method for manufacturing a carbon-based catalyst having a metal supported thereon from an exhaust gas containing carbon dioxide and waste gas from a production process, and more particularly, At high temperature to obtain a carbon material catalyst supported on a carbon material and utilize it for hydrogen production or hydrocarbon reforming reaction through hydrocarbon decomposition.
현대 사회에서 사용되는 에너지의 대부분은 석탄, 석유, 천연가스등의 화석연료에 의존하고 있다. 화석연료로부터 에너지를 얻기 위해서는 주성분이 탄화수소인 화석연료를 산소와 반응시키는데, 이러한 과정에서 이산화탄소가 필연적으로 생성되게 된다. 생성된 이산화탄소는 공기 중으로 배출되게 되는데 이는 최근 에너지 사용량의 급격한 증가에 편승하여 대기 중 이산화탄소 농도의 증가를 야기하였다. 대기 중 이산화탄소 농도의 증가는 생태계 파괴, 해수면 상승, 기후변화 등을 동반하는 온실효과를 발생시키는 주원인으로 지목 받고 있다.Most of the energy used in modern society depends on fossil fuels such as coal, oil, and natural gas. To obtain energy from fossil fuels, the main component reacts fossil fuels, which are hydrocarbons, with oxygen, which inevitably produces carbon dioxide. The resulting carbon dioxide is released into the air, which has been accompanied by an abrupt increase in recent energy use, resulting in an increase in the atmospheric carbon dioxide concentration. The increase in atmospheric carbon dioxide concentration is considered to be the main cause of the greenhouse effect accompanied by ecosystem destruction, sea level rise, and climate change.
이러한 문제를 해결하기 위해서 최근 학계에서는 화석연료를 대체할 수 있는 친환경 에너지원에 대한 연구가 활발히 이루어지고 있다. 하지만 현재 연구 중인 태양열, 수력, 지열과 같은 친환경에너지원은 화석연료에 비해 에너지 효율이 떨어지며 저장 및 이송이 힘들다. 또한 세일가스 개발로 인한 천연가스 생산량의 급격한 증가는 화석연료의 가격 인하로 이어지게 되었고 이는 친환경에너지원의 경쟁력을 더욱 떨어 감소시키는 계기가 되었다. 따라서 향후에도 주 에너지원으로 사용 될 것으로 예상되는 화석연료로 인한 온실효과를 막기 위해서는, 이산화탄소를 분리 및 포집하고 포집된 이산화탄소를 부가가치가 높은 물질로 전환하는 제조공정을 개발하는 연구가 필요로 하게 되었다. 특히, 포집된 이산화탄소의 대부분을 압축하여 매장하려는 연구가 활발한 현재 상황에서 열역학적으로 안정한 이산화탄소를 부가가치가 높은 물질로 전환하는 기술은 많은 연구진들의 관심을 끌고 있다.In order to solve these problems, researches on environmentally friendly energy sources that can replace fossil fuels have been actively conducted in academia recently. However, eco-friendly energy sources such as solar, hydro, and geothermal are under study and energy efficiency is less than fossil fuels and storage and transportation are difficult. In addition, the rapid increase in natural gas production due to the development of sales gas led to the reduction of the price of fossil fuels, which further reduced the competitiveness of environmentally friendly energy sources. Therefore, in order to prevent the greenhouse effect caused by fossil fuel, which is expected to be used as a main energy source in the future, it is necessary to develop a manufacturing process of separating and collecting carbon dioxide and converting the collected carbon dioxide into a high value-added substance . In particular, the technology to convert thermodynamically stable carbon dioxide into a high value-added substance in the current situation where research to bury most of the captured carbon dioxide is actively attracted attention of many researchers.
이산화탄소를 탄소소재로 전환하는 기술은 탄소소재의 높은 부가가치와 넓은 활용성으로 인하여 과거로부터 많은 관심을 받아왔다. 기존의 이산화탄소의 탄소소재 전환기술은 열역학적으로 안정한 이산화탄소를 환원하기 위해 고비용의 알칼리 금속 또는 고온, 고압을 필요로 하였고 이는 산업화의 어려움으로 직결되었다.(Z. Lou, Q. Chen, Y. Zhang, W. Wang, and Y. Qian, J. Am. Chem . Soc., 125(31):9302-9303(2003), L. Wei, Q. Chen, and X. Kong, J. Am. Ceram . Soc ., 94(9):3078-3083(2011)). 하지만 본 발명에서는 환원제를 이용하여 비교적 온건한 조건(상압)에서 이산화탄소를 환원시킴과 동시에 금속 전구체와 반응시켜 금속 담지 탄소소재를 합성하거나 이산화탄소로부터 합성 된 탄소소재(특허 10-1340009)에 금속을 담지시킴으로써 금속 담지 탄소소재를 합성하여 이를 촉매로 사용할 수 있음을 확인하였다. The technology to convert carbon dioxide to carbon has attracted much attention from the past due to the high added value of carbon materials and wide usability. Conventional carbon material conversion technology of carbon dioxide required expensive alkali metal, high temperature and high pressure to reduce thermodynamically stable carbon dioxide, which is directly related to industrialization difficulty (Z. Lou, Q. Chen, Y. Zhang, ... W. Wang, and Y. Qian, J. Am Chem Soc, 125 (31):.. 9302-9303 (2003), L. Wei, Q. Chen, and X. Kong, J. Am Ceram Soc ., 94 (9): 3078-3083 (2011)). However, in the present invention, carbon dioxide is reduced at relatively moderate conditions (atmospheric pressure) using a reducing agent, and at the same time, a metal-supported carbon material is synthesized by reacting with a metal precursor, or a carbon material (Patent No. 10-1340009) synthesized from carbon dioxide To synthesize a metal-supported carbon material and confirm that it can be used as a catalyst.
상세하게는 상기 촉매가 탄화수소분해를 통한 수소생산 반응 또는 탄화수소 개질반응에서 활용될 수 있음을 확인하였고 이를 시연함을 통해 본 발명을 완성하게 되었다.Specifically, it has been confirmed that the catalyst can be utilized in a hydrogen production reaction or a hydrocarbon reforming reaction through hydrocarbon decomposition.
본 발명의 목적은 환원제를 이용하여 이산화탄소가 포함된 가스를 탄소소재로 전환시킴과 동시에 열처리를 통해 금속전구체를 상기 탄소소재에 담지시킴으로써 금속 담지 탄소소재 촉매를 합성하는 방법을 제공하는 것에 있다.An object of the present invention is to provide a method for synthesizing a metal-supported carbon material catalyst by converting a gas containing carbon dioxide into a carbon material by using a reducing agent and simultaneously carrying a metal precursor on the carbon material through heat treatment.
본 발명의 목적은 이산화탄소가 포함된 가스로부터 합성된 탄소소재에 금속전구체를 담지시켜 금속 담지 탄소소재 촉매를 합성하는 방법을 제공하는 것에 있다.An object of the present invention is to provide a method of synthesizing a metal-supported carbon material catalyst by supporting a metal precursor on a carbon material synthesized from a gas containing carbon dioxide.
본 발명은 합성된 상기 금속 담지 탄소소재 촉매를 탄화수소분해 반응에 이용하여 고순도의 수소를 탄화수소로부터 얻는 방법을 제공하는 것에 목적을 두고 있다.It is an object of the present invention to provide a method for obtaining hydrogen of high purity from hydrocarbons by using the synthesized metal supported carbon material catalyst in a hydrocarbon cracking reaction.
본 발명의 목적은 합성된 상기 금속 담지 탄소소재 촉매를 이산화탄소, 수증기와 같은 산화가스에서 탄화수소 개질 반응에 이용하여 수소와 일산화탄소를 얻는 방법을 제공하는 것이다. An object of the present invention is to provide a method for obtaining hydrogen and carbon monoxide by using the synthesized carbon-supported metal-oxide catalyst in a hydrocarbon reforming reaction in an oxidizing gas such as carbon dioxide or water vapor.
상기 목적을 달성하기 위하여, 본 발명은 환원제와 금속전구체를 고온에서 이산화탄소가 포함된 가스와 반응시킴으로써 금속 담지 탄소소재 촉매 제조방법을 제공한다. In order to achieve the above object, the present invention provides a method for preparing a metal-supported carbon material catalyst by reacting a reducing agent and a metal precursor with a gas containing carbon dioxide at a high temperature.
또한, 본 발명은 환원제를 이산화탄소가 포함된 가스와 반응시켜 탄소소재를 얻고 이에 금속을 담지하여 금속 담지 탄소소재 촉매를 제조하는 방법을 제공한다.In addition, the present invention provides a method for producing a metal-supported carbon material catalyst by reacting a reducing agent with a gas containing carbon dioxide to obtain a carbon material and then supporting the metal.
본 발명은 환원제를 이용하여 이산화탄소가 포함된 가스와 금속전구체를 동시에 반응시켜 금속 담지 탄소소재를 합성하는 방법을 제공한다.The present invention provides a method for synthesizing a metal-supported carbon material by simultaneously reacting a gas containing carbon dioxide with a metal precursor using a reducing agent.
본 발명은 환원제를 이용하여 이산화탄소가 포함된 가스로부터 탄소소재를 합성한 후 금속을 담지시켜 금속 담지 탄소소재를 합성하는 방법을 제공한다.The present invention provides a method of synthesizing a carbon material from a gas containing carbon dioxide using a reducing agent, and then supporting the metal to synthesize a metal-supported carbon material.
본 발명은 상기에서 제조된 금속 담지 탄소소재를 염 제거 세척, 건조, 및 소성하는 단계를 제공한다. The present invention provides a step of desalt washing, drying, and calcining the metal supported carbon material produced above.
상기 금속 담지 탄소소재는 탄화수소분해 반응의 촉매 또는 탄화수소 개질 반응의 촉매로 사용될 수 있다.The metal-supported carbon material may be used as a catalyst for a hydrocarbon decomposition reaction or as a catalyst for a hydrocarbon reforming reaction.
본 발명은 금속 담지 탄소소재를 상압의 온전한 조건에서 이산화탄소가 포함된 가스로부터 제조함으로써 친환경적이고 경제적인 방법으로 이산화탄소를 전환 시킬 수 있다.The present invention can convert carbon dioxide in an environmentally-friendly and economical manner by preparing a metal-supported carbon material from carbon dioxide-containing gas under intact conditions at normal pressure.
상기 합성된 금속 담지 탄소소재는 금속이 금속산화물이 아닌 금속자체의 상태로 존재하므로 촉매를 사용하기에 앞서 일반적으로 진행되는 수소를 통한 촉매 환원공정 없이 탄화수소분해를 통한 수소 생산 및 탄화수소 개질 반응에 사용될 수 있다.Since the metal is not a metal oxide but a metal itself, the synthesized metal-supported carbon material can be used for hydrogen production and hydrocarbon reforming through hydrocarbon decomposition without a catalytic reduction process through hydrogen, .
또한, 상기 합성된 금속 담지 탄소소재는 수증기, 이산화탄소와 같은 산화가스를 이용한 탄화수소 개질공정의 촉매로 사용될 수 있다.In addition, the synthesized metal-supported carbon material can be used as a catalyst in a hydrocarbon reforming process using an oxidizing gas such as steam or carbon dioxide.
도 1은 본 발명의 <실시예 1>인 BC(Boron-doped porous carbon)의 제작방법을 도식화 한 것이다.
도 2는 본 발명의 <실시예 2, 3, 4, 5>인 2,3,4Ni/BC(Nickel and Boron-doped porous carbon)와 Ni-Ce/BC(Nickel, Cerium and Boron-doped porous carbon)의 제작방법을 도식화 한 것이다.
도 3은 본 발명의 <실시예 6>인 imp-Ni/BC(Nickel impregnated Boron-doped porous carbon)의 제작방법을 도식화 한 것이다.
도 4는 본 발명의 <실시예 7>인 2Ni/BC의 메탄분해반응 결과를 메탄의 전환율로 나타낸 것이다.
도 5는 본 발명의 <실시예 8>인 3Ni/BC의 메탄분해반응 결과를 메탄의 전환율로 나타낸 것이다.
도 6는 본 발명의 <실시예 9>인 4Ni/BC의 메탄분해반응 결과를 메탄의 전환율로 나타낸 것이다.
도 7는 본 발명의 <실시예 10>인 Ni-Ce/BC의 메탄분해반응 결과를 메탄의 전환율로 나타낸 것이다.
도 8는 본 발명의 <실시예 11>인 imp-Ni/BC의 메탄분해반응 결과를 메탄의 전환율로 나타낸 것이다.
도 9는 상기 <실시예 2>의 동시 반응에 의해 합성된 2Ni/BC(왼쪽)과 실시예 6의 imp_Ni/BC(오른쪽)를 촬영한 이미지이다.
도 10은 <실시예 12> (3Ni/BC, 니켈 함유량 7wt%)과 <비교예 1> (Al2O3, 니켈 함유량 12wt%)의 메탄 전환율을 비교하여 나타낸 것이다.
도 11은 본 발명의 <실시예 13>인 2Ni/BC의 메탄개질 반응 결과를 메탄 및 이산화탄소의 전환율로 나타낸 것이다.
도 12는 동시반응으로 생성된 탄소촉매를 나타내는 TEM 이미지이다.1 is a diagram illustrating a method of manufacturing a boron-doped porous carbon (BC) according to a first embodiment of the present invention.
FIG. 2 is a graph showing the relationship between the transmittance of Ni, Ce, and BC (Nickel, Cerium and Boron-doped porous carbon), which are 2,3,4 Ni / BC (Examples 2, 3, 4 and 5) ) Is schematically illustrated.
FIG. 3 is a diagram illustrating a method of manufacturing an imp-Ni / BC (Nickel impregnated boron-doped porous carbon) according to a sixth embodiment of the present invention.
FIG. 4 shows the methane conversion of 2Ni / BC, which is Example 7 of the present invention, as a result of methane decomposition.
FIG. 5 shows the methane conversion of 3Ni / BC, which is Example 8 of the present invention, as a conversion rate of methane.
6 is a graph showing the conversion of 4Ni / BC, which is Example 9 of the present invention, by methane conversion.
FIG. 7 is a graph showing the methane conversion rate of the Ni-Ce / BC decomposition reaction of Example 10 of the present invention.
FIG. 8 is a graph showing the methane conversion rate of imp-Ni / BC, which is Example 11 of the present invention.
FIG. 9 is an image of 2Ni / BC (left) synthesized by the simultaneous reaction of Example 2 and imp_Ni / BC (right) of Example 6. FIG.
10 shows the methane conversion ratios of <Example 12> (3Ni / BC, nickel content 7wt%) and <Comparative Example 1> (Al2O3, nickel content 12wt%).
Fig. 11 shows the results of methane reforming of 2Ni / BC, which is Example 13 of the present invention, as conversion rates of methane and carbon dioxide.
12 is a TEM image showing the carbon catalyst produced by the simultaneous reaction.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 금속 담지 탄소 촉매의 제조방법은 환원제를 이용하여 이산화탄소가 포함된 가스와 금속전구체를 동시에 반응시키는 단계를 포함한다(이하 동시 제조 방법).The method for producing a metal-supported carbon catalyst of the present invention comprises simultaneously reacting a gas containing carbon dioxide and a metal precursor using a reducing agent (hereinafter, referred to as a simultaneous production method).
또한, 금속 담지 탄소 촉매의 제조방법은 이산화탄소를 포함한 가스에 환원제를 반응시켜 탄소 소재를 먼저 제조하는 단계 및 상기 탄소소재에 금속 전구체를 담지하는 단계를 포함한다(이하, 2 단계 제조 방법).In addition, the method for producing a metal-supported carbon catalyst includes a step of reacting a reducing agent with a gas containing carbon dioxide to prepare a carbon material first, and a step of supporting a metal precursor on the carbon material.
상기 동시 제조 방법은 상기 금속 전구체 분말과 상기 환원제 분말을 섞어 혼합 분말을 제조한 후 상기 이산화탄소를 공급하여 고온에서 반응시켜 금속과 환원물질이 담지된 다공성 탄소소재를 제조한다. In the simultaneous production method, the metal precursor powder and the reducing agent powder are mixed to prepare a mixed powder, and the carbon dioxide is supplied and reacted at a high temperature to produce a porous carbon material carrying a metal and a reducing material.
상기 2 단계 제조 방법은 먼저 이산화탄소를 포함한 가스에 환원제를 고온에서 반응시켜 다공성의 탄소 소재를 제조한다. In the above two-step manufacturing method, a reducing agent is first reacted with a gas containing carbon dioxide at a high temperature to prepare a porous carbon material.
본 발명에 사용되는 환원제는 마그네슘(Mg), 마그네슘 하이드라이드(MgH2), 붕소 하이드라이드 환원제를 포함한다. 자세하게 붕소 하이드라이드는 알칼리금속 또는 알칼리토금속 붕소 하이드라이드가 가능하며, 구체적으로는 리튬 붕소 하이드라이드(LiBH4), 나트륨 붕소 하이드라이드(NaBH4), 칼륨 붕소 하이드라이드(KBH4), 마그네슘 붕소 하이드라이드(Mg(BH4)2), 칼슘 붕소 하이드라이드(Ca(BH4)2) 및 스트론튬 붕소 하이드라이드(Sr(BH4)2) 등의 금속 하이드라이드 일 수 있다. 또한 위의 항목 중 2종 이상을 혼합하여 사용 할 수 있다. The reducing agent used in the present invention includes magnesium (Mg), magnesium hydride (MgH 2 ), and boron hydride reducing agent. Specifically, the boron hydride can be an alkali metal or an alkaline earth metal boron hydride. Specifically, the boron hydride (LiBH 4 ), sodium boron hydride (NaBH 4), potassium boron hydride (KBH 4 ), magnesium boron hydride (Mg (BH 4 ) 2 ), calcium boron hydride (Ca (BH 4 ) 2 ) and strontium boron hydride (Sr (BH 4 ) 2 ). In addition, two or more of the above items can be mixed and used.
상기 환원제를 이용한 환원반응은 절대압력 0.01 ~ 100기압에서 수행될 수 있다.The reduction using the reducing agent may be performed at an absolute pressure of 0.01 to 100 atm.
이산화탄소를 포함한 가스는 순수 이산화탄소나 배가스(flue gas)일수 있다. The gas containing carbon dioxide can be pure carbon dioxide or flue gas.
상기 환원반응에서는 이산화탄소를 포함한 가스의 압력은 0.01 내지 100기압, 바람직하게는 0.05 ~ 50 기압일 수 있다.In the reduction reaction, the pressure of the gas containing carbon dioxide may be 0.01 to 100 atm, preferably 0.05 to 50 atm.
상기 가스에 포함된 이산화탄소 함량은 1 내지 100몰%일 수 있다. The carbon dioxide contained in the gas may be 1 to 100 mol%.
상기 환원반응은 300 내지 400℃ 이상, 바람직하게는 400℃, 더욱 바람직하게는 400 ~ 1000에서 수행될 수 있다. 상기 환원반응이 일어날 수 있는 온도는 300도 내지 400도, 바람직하게는 400도 이상인 것으로 예측되며, 이산화탄소가 카본으로 완전히 전환되기 위해서는 500℃ 이상의 온도가 필요하다. The reduction reaction may be carried out at a temperature of 300 to 400 ° C., preferably 400 ° C., more preferably 400 to 1000. The temperature at which the reduction reaction can occur is predicted to be 300 ° C to 400 ° C, preferably 400 ° C or more, and a temperature of 500 ° C or more is required for carbon dioxide to be completely converted to carbon.
상기 환원반응에서 상기 온도는 1 ~ 30/min, 바람직하게는 1~10 /min의 속도로 상승시킬 수 있다.In the reduction reaction, the temperature may be increased at a rate of 1 to 30 / min, preferably 1 to 10 / min.
상기 환원반응은 환원제를 가열로에 위치시키는 단계 ; 및 상기 가열로의 온도를 500℃까지 상승시킨 후 2~3시간 동안 상기 온도를 유지시키는 반응 단계를 포함할 수 있다. 상기 반응단계는 이산화탄소를 포함하는 가스를 가열로에 주입하는 단계를 포함한다.Wherein the reduction reaction comprises: placing a reducing agent in a heating furnace; And a reaction step of raising the temperature of the heating furnace to 500 캜 and maintaining the temperature for 2 to 3 hours. The reaction step includes injecting a gas containing carbon dioxide into a heating furnace.
상기 동시 반응의 환원반응에 의해 환원제가 붕소 하이드라이드인 경우, 붕소와 금속이 도핑된 다공성 탄소가 생성되고, 부산물로 NaBO2, Na2CO3, B2O3가 생성될 수 있다. When the reducing agent is boron hydride by the reduction reaction of the simultaneous reaction, boron and metal-doped porous carbon are produced, and by-products NaBO 2, Na 2 CO 3, B2O3 can be generated.
상기 2단계 반응의 환원반응에 의해 환원제가 붕소 하이드라이드인 경우, 붕소가 도핑된 다공성 탄소가 생성되고, 부산물로 NaBO2, Na2CO3, B2O3가 생성될 수 있다. When the reducing agent is boron hydride by the reduction reaction in the above two-step reaction, boron-doped porous carbon is produced, and NaBO 2, Na 2 CO 3, and B 2 O 3 can be produced as by-products.
상기 반응에서 이산화탄소의 전환율 또는 탄소소재의 수율은 온도와 압력의 증가에 따라 증가할 수 있으며 수득된 탄소소재의 형상은 반응조건에 따라 변할 수 있다.In this reaction, the conversion of carbon dioxide or the yield of the carbon material may increase with increasing temperature and pressure, and the shape of the obtained carbon material may vary depending on the reaction conditions.
상기 동시반응에서는 상기 환원반응에 의해 이산화탄소와 환원제와의 반응에 의해 카본이 형성됨과 동시에 상기 환원제와 혼합된 금속전구체로부터 금속이 상기 카본 물질 내부에 담지 또는 도핑된다.In the simultaneous reaction, carbon is formed by the reaction between the carbon dioxide and the reducing agent by the reduction reaction, and the metal is supported or doped in the carbon material from the metal precursor mixed with the reducing agent.
상기 2 단계 반응에서는 금속 전구체 용액을 이용하여 환원반응에 의해 형성된 탄소 소재에 금속이 담지된다. In the two-step reaction, a metal is supported on the carbon material formed by the reduction reaction using the metal precursor solution.
동시반응에서는 환원반응 과정을 통해 상기 금속이 카본 물질에 함유되는데, 결과적으로 금속은 상기 카본 물질 내부나 표면에 함유될 수 있다. 좀 더 구체적으로는, 금속이 내부 코어가 되고, 탄소가 상기 금속을 둘러싸는 코어-쉘 구조일 수 있다. 동시반응으로 촉매합성 시, 금속 전구체의 표면에 CO2로부터 형성된 탄소가 쌓이면서 core-shell 구조로 형성될 수 있다. In the simultaneous reaction, the metal is contained in the carbon material through a reduction reaction process. As a result, the metal may be contained in the carbon material or on the surface. More specifically, the metal may be an inner core, and carbon may be a core-shell structure surrounding the metal. During the catalyst synthesis by the simultaneous reaction, the carbon formed from the CO 2 may accumulate on the surface of the metal precursor to form a core-shell structure.
한편, 2 단계 반응에서는 이미 제조된 탄소 소재의 세공을 통해 탄소 내부로 금속이 담지된다.On the other hand, in the two-step reaction, the metal is carried into the carbon through the pores of the carbon material already produced.
본 발명에서 사용되는 함유, 도핑, 또는 담지는 금속이 탄소 소재 내부 또는 표면에 포함되어 있음을 나타낸다. 즉, 본 발명에서는 "담지"라는 용어가 침지, 분무, 침적 등에 의해 탄소 소재의 세공 또는 표면에 금속이 침투하여 고정되는 것을 나타내는 것뿐만이 아니라 상기 동시 반응에 의해 탄소 소재 내부에 균일하게 도핑되어 함유된 것을 포함하는 의미로 사용될 수 있으며, 또한, 금속의 코어 형태로 존재하는 경우도 포함하는 의미로 사용될 수 있다. The contained, doped, or supported metal used in the present invention indicates that the metal is contained in or on the surface of the carbon material. That is, in the present invention, the term "supported" means not only that the metal penetrates and is fixed to the pores or the surface of the carbon material by immersion, spraying, dipping or the like, but is also uniformly doped into the carbon material by the simultaneous reaction And may also be used in the meaning including the case of a core of a metal.
상기 동시 반응과 2단계 반응은 금속이 탄소 소재 내부에 담지되는 양태가 서로 다르다. 좀 더 구체적으로는, 상기 동시반응에서는 코어-쉘 구조로 형성되거나 또는 세공뿐만 아니라 탄소 소재 내부 또는 표면 전체에 걸쳐 균일하게 금속이 담지될 수 있으며, 상기 2 단계 반응에서는 주로 탄소 소재의 세공을 통해 금속이 담지될 수 있다. 특히, 2 단계 반응에서는 세공을 통해 금속이 담지되므로 외부에 노출된 금속의 일부는 금속 산화물 형태로 존재할 수 있다. 후술하는 실시예를 참고하면, 동시반응에서 형성된 금속 단지 탄소 촉매가 2 단계 반응에서의 촉매에 비해 반응 효율(전환율)이 월등히 높다.The simultaneous reaction and the two-step reaction differ in the manner in which the metal is supported in the carbon material. More concretely, in the simultaneous reaction, the metal may be formed in a core-shell structure or may be uniformly supported not only in the pores but also in the carbon material or the entire surface. In the two-step reaction, Metal may be carried. Particularly, in the two-step reaction, since the metal is supported through the pores, a part of the metal exposed to the outside may exist in the form of metal oxide. Referring to Examples described later, the metal complex carbon catalyst formed in the simultaneous reaction is much higher in reaction efficiency (conversion ratio) than the catalyst in the two-step reaction.
상기 금속 전구체로는 전이금속, 알칼리 금속, 알칼리토금속 또는 귀금속 일 수 있으며, 구체적으로는 전이금속은 니켈(Ni), 코발트(Co), 구리(Cu), 아연(Zn), 티타늄(Ti), 철(Fe) 또는 망간(Mn)이며, 알칼리금속은 리튬(Li), 나트륨(Na) 또는 세슘(Cs)이고, 알칼리토금속은 마그네슘(Mg), 칼슘(Ca) 또는 스트론튬(Sr)이며 귀금속은 금(Au), 백금(Pt) 또는 은(Ag)일 수 있다. 또한 위의 항목 중 단일종이나 2종 이상을 혼합하여 사용 할 수 있다.The metal precursor may be a transition metal, an alkali metal, an alkaline earth metal, or a noble metal. Specifically, the transition metal may be Ni, Co, Cu, Zn, (Mg), calcium (Ca), or strontium (Sr), and the noble metal is selected from the group consisting of iron (Fe) and manganese (Mn), and the alkali metal is lithium Gold (Au), platinum (Pt), or silver (Ag). In addition, one of the above items or a mixture of two or more species can be used.
상기 이산화탄소가 포함된 가스로부터 합성된 탄소소재를 합성 후, 금속 전구체를 담지하여 금속 담지 탄소소재를 합성할 때 적합한 금속은 전이금속, 알칼리 금속, 알칼리토금속 또는 귀금속 일 수 있으며, 구체적으로는 전이금속은 니켈(Ni), 코발트(Co), 구리(Cu), 아연(Zn), 티타늄(Ti), 철(Fe) 또는 망간(Mn)이며, 알칼리금속은 리튬(Li), 나트륨(Na) 또는 세슘(Cs)이고, 알칼리토금속은 마그네슘(Mg), 칼슘(Ca) 또는 스트론튬(Sr)이며 귀금속은 금(Au), 백금(Pt) 또는 은(Ag)일 수 있다. 또한 위의 항목 중 단일종이나 2종 이상을 혼합하여 사용 할 수 있다.When synthesizing a carbon material synthesized from the gas containing carbon dioxide and synthesizing a metal-supported carbon material by supporting a metal precursor, the metal may be a transition metal, an alkali metal, an alkaline earth metal, or a noble metal, And the alkali metal is lithium (Li), sodium (Na), or nickel (Ni), cobalt (Co), copper (Cu), zinc Cesium (Cs), the alkaline earth metal is magnesium (Mg), calcium (Ca) or strontium (Sr) and the noble metal may be gold (Au), platinum (Pt) or silver (Ag). In addition, one of the above items or a mixture of two or more species can be used.
상기 언급된 금속의 전구체는 상기에 언급된 순수한 금속, 금속염, 수화물 및 산화물 등에서 1종 이상 선택할 수 있다. 금속염 중 염화물은 PtCl2,PtCl4,AuCl2,AuCl3등을 예로 들 수 있으며, 탄산염은 NiCO3,CoCO3,Li2CO3,FeCO3등을 예로 들 수 있으며, 수화물은 Ni(NO3)2*6H2O, NiCl2*xH2O, NiBr2*3H2O등을 예로 들 수 있으며 산화물은 NiO, FeO, Fe2O3등을 예로 들 수 있다. 하지만 이러한 예시에 국한되지 않으며 상기에 언급된 금속을 포함한 어떤 형태의 물질도 사용될 수 있다. The above-mentioned metal precursors may be selected from one or more of the above-mentioned pure metals, metal salts, hydrates and oxides. Metal salts of chloride, and the like are exemplified PtCl 2, PtCl 4, AuCl 2 , AuCl 3, carbonate and the like are exemplified NiCO 3, CoCO 3, Li 2 CO 3, FeCO 3, a hydrate is Ni (NO 3 ) 2 * 6H 2 O, NiCl 2 * xH 2 O, and NiBr 2 * 3H 2 O. Examples of the oxide include NiO, FeO, Fe 2 O 3 and the like. However, it is not limited to these examples and any type of material including the above-mentioned metals may be used.
다만, 바람직하게는, 상기 동시반응에서는 무수화물 금속전구체를 사용하고, 2 단계 반응에서는 수화물과 같은 용액에 녹을 수 있는 금속 전구체를 사용할 수 있다. 이는 동시반응에 수화물 금속 전구체를 사용하는 경우 NaBH4등의 환원제와 만나서 발화의 위험성 및 이산화탄소 전환율이 떨어질 수 있고 2단계 반응에서는 수화물을 사용하여야 물과 같은 용매에 잘 녹아 분산이 용이하기 때문이다.Preferably, however, a precursor metal precursor is used in the simultaneous reaction and a metal precursor which can be dissolved in a solution such as a hydrate in the two-step reaction. This is because, if a hydrate metal precursor is used in the simultaneous reaction, the risk of ignition and the conversion of carbon dioxide may be lowered by contacting with a reducing agent such as NaBH4, and in the case of the second step reaction, hydration should be used to facilitate dissolution in a solvent such as water.
상기 언급된 금속전구체의 사용량은 환원제 대비 1~ 200몰%일 수 있으며 사용량에 따라 최종 생성물의 금속 담지 정도가 결정된다. The amount of the metal precursor used may be 1 to 200 mol% based on the reducing agent, and the degree of metal deposition of the final product is determined according to the amount of the metal precursor used.
상기 2 단계 반응에서 상기 금속 담지 방법은 공지된 방법을 사용할 수 있다. 예를 들면, 상기 담지 방법으로 합침 또는 공침법을 이용할 수 있다. In the two-step reaction, the metal supporting method may be a known method. For example, coalescence or coprecipitation can be used as the above-mentioned supporting method.
좀 더 구체적으로, 상기 담지 방법은 분무법, 증발건조법, 단순침적법, 침전법으로 이루어진 군에서 1종 이상 선택될 수 있다.More specifically, one or more of the above-mentioned methods of supporting can be selected from the group consisting of spraying, evaporation drying, simple deposition, and precipitation.
상기 분무법은 상기 탄소소재에 금속전구체를 포함하는 용액을 분무하는 방법이다.The spraying method is a method of spraying a solution containing a metal precursor on the carbon material.
상기 증발건조법은 상기 탄소소재를 금속전구체 용액에 넣은 후 가열하여 용매를 증발시켜 금속을 담지하는 방법이다.In the evaporation and drying method, the carbon material is put in a metal precursor solution and heated to evaporate the solvent to carry the metal.
상기 단순침적법은 상기 탄소소재를 금속전구체 용액에 넣어 탄소 소재 세공에 금속을 담지시키는 방법이다.In the simple deposition method, the carbon material is placed in a metal precursor solution to support the metal material in the carbon material pores.
상기 침전법은 상기 탄소소재를 금속전구체 용액에 넣은 후 침전제를 가하여 금속을 침전시켜 담지시키는 방법이다.In the precipitation method, the carbon material is placed in a metal precursor solution, and a precipitant is added to precipitate the metal to support the carbon precursor solution.
본 발명에 의해 합성된 금속 담지 탄소소재는 합성과정에 포함될 수 있는 불순물 염을 제거하여 순도를 높이기 위해 산, 온수, 냉수 또는 알코올 세척 할 수 있다. The metal-supported carbon material synthesized by the present invention can be washed with acid, hot water, cold water or alcohol to remove impurity salts which may be included in the synthesis process and thereby increase the purity.
상기 산은 구체적으로 염산, 황산 등이 사용가능하며 알코올은 메탄올, 에탄올 등이 사용 가능하다. 이 때 산 또는 알코올의 순도는 1 ~ 100몰%, 온도는 0 ~ 100 일 수 있다.Specifically, hydrochloric acid, sulfuric acid and the like can be used as the acid, and methanol, ethanol and the like can be used as the alcohol. In this case, the purity of the acid or alcohol may be 1 to 100 mol%, and the temperature may be 0 to 100.
상기 과정에 의해 세척된 금속 담지 탄소소재를 건조하는 단계는 절대압력 0 ~ 1기압에서 50 ~ 150℃, 바람직하게는 90 ~ 120℃에서 액체가 모두 제거될 때까지 진행한다.The step of drying the metal-supported carbonaceous material washed by the above process proceeds until the liquid is completely removed at a pressure of 0-1 at an absolute pressure of 50-150 ° C, preferably at a temperature of 90-120 ° C.
상기 과정에서 건조된 금속 담지 탄소소재는 절대압력 1 ~ 10기압의 비활성 가스, 구체적으로 질소, 아르곤 등의 흐름에서 300 ~ 1200℃의 조건에서 소성된다.The metal-supported carbon material dried in the above process is calcined under the conditions of an inert gas having an absolute pressure of 1 to 10 atm, specifically, a flow of nitrogen or argon at a temperature of 300 to 1200 ° C.
다른 양상에서, 본 발명은 상기 방법에서 제조된 탄소 촉매에 관계한다. In another aspect, the present invention relates to a carbon catalyst prepared in the process.
도 12는 동시반응으로 생성된 탄소촉매를 나타내는 TEM 이미지이다. 도 12를 참고하면, 상기 탄소 촉매는 금속이 내부 코어가 되고, 탄소가 상기 금속을 둘러싸는 코어-쉘 구조일 수 있다. 동시반응으로 촉매합성 시, 금속 전구체의 표면에 CO2로부터 형성된 탄소가 쌓이면서 core-shell 구조로 형성된다. 12 is a TEM image showing the carbon catalyst produced by the simultaneous reaction. Referring to FIG. 12, the carbon catalyst may be a core-shell structure in which the metal becomes an inner core and carbon surrounds the metal. During the catalyst synthesis by the simultaneous reaction, carbon formed from CO 2 is accumulated on the surface of the metal precursor and formed into a core-shell structure.
상기 탄소 촉매는 그 내부 또는 표면에 상기 금속이 담지되거나 상기 탄소 소재의 세공에 금속이 담지된다.The metal catalyst is supported on the inside or the surface of the carbon catalyst or the metal is supported on the pores of the carbon material.
상기 금속은 환원 상태로 존재할 수 있다.The metal may be in a reduced state.
상기 촉매는 열분해 반응을 통해 탄화수소로부터 수소와 탄소를 생산하는 탄화수소 분해 반응의 촉매로 사용 할 수 있다.The catalyst can be used as a catalyst for hydrocarbon decomposition reaction which produces hydrogen and carbon from hydrocarbons through pyrolysis reaction.
상기 탄화수소는 절대압력 1 ~ 10기압, 500 ~ 1100도의 조건에서 하기 반응식 1을 통해 수소와 탄소로 분해된다.The hydrocarbons are decomposed into hydrogen and carbon through the following
상기 탄화수소는 탄소수 1~20인 선형 또는 분지형 알킬기, 탄소수 2~10인알켄기일 수 있으며, 바람직하게는 메탄을 사용한다.The hydrocarbon may be a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, preferably methane.
<반응식 1><
CxHy → xC + y/2H2CxHy? XC + y / 2H2
이때, 생성된 탄소는 촉매에 코킹되어 있으며 절대압력 1 ~ 10기압와 500 ~ 1100℃ 조건에서 수증기나 산소, 이산화탄소등과 반응하여 제거된다. 재생된 촉매는 공정에 재사용될 수 있다.At this time, the generated carbon is caulked to the catalyst and is removed by reacting with water vapor, oxygen, carbon dioxide, etc. under the conditions of absolute pressure of 1 to 10 atm and 500 to 1100 ° C. The regenerated catalyst can be reused in the process.
또한, 본 발명에서 합성된 금속 담지 탄소 촉매는 1 ~ 10기압 500 ~ 1100℃ 조건에서 이산화탄소나 수증기를 탄화수소와 반응시켜 수소와 일산화탄소를 생산하는 하기 반응식 2의 촉매로 사용될 수 있다. 상기 탄화수소는 탄소수 1~20인 선형 또는 분지형 알킬기, 탄소수 2~10인 알켄기일 수 있으며, 바람직하게는 메탄을 사용한다. The metal-supported carbon catalyst synthesized in the present invention can be used as a catalyst of Reaction Scheme 2 for producing hydrogen and carbon monoxide by reacting carbon dioxide or water vapor with hydrocarbons under the conditions of 1 to 10 atm and 500 to 1100 ° C. The hydrocarbon may be a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, preferably methane.
<반응식 2><Reaction Scheme 2>
CH4 + CO2 → 2H2 + 2COCH4 + CO2 - > 2H2 + 2CO
또한, 본 발명에서 고안된 방법을 통해 합성된 금속 담지 탄소소재는 1 ~ 30기압 500 ~ 1100℃ 조건에서 물과 메탄과 반응시켜 수소와 일산화탄소를 생산하는 하기 반응식 3의 합성가스 제조 촉매로 사용될 수 있다.In addition, the metal-supported carbon material synthesized through the process of the present invention can be used as a synthesis gas-producing catalyst of the following reaction scheme 3, which produces hydrogen and carbon monoxide by reacting with water and methane under the conditions of 1 to 30 atmospheres and 500 to 1100 ° C .
<반응식 3><Reaction Scheme 3>
CH4 + H2O → 3H2 + COCH4 + H2O - > 3H2 + CO
본 발명을 통해 합성된 금속 담지 탄소소재는 상기 탄화수소를 이용한 수소 생성 또는 탄화수소 개질 반응의 촉매로 사용될 수 있기 때문에 이산화탄소를 가치 있는 물질로 변환시키는 이산화탄소 전환기술의 발명의 목적에 부합한다. Since the metal-supported carbon material synthesized through the present invention can be used as a catalyst for hydrogen generation using hydrocarbon or hydrocarbon reforming reaction, it meets the object of the invention of carbon dioxide conversion technology for converting carbon dioxide into valuable materials.
이하 본 발명을 하기 실시예를 통하여 구체적으로 설명하겠으나, 하기 실시 예는 본 발명을 예시하기 위한 것이며 본 발명이 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
<실시예 1>≪ Example 1 >
붕소 하이드라이드를 이용하여 이산화탄소로부터 탄소소재를 제조하는 방법을 다음과 같이 구체적으로 기재한다.A method for producing a carbon material from carbon dioxide using boron hydride will be described in detail as follows.
상기 언급된 붕소 하이드라이드 중 나트륨 붕소 하이드라이드 5.21g(NaBH4, >96%, Sigma-Aldrich)을 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 이산화탄소(CO2, >99.8%, 삼오가스)를 76㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 500까지 올려준 뒤 2시간 동안 500℃로 유지시켰다. 반응기가 식은 후 생성된 BC(Boron-doped porous carbon)를 온수, 냉수 및 에탄올로 세척하였다. 5.21 g of sodium boron hydride (NaBH4,> 96%, Sigma-Aldrich) in the above-mentioned boron hydride was charged into an alumina crucible and placed in a furnace and 76 ml of carbon dioxide (CO2,> 99.8% / min < / RTI > for 1 hour. The temperature of the reactor was then increased from 25 to 500 at 5 / min and maintained at 500 ° C for 2 hours. After the reactor was cooled, the resulting boron-doped porous carbon (BC) was washed with hot water, cold water and ethanol.
온수 세척은 250㎖ 비커에 200㎖ 증류수를 넣고 80℃로 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다. 이 후 상기 세척과정을 4회 더 반복하였다. 다음으로 냉수 세척은 250㎖ 비커에 200㎖ 증류수를 넣고 상온에서 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다. 이 후 상기 세척과정을 3회 더 반복하였다. 마지막으로 에탄올 세척은 250㎖ 비커에 200㎖ 에탄올(Ethanol, >99%, 대정)을 넣고 상온에서 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다.For hot water washing, 200 ml of distilled water was added to a 250 ml beaker, and the mixture was stirred at 80 ° C for 30 minutes at 300 rpm, and the washed material was filtered through a 1 μm filter paper. The washing process was then repeated four more times. Next, cold water washing was performed by adding 200 ml of distilled water to a 250 ml beaker, stirring the mixture at 300 rpm for 30 minutes at room temperature, and then washing the washed material with 1 쨉 m filter paper. The washing process was then repeated three more times. Finally, 200 ml ethanol (Ethanol,> 99%, Daejung) was added to a 250 ml beaker, and the mixture was stirred at 300 rpm for 30 minutes at room temperature. Then, the washings were filtered through a 1 占 퐉 filter paper.
상기 세척과정을 통해 염을 제거한 침전물을 절대압력 1기압, 120 오븐에서 하루 동안 건조시켰다. 건조된 BC는 소성의 과정을 거치는데 소성의 자세한 과정은 아래와 같다.The precipitate from which the salt was removed through the above washing process was dried for one day under an absolute pressure of 1 atm at 120 oven. The dried BC is subjected to a calcination process. The detailed procedure of calcination is as follows.
건조된 BC를 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 아르곤(Ar, >99.9, 삼오가스)을 50㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 1000℃까지 올려준 뒤 2시간 동안 1000℃로 유지키고 상온까지 냉각하였다.The dried BC was immersed in an alumina crucible and placed in a furnace, and argon (Ar, > 99.9, tri-ozone gas) was purged for 1 hour while flowing at 50 ml / min. The temperature of the reactor was increased from 25 to 1000 ° C at a rate of 5 / min, maintained at 1000 ° C for 2 hours, and then cooled to room temperature.
상기 과정을 통해 이산화탄소로부터 탄소재료를 합성하였으며 이를 [도 1]에서 도식화하였다. Through the above process, a carbon material was synthesized from carbon dioxide, which was illustrated in FIG.
<실시예 2,3,4><Examples 2, 3, and 4>
붕소 하이드라이드를 이용하여 이산화탄소로부터 니켈 담지 탄소소재를 제조하는 방법을 다음과 같이 구체적으로 기재한다.A method for producing a nickel-supported carbon material from carbon dioxide using boron hydride will be described in detail as follows.
상기 언급된 붕소 하이드라이드 중 나트륨 붕소 하이드라이드 5.21g(NaBH4, >96%, Sigma-Aldrich)과 니켈 카보네이트(NiCO3) 0.25g<실시예 2>, 0.5g<실시예 3>, 0.75g<실시예 4>, (NiCO3, 99%>, Sigma-Aldrich)을 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 이산화탄소(CO2, >99.8%, 삼오가스)를 76㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 500℃까지 올려준 뒤 2시간 동안 500℃로 유지시켰다. 반응기가 식은 후 생성된 2Ni/BC<실시예 2>, 3Ni/BC<실시예 3>, 4Ni/BC<실시예 4> (Nickel and Boron-doped porous carbon)를 온수, 냉수 및 에탄올로 세척하였다. The above-mentioned boron hydride, sodium boron hydride 5.21g (NaBH4,> 96%, Sigma-Aldrich) and nickel carbonate (NiCO 3) 0.25g <Example 2>, 0.5g <Example 3>, 0.75g < (CO 2 , > 99.8%, tri-ozone gas) at 76 ml / min in a furnace, and then fired for 1 hour in a furnace. Respectively. After that, the temperature of the reactor was increased from 25 to 500 ° C at 5 / min and then maintained at 500 ° C for 2 hours. After the reactor was cooled, 2Ni / BC (Example 2), 3Ni / BC (Example 3), 4Ni / BC (Nickel and Boron-doped porous carbon) were washed with hot water, cold water and ethanol .
온수 세척은 250㎖ 비커에 200㎖ 증류수를 넣고 80로 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다. 이 후 상기 세척과정을 4회 더 반복하였다. 다음으로 냉수 세척은 250㎖ 비커에 200㎖ 증류수를 넣고 상온에서 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다. 이 후 상기 세척과정을 3회 더 반복하였다. 마지막으로 에탄올 세척은 250㎖ 비커에 200㎖ 에탄올(Ethanol, >99%, 대정)을 넣고 상온에서 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다.In hot water washing, 200 ml of distilled water was added to a 250 ml beaker, and the mixture was stirred at 300 rpm for 30 minutes at 80 ° C, and the washed material was filtered through a 1 μm filter paper. The washing process was then repeated four more times. Next, cold water washing was performed by adding 200 ml of distilled water to a 250 ml beaker, stirring the mixture at 300 rpm for 30 minutes at room temperature, and then washing the washed material with 1 쨉 m filter paper. The washing process was then repeated three more times. Finally, 200 ml ethanol (Ethanol,> 99%, Daejung) was added to a 250 ml beaker, and the mixture was stirred at 300 rpm for 30 minutes at room temperature. Then, the washings were filtered through a 1 占 퐉 filter paper.
상기 세척과정을 통해 염을 제거한 침전물을 절대압력 1기압, 120 오븐에서 하루 동안 건조시켰다. 건조된 Ni/BC는 소성의 과정을 거치는데 소성의 자세한 과정은 아래와 같다.The precipitate from which the salt was removed through the above washing process was dried for one day under an absolute pressure of 1 atm at 120 oven. The dried Ni / BC undergoes the firing process. The detailed process of firing is as follows.
건조 된 Ni/BC를 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 아르곤(Ar, >99.9, 삼오가스)을 50㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 1000℃까지 올려준 뒤 2시간 동안 1000℃로 유지키고 상온까지 냉각하였다.The dried Ni / BC was immersed in an alumina crucible and then placed in a furnace and argon (Ar, > 99.9, tri-ozone gas) was purged for 1 hour while flowing at 50 ml / min. The temperature of the reactor was increased from 25 to 1000 ° C at a rate of 5 / min, maintained at 1000 ° C for 2 hours, and then cooled to room temperature.
상기 과정을 통해 나트륨 붕소 하이드라이드를 이용하여 이산화탄소로부터 니켈 담지 탄소재료를 합성하였으며 이를 [도 2]에서 도식화 하였다. Through the above process, a nickel-supported carbon material was synthesized from carbon dioxide using sodium boron hydride, and this was illustrated in FIG. 2.
<실시예 5>≪ Example 5 >
붕소 하이드라이드를 이용하여 이산화탄소로부터 니켈 및 세륨 담지 탄소소재를 제조하는 방법을 다음과 같이 구체적으로 기재한다.A method for producing nickel and cerium-supported carbon materials from carbon dioxide using boron hydride will be described in detail as follows.
상기 언급된 붕소 하이드라이드 중 나트륨 붕소 하이드라이드 5.21g(NaBH4, >96%, Sigma-Aldrich)과 니켈 카보네이트(NiCO3, Sigma-Aldrich) 0.5g, 세륨 옥사이드(CeO2) 0.2g, Sigma-Aldrich)을 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 이산화탄소(CO2, >99.8%, 삼오가스)를 76㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 500℃까지 올려준 뒤 2시간 동안 500℃로 유지시켰다. 반응기가 식은 후 생성된 Ni-Ce/BC (Nickel, Cerium and Boron-doped porous carbon)를 온수, 냉수 및 에탄올로 세척하였다. Hyde sodium fluoride, boron fluoride of the above-mentioned boron-hydroxy 5.21g (NaBH4,> 96%, Sigma-Aldrich) and nickel carbonate (NiCO 3, Sigma-Aldrich) 0.5g, cerium oxide (CeO 2) 0.2g, Sigma- Aldrich ) Was placed in an alumina crucible and then put into a furnace and purged for 1 hour while flowing carbon dioxide (CO 2 ,> 99.8%, and samarium gas) at 76 ml / min. After that, the temperature of the reactor was increased from 25 to 500 ° C at 5 / min and then maintained at 500 ° C for 2 hours. After the reactor was cooled, the resulting Ni-Ce / BC (nickel, cerium and boron-doped porous carbon) was washed with hot water, cold water and ethanol.
온수 세척은 250㎖ 비커에 200㎖ 증류수를 넣고 80℃로 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다. 이 후 상기 세척과정을 4회 더 반복하였다. 다음으로 냉수 세척은 250㎖ 비커에 200㎖ 증류수를 넣고 상온에서 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다. 이 후 상기 세척과정을 3회 더 반복하였다. 마지막으로 에탄올 세척은 250㎖ 비커에 200㎖ 에탄올(Ethanol, >99%, 대정)을 넣고 상온에서 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다.For hot water washing, 200 ml of distilled water was added to a 250 ml beaker, and the mixture was stirred at 80 ° C for 30 minutes at 300 rpm, and the washed material was filtered through a 1 μm filter paper. The washing process was then repeated four more times. Next, cold water washing was performed by adding 200 ml of distilled water to a 250 ml beaker, stirring the mixture at 300 rpm for 30 minutes at room temperature, and then washing the washed material with 1 쨉 m filter paper. The washing process was then repeated three more times. Finally, 200 ml ethanol (Ethanol,> 99%, Daejung) was added to a 250 ml beaker, and the mixture was stirred at 300 rpm for 30 minutes at room temperature. Then, the washings were filtered through a 1 占 퐉 filter paper.
상기 세척과정을 통해 염을 제거한 침전물을 절대압력 1기압, 120℃ 오븐에서 하루 동안 건조시켰다. 건조된 Ni/BC는 소성의 과정을 거치는데 소성의 자세한 과정은 아래와 같다.The precipitate from which the salt was removed through the above washing process was dried in an oven at 120 ° C for 1 day under an absolute pressure of 1 atm. The dried Ni / BC undergoes the firing process. The detailed process of firing is as follows.
건조된 Ni/BC를 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 아르곤(Ar, >99.9, 삼오가스)을 50㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 1000℃까지 올려준 뒤 2시간 동안 1000℃로 유지시키고 상온까지 냉각하였다.The dried Ni / BC was immersed in an alumina crucible and then placed in a furnace and argon (Ar, > 99.9, tri-ozone gas) was purged for 1 hour while flowing at 50 ml / min. After that, the temperature of the reactor was increased from 25 to 1000 ° C at a rate of 5 / min, maintained at 1000 ° C for 2 hours, and then cooled to room temperature.
상기 과정을 통해 나트륨 붕소 하이드라이드를 이용하여 이산화탄소로부터 니켈 세륨 담지 탄소재료를 합성하였으며 이를 [도 2]에서 도식화 하였다. Through the above process, a nickel cerium-supported carbon material was synthesized from carbon dioxide using sodium borohydride, and this was illustrated in FIG. 2.
<실시예 6>≪ Example 6 >
붕소 하이드라이드를 이용하여 이산화탄소로부터 담지 탄소소재를 제조하는 방법을 다음과 같이 구체적으로 기재한다.A method for producing a supported carbon material from carbon dioxide using boron hydride will be described in detail as follows.
상기 언급된 붕소 하이드라이드 중 나트륨 붕소 하이드라이드 5.21g(NaBH4, >96%, Sigma-Aldrich)을 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 이산화탄소(CO2, >99.8%, 삼오가스)를 76㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 500℃까지 올려준 뒤 2시간 동안 500℃로 유지시켰다. 반응기가 식은 후 생성된 BC를 온수, 냉수 및 에탄올로 세척하였다. 5.21 g of sodium boron hydride (NaBH4,> 96%, Sigma-Aldrich) in the above-mentioned boron hydride was charged into an alumina crucible and placed in a furnace and 76 ml of carbon dioxide (CO2,> 99.8% / min < / RTI > for 1 hour. After that, the temperature of the reactor was increased from 25 to 500 ° C at 5 / min and then maintained at 500 ° C for 2 hours. After the reactor was cooled, the resulting BC was washed with hot water, cold water and ethanol.
온수 세척은 250㎖ 비커에 200㎖ 증류수를 넣고 80로 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다. 이 후 상기 세척과정을 4회 더 반복하였다. 다음으로 냉수 세척은 250㎖ 비커에 200㎖ 증류수를 넣고 상온에서 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다. 이 후 상기 세척과정을 3회 더 반복하였다. 마지막으로 에탄올 세척은 250㎖ 비커에 200㎖ 에탄올(Ethanol, >99%, 대정)을 넣고 상온에서 30분 동안 300rpm으로 교반한 뒤 세척물을 1㎛ 여과지에 여과하였다.In hot water washing, 200 ml of distilled water was added to a 250 ml beaker, and the mixture was stirred at 300 rpm for 30 minutes at 80 ° C, and the washed material was filtered through a 1 μm filter paper. The washing process was then repeated four more times. Next, cold water washing was performed by adding 200 ml of distilled water to a 250 ml beaker, stirring the mixture at 300 rpm for 30 minutes at room temperature, and then washing the washed material with 1 쨉 m filter paper. The washing process was then repeated three more times. Finally, 200 ml ethanol (Ethanol,> 99%, Daejung) was added to a 250 ml beaker, and the mixture was stirred at 300 rpm for 30 minutes at room temperature. Then, the washings were filtered through a 1 占 퐉 filter paper.
상기 세척과정을 통해 염을 제거한 침전물을 절대압력 1기압, 120℃오븐에서 하루 동안 건조시켰다. 건조된 BC는 소성의 과정을 거치는데 소성의 자세한 과정은 아래와 같다.The precipitate from which the salt was removed through the above washing process was dried in an oven at 120 ° C for 1 day under an absolute pressure of 1 atm. The dried BC is subjected to a calcination process. The detailed procedure of calcination is as follows.
건조된 BC를 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 아르곤(Ar, >99.9, 삼오가스)을 50㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 1000℃까지 올려준 뒤 2시간 동안 1000℃로 유지키고 상온까지 냉각하였다.The dried BC was immersed in an alumina crucible and placed in a furnace, and argon (Ar, > 99.9, tri-ozone gas) was purged for 1 hour while flowing at 50 ml / min. The temperature of the reactor was increased from 25 to 1000 ° C at a rate of 5 / min, maintained at 1000 ° C for 2 hours, and then cooled to room temperature.
소성된 BC 0.2g과 니켈나이트라이트 헥사하이드라이드(Ni(NO3)2*6H2O,) 0.1616g을 20㎖ 바이알에 넣고 10㎖ 증류수를 투입하였다. 이후 30에서 500rpm으로 교반하여 하루 동안 담지시켰다.0.2 g of calcined BC and 0.1616 g of nickel nitrite hexahydride (Ni (NO 3 ) 2 * 6H 2 O,) were placed in a 20 mL vial and 10 mL of distilled water was added. Thereafter, the mixture was stirred at 30 to 500 rpm for a day.
담지 된 imp-Ni/BC(Ni impregnated boron-doped porous carbon)을 절대압력 1기압, 120 오븐에서 하루 동안 건조시켰다. 건조된 imp-Ni/BC는 소성의 과정을 거치는데 소성의 자세한 과정은 아래와 같다.The supported imp-Ni / BC (Ni impregnated boron-doped porous carbon) was dried for one day under an absolute pressure of 1 atm in a 120 oven. The dried imp-Ni / BC undergoes a firing process. The detailed process of firing is as follows.
건조된 imp-Ni/BC를 알루미나 도가니에 담은 뒤 반응기(Furnace)에 넣고 아르곤(Ar, >99.9, 삼오가스)을 50㎖/min로 흘리며 1시간 퍼지하였다. 이 후 반응기의 온도는 5/min으로 25에서 1000℃까지 올려준 뒤 2시간 동안 1000℃로 유지키고 상온까지 냉각하였다.The imp-Ni / BC dried was impregnated in an alumina crucible and then placed in a furnace and purged with argon (Ar,> 99.9, tri-ozone) at 50 ml / min for 1 hour. The temperature of the reactor was increased from 25 to 1000 ° C at a rate of 5 / min, maintained at 1000 ° C for 2 hours, and then cooled to room temperature.
상기 과정을 통해 이산화탄소로부터 니켈 담지 탄소재료를 합성하였으며 이를 [도 3]에서 도식화 하였다. Through the above process, a nickel-supported carbon material was synthesized from carbon dioxide, which was illustrated in FIG.
<실시예 7, 8, 9, 10, 11, 12, 비교예 1><Examples 7, 8, 9, 10, 11, and 12, Comparative Example 1>
상기 <실시예 2, 3, 4, 5, 6>를 통해 합성된 2Ni/BC, 3Ni/BC, 4Ni/BC, Ni-Ce/BC, imp-Ni/BC 의 탄화수소 중 메탄 분해를 통한 수소생산<반응식 1>에서 촉매로 사용되는 구체적으로 기재한다.Hydrogen production through hydrocarbons of 2Ni / BC, 3Ni / BC, 4Ni / BC, Ni-Ce / BC and imp-Ni / BC synthesized through Examples 2, 3, 4, 5 and 6 Specific examples of the catalyst used in
2Ni/BC<실시예 7>, 3Ni/BC<실시예 8>, 4Ni/BC<실시예 9>, Ni-Ce/BC<실시예 10>, imp_Ni/BC<실시예 11>, 각 0.1g 또는 0.2g의 3Ni/BC<실시예 12>, 0.667g의 Ni/Al2O3(상용촉매)<비교예 1>을 외경 1.27cm, 길이 380cm의 Inconel재질 반응기에 넣고 양단을 Quartz Wool(SHIMADZU, P/N638-60074)을 통해 패킹하였다. 패킹 된 반응기를 가열이 가능한 퍼니스에 넣고 질소(N2, >99.999, 삼오가스) 40㎖/min로 흘리며 1시간 퍼지하였다. 이 후 질소를 계속 흘리며 반응기를 절대압력 1기압에서 온도는 10/min으로 25에서 850℃까지 올려준 뒤, 메탄(CH4, >99.95, 삼오가스) 10㎖/min를 질소 40㎖/min와 함께 흘리며 210분<실시예 7, 8>, 240분<실시예 10>, 300분<실시예 9, 11> 또는 60분<실시예 12, 비교예 1> 동안 850℃로 유지시켰다. 반응종료 후 메탄 밸브를 잠그고 질소만 상기 유량으로 흘리며 상온까지 냉각하였다.2Ni / BC <Example 7>, 3Ni / BC <Example 8>, 4Ni / BC <Example 9>, Ni-Ce / BC <Example 10>, imp_Ni / BC <Example 11> or 3Ni / BC of 0.2g <example 12>, Ni / Al2O3 (a commercial catalyst) <Comparative example 1> an outside diameter of 1.27cm 0.667g, Inconel material into a reactor length of 380cm both ends Quartz Wool (SHIMADZU, P / N638-60074). The packed reactor was placed in a heatable furnace and purged with nitrogen (N2, > 99.999, ternary gas) at 40 ml / min for 1 hour. Thereafter, the reactor was continuously fed with nitrogen at a pressure of 1 atm and the temperature was raised from 25 to 850 ° C at a rate of 10 / min. Then, 10 ml / min of methane (CH4,> 99.95, And kept at 850 DEG C for 210 minutes (Examples 7 and 8), 240 minutes (Example 10), 300 minutes (Examples 9 and 11), or 60 minutes (Example 12, Comparative Example 1). After the completion of the reaction, the methane valve was closed, and only the nitrogen was flowed at the above-mentioned flow rate and cooled to room temperature.
반응 후 생성된 가스는 On-line GC(Agilent 7890A)를 통해 정량 분석되었고 Wet gas meter(Shinagawa, W-NK-0.5B)를 통해 실시간 유량이 측정 되었다. 이를 통해 계산된 메탄의 전환율은 2Ni/BC<실시예 7>의 경우 <도4>, 3Ni/BC(유량: 6L/hr*gcat)<실시예 8>의 경우 <도5>, 4Ni/BC<실시예 9>의 경우 <도6>, Ni-Ce/BC<실시예 10>의 경우 <도7>, imp-Ni/BC<실시예 11>의 경우 <도8>, 3Ni/BC(유량:3L/hr*gcat)<실시예 12> 및 Ni/Al2O3<비교예1>의 경우 <도10>에 각각 정리 되었다.The gas produced after the reaction was quantitatively analyzed on-line GC (Agilent 7890A) and the real-time flow rate was measured using a wet gas meter (Shinagawa, W-NK-0.5B). The conversion rate of methane calculated from the above results in the conversion rate of 2Ni / BC (Example 7), 3Ni / BC (flow rate: 6L / hr * gcat) Ni-Ce / BC in Example 9, Ni-Ce / BC in Example 10, Ni-Ce / BC in Example 11, Flow rate: 3 L / hr * gcat) Example 12 and Ni / Al 2 O 3 <Comparative Example 1> are shown in FIG.
도 4 내지 도 8의 결과로부터 볼 수 있듯이 담지된 니켈의 양이 많을수록 전환율 및 최고 전환율에서 반응지속 시간이 길어짐을 알 수 있다. 또한 세륨을 첨가하는 경우 도 4와 도 5에 비해 전환율 및 반응지속 시간이 길어짐을 알 수 있다. 도 8의 imp_Ni/BC(실시예 6과 실시예 11)의 경우는 동시 반응에 의해 금속이 함유된 도 4 내지 도 7(실시예 2~5, 실시예 7~10)에 비해 전환율이 상대적으로 낮음을 알 수 있다. As can be seen from the results of FIGS. 4 to 8, it can be seen that as the amount of supported nickel increases, the reaction duration becomes longer at the conversion rate and the highest conversion rate. In addition, when cerium was added, the conversion rate and the reaction duration time were longer than those of Figs. 4 and 5. In the case of imp_Ni / BC (Example 6 and Example 11) in Fig. 8, the conversion rate is relatively higher than that in Figs. 4 to 7 (Examples 2 to 5 and Examples 7 to 10) Low.
이산화탄소로부터 합성된 금속 담지 다공성 탄소소재(특히, 동시 반응에 의해 형성된 촉매)가 비교적 온건한 조건(상압)에서 매우 높은 전환율로 메탄을 수소와 탄소로 분해하는 촉매 역할을 할 수 있음을 확인하였다.It has been confirmed that the metal-supported porous carbon material synthesized from carbon dioxide (especially the catalyst formed by the simultaneous reaction) can act as a catalyst for decomposing methane into hydrogen and carbon at a very high conversion rate under relatively moderate conditions (atmospheric pressure).
도 9는 상기 <실시예 2>의 동시 반응에 의해 합성된 2Ni/BC(왼쪽)과 실시예 6의 imp_Ni/BC(오른쪽)를 촬영한 이미지이다. 두 경우 모두 니켈이 탄소에 잘 분산되어 있음을 확인할 수 있다. 다만, 실시예 6(도 8)에 의해 제조된 촉매가 실시예 2에 의해 제조된 촉매(도 4)에 비해 메탄 전환율이 상대적으로 낮은데, 이것은 실시예 6(도 8)의 촉매에 담지된 금속이 금속 산화물 형태로 더 많이 존재하기 때문인 것으로 파악된다. FIG. 9 is an image of 2Ni / BC (left) synthesized by the simultaneous reaction of Example 2 and imp_Ni / BC (right) of Example 6. FIG. In both cases, it can be seen that nickel is well dispersed in carbon. However, the catalyst prepared according to Example 6 (FIG. 8) has a relatively low methane conversion rate compared to the catalyst prepared according to Example 2 (FIG. 4) Is present in the form of metal oxide.
도 10은 실시예 12(3Ni/BC, 니켈 함유량 7wt%, 3L/hr*gcat)과 비교예 1(Ni/Al2O3, 니켈 함유량 12wt%, 0.9L/hr*gcat)의 메탄 전환율을 비교하여 나타낸 것이다. 도 10을 참고하면, 상용촉매에 담지된 니켈의 함유량(12wt%)이 본원발명의 3Ni/BC에 담지된 니켈 함유량(7wt%) 보다 많고 촉매 당 반응가스 유량도 적음에도 불구하고 본원발명의 촉매가 메탄 전환율 및 지속시간이 2배 이상 우수함을 확인할 수 있다.10 shows the methane conversion rates of Example 12 (3Ni / BC, 7 wt% nickel, 3L / hr * gcat) and Comparative Example 1 (Ni / Al2O3,
<실시예 13>≪ Example 13 >
상기 <실시예 2>를 통해 합성된 2Ni/BC를 이산화탄소를 이용한 메탄 개질<반응식 2>의 촉매로 사용되는 과정을 구체적으로 기재한다.The process of using 2Ni / BC synthesized through Example 2 as a catalyst of methane reforming using carbon dioxide (Reaction Scheme 2) will be described in detail.
2Ni/BC 0.1g을 외경 1.27cm, 길이 380cm의 Inconel재질 반응기에 넣고 양단을 Quartz Wool(SHIMADZU, P/N638-60074)을 통해 패킹하였다. 패킹 된 반응기를 가열이 가능한 퍼니스에 넣고 질소(N2, >99.999, 삼오가스) 30㎖/min로 흘리며 1시간 퍼지하였다. 이 후 질소를 계속 흘리며 반응기를 절대압력 1기압에서 온도는 10/min으로 25에서 800℃까지 올려준 뒤, 메탄(CH4, >99.95, 삼오가스) 10㎖/min와 이산화탄소(CO2, >99.99, 삼오가스) 10㎖/min와 함께 흘리며 390분 동안 800℃로 유지시켰다. 반응종료 후 메탄과 이산화탄소 밸브를 잠그고 질소만 상기 유량으로 흘리며 상온까지 냉각하였다.2Ni / BC was loaded into an Inconel material reactor having an outer diameter of 1.27 cm and a length of 380 cm and both ends were packed through a Quartz Wool (SHIMADZU, P / N638-60074). The packed reactor was placed in a heatable furnace and purged with nitrogen (N2, > 99.999, tri-ozone gas) at 30 ml / min for 1 hour. After that, the reactor was continuously fed with nitrogen and the temperature was raised from 25 to 800 ° C. at a pressure of 1 atm under a pressure of 1 atm. After that, methane (CH 4,> 99.95, ≪ / RTI > 3Og gas) at < RTI ID = 0.0 > 800 C < / RTI > for 390 minutes. After the completion of the reaction, the methane and carbon dioxide valves were closed, and only the nitrogen was flowed at the above-mentioned flow rate and cooled to room temperature.
반응 후 생성된 가스는 On-line GC(Agilent 7890A)를 통해 정량 분석되었고 Wet gas meter(Shinagawa, W-NK-0.5B)를 통해 실시간 유량이 측정 되었다. 이를 통해 계산된 메탄 및 이산화탄소의 전환율은 <도 11> 나타내었다. The gas produced after the reaction was quantitatively analyzed on-line GC (Agilent 7890A) and the real-time flow rate was measured using a wet gas meter (Shinagawa, W-NK-0.5B). The calculated conversion rates of methane and carbon dioxide are shown in FIG.
도 11을 참고하면, 본 발명의 탄소 소재 촉매는 메탄 개질 반응의 촉매로 사용될 수 있음을 확인할 수 있다.Referring to FIG. 11, it is confirmed that the carbon material catalyst of the present invention can be used as a catalyst for methane reforming reaction.
Claims (24)
상기 촉매는 열분해 반응을 통해 탄화수소로부터 수소와 탄소를 생산하는 탄화수소 분해 반응의 촉매이거나, 상기 촉매는 이산화탄소 또는 수증기를 탄화수소와 반응시켜 수소와 일산화탄소를 생산하는 합성가스 제조 촉매인 것을 특징으로 하는 금속 담지 탄소 촉매의 제조방법.
A method for producing a metal-supported carbon catalyst comprising the steps of reacting a reducing agent and a metal precursor with a gas containing carbon dioxide,
Wherein the catalyst is a catalyst for hydrocarbon decomposition reaction for producing hydrogen and carbon from hydrocarbons through pyrolysis reaction or the catalyst is a synthesis gas producing catalyst for producing hydrogen and carbon monoxide by reacting carbon dioxide or steam with hydrocarbons. Carbon catalyst.
상기 탄소소재에 금속 전구체를 담지하는 단계를 포함하는 금속 담지 탄소 촉매의 제조방법으로서,
상기 촉매는 열분해 반응을 통해 탄화수소로부터 수소와 탄소를 생산하는 탄화수소 분해 반응의 촉매이거나, 상기 촉매는 이산화탄소 또는 수증기를 탄화수소와 반응시켜 수소와 일산화탄소를 생산하는 합성가스 제조 촉매인 것을 특징으로 하는 금속 담지 탄소 촉매의 제조방법.
Reacting a gas containing carbon dioxide with a reducing agent to produce a carbon material; And
Supporting a metal precursor on the carbon material, the method comprising the steps of:
Wherein the catalyst is a catalyst for hydrocarbon decomposition reaction for producing hydrogen and carbon from hydrocarbons through pyrolysis reaction or the catalyst is a synthesis gas producing catalyst for producing hydrogen and carbon monoxide by reacting carbon dioxide or steam with hydrocarbons. Carbon catalyst.
The method of claim 1, wherein the metal precursor powder and the reducing agent powder are mixed to prepare a mixed powder, and then the carbon dioxide is supplied to perform the reaction.
The method of claim 1 or 2, wherein the reaction is performed at 400 ° C or higher.
The method of claim 1 or 2, wherein the pressure of the gas containing carbon dioxide is 0.01 to 100 atm and the carbon dioxide content of the gas is 1 to 100 mol%.
The method of claim 1 or 2, wherein the metal precursor is used in an amount of 1 to 200 mol% based on the reducing agent.
The metal precursor according to claim 1 or 2, wherein the metal precursor is at least one selected from the group consisting of transition metals, alkali metals, alkaline earth metals, noble metals, salts of these metals, hydrates of these metals and oxides of these metals By weight based on the total weight of the catalyst.
The method of claim 7, wherein the transition metal is selected from the group consisting of nickel (Ni), cobalt (Co), copper (Cu), zinc (Zn), titanium (Ti), iron (Fe) And the noble metal is at least one selected from the group consisting of gold, platinum, and silver.
The method of claim 7, wherein the alkali metal is selected from the group consisting of lithium (Li), sodium (Na), and cesium (Cs), and the alkaline earth metal is selected from the group consisting of magnesium, calcium (Ca), and strontium Wherein at least one of the catalysts is selected from the group consisting of a metal catalyst and a catalyst.
The method of claim 1 or 2, wherein the reducing agent is at least one selected from the group consisting of magnesium (Mg), magnesium hydride (MgH2), and boron hydride.
The method of claim 10, wherein said boron hydride, lithium boron hydride (LiBH 4), sodium boron hydride (NaBH 4), potassium boron hydride (KBH 4), magnesium boron hydride (Mg (BH 4) 2) , Calcium boron hydride (Ca (BH 4 ) 2 ) and strontium boron hydride (Sr (BH 4 ) 2 ).
The method according to claim 1 or 2, further comprising the step of washing the catalyst produced after the reaction step or the supporting step by using one selected from the group consisting of acid, hot water, cold water and alcohol, followed by drying Wherein the metal-supported carbon catalyst is a metal catalyst.
13. The method of claim 12, wherein the method further comprises a heat treatment step after the drying step.
14. The method of claim 13, wherein the heat treatment is performed at a temperature of 300 to 1500 占 폚.
The method of claim 2, wherein the supporting method is selected from the group consisting of a spraying method, an evaporation drying method, a simple deposition method, and a precipitation method.
16. The method of claim 15, wherein the spraying method comprises spraying a solution containing a metal precursor on the carbon material.
[16] The method of claim 15, wherein the carbon material is loaded in a metal precursor solution and then heated to evaporate the solvent to carry the metal.
16. The method of claim 15, wherein the simple deposition method comprises placing the carbon material in a metal precursor solution to deposit a metal on the carbon material pores.
[16] The method of claim 15, wherein the precipitation method comprises: placing the carbon material in a metal precursor solution and then adding a precipitant to precipitate and support the metal.
상기 촉매는 열분해 반응을 통해 탄화수소로부터 수소와 탄소를 생산하는 탄화수소 분해 반응의 촉매이거나, 상기 촉매는 이산화탄소 또는 수증기를 탄화수소와 반응시켜 수소와 일산화탄소를 생산하는 합성가스 제조 촉매인 것을 특징으로 하는 금속 담지 탄소 촉매.
The carbon catalyst produced by the method of claim 1, wherein the carbon catalyst is a core-shell structure in which the metal becomes an inner core and carbon surrounds the metal,
Wherein the catalyst is a catalyst for hydrocarbon decomposition reaction for producing hydrogen and carbon from hydrocarbons through pyrolysis reaction or the catalyst is a synthesis gas producing catalyst for producing hydrogen and carbon monoxide by reacting carbon dioxide or steam with hydrocarbons. Carbon catalyst.
상기 촉매는 열분해 반응을 통해 탄화수소로부터 수소와 탄소를 생산하는 탄화수소 분해 반응의 촉매이거나, 상기 촉매는 이산화탄소 또는 수증기를 탄화수소와 반응시켜 수소와 일산화탄소를 생산하는 합성가스 제조 촉매인 것을 특징으로 하는 금속 담지 탄소 촉매.
The carbon catalyst according to claim 2, wherein the carbon catalyst has a structure in which the metal is supported on the inside or the surface thereof, or a metal is supported on the pores of the carbon catalyst,
Wherein the catalyst is a catalyst for hydrocarbon decomposition reaction for producing hydrogen and carbon from hydrocarbons through pyrolysis reaction or the catalyst is a synthesis gas producing catalyst for producing hydrogen and carbon monoxide by reacting carbon dioxide or steam with hydrocarbons. Carbon catalyst.
21. The metal-supported carbon catalyst according to claim 20, wherein the metal is in a reduced state.
The metal-supported carbon catalyst according to claim 20 or 21, wherein the hydrocarbon is a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.
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