KR20150087557A - Metal-doped titanium oxide nanowire catalyst, preparing method of the same and method for oxidative coupling reaction of methane using the same - Google Patents
Metal-doped titanium oxide nanowire catalyst, preparing method of the same and method for oxidative coupling reaction of methane using the same Download PDFInfo
- Publication number
- KR20150087557A KR20150087557A KR1020140007653A KR20140007653A KR20150087557A KR 20150087557 A KR20150087557 A KR 20150087557A KR 1020140007653 A KR1020140007653 A KR 1020140007653A KR 20140007653 A KR20140007653 A KR 20140007653A KR 20150087557 A KR20150087557 A KR 20150087557A
- Authority
- KR
- South Korea
- Prior art keywords
- metal
- methane
- titanium oxide
- catalyst
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 38
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002070 nanowire Substances 0.000 title abstract description 20
- 238000005691 oxidative coupling reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 13
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims description 47
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000010936 titanium Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 238000011002 quantification Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000010948 rhodium Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 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 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- -1 for example V 2 O 5 Substances 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001165 gas chromatography-thermal conductivity detection Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 108010063955 thrombin receptor peptide (42-47) Proteins 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
본 발명은 금속 첨가 티타늄산화물 나노와이어를 포함하는 메탄 산화이량화 반응 촉매, 이의 제조방법 및 이를 이용한 메탄 산화이량화 반응방법에 관한 것으로, 본 발명에 따르면 금속이 첨가된 티타늄산화물 나노와이어 촉매를 메탄의 산화이량화 반응에 사용함으로써 촉매의 반응활성 및 C2 탄화수소의 수율, 선택도를 높이고, 높은 반응온도에서도 안정적인 촉매를 제공할 수 있다.The present invention relates to a methane oxidation quantitative reaction catalyst comprising metal-doped titanium oxide nanowires, a method for producing the same, and a methanation method for quantifying methane using the same. The present invention relates to a titanium oxide nanowire catalyst, The reaction activity of the catalyst, the yield and selectivity of C 2 hydrocarbons can be increased, and a stable catalyst can be provided even at a high reaction temperature.
Description
본 발명은 금속 첨가 티타늄산화물 나노와이어 촉매, 이의 제조방법 및 이를 이용한 메탄 산화이량화 반응방법에 관한 것으로, 보다 구체적으로 금속이 첨가된 티타늄산화물 나노와이어 촉매를 제조하고 메탄의 산화이량화 반응에 제조된 촉매를 이용하여 메탄으로부터 에틸렌, 에탄과 같은 C2 화합물을 제조하는 방법에 관한 것이다.The present invention relates to a metal-added titanium oxide nanowire catalyst, a method for producing the same, and a methanation method for quantifying methane using the same. More specifically, the present invention relates to a titanium oxide nanowire catalyst to which a metal is added, To a method for producing C 2 compounds such as ethylene and ethane from methane.
천연가스 및 쉐일가스의 주성분인 메탄은 석유, 석탄 등과 같이 매장량이 풍부하며 직접 연료로 사용하거나 화학적 전환 공정을 통해 고부가가치 생산물로 전환될 수 있는 유용한 천연자원이다. 예를 들어, 메탄은 전력 발전소, 산업체 및 가정으로 공급되어 연료 자원으로 사용되거나, 직접 및 간접 전환 반응을 통하여 올레핀과 같은 석유자원의 기초 원료로 사용될 수도 있다. 또한, 최근에는 메탄을 전환하여 석유화학제품을 생산하는 비중이 커지고 있는 추세이다.Methane, a major component of natural gas and shale gas, is rich in reserves, such as petroleum and coal, and is a useful natural resource that can be converted directly into high value-added products through chemical conversion processes. Methane, for example, can be supplied to power plants, industries and homes and used as fuel resources or as a basis for petroleum resources such as olefins through direct and indirect conversion reactions. In recent years, the proportion of producing petrochemical products by converting methane is increasing.
메탄을 전환하는 방법은 크게 두 가지로 분류된다. 첫 번째는, 증기 개질 (steam reforming), 산소 개질 (oxy-reforming), 이산화탄소 개질 (CO2-reforming) 등과 같은 메탄 개질반응을 통하여 메탄을 합성가스 (H2, CO)로 전환하고, 추가적인 전환반응을 거쳐 석유화학 기초원료들을 얻는 방법이다. 이와 같은 방법을 간접전환방법이라 하는데, 합성가스를 얻는 과정에서 대량의 에너지가 요구되며, 초기 투자비용이 많이 소요된다는 단점이 있다. 두 번째는, 합성가스와 같은 중간 생성물을 거치지 않고, 메탄을 원하는 탄화수소 물질로 직접전환시키는 방법으로서, 이러한 방법을 직접전환방법이라 한다. 직접전환방법은 단일 공정을 통해서 최종 생성물을 얻을 수 있다는 장점이 있지만, 아직까지는 간접 전환 방법에 비해서 경제성이 떨어진다는 한계점을 지니고 있다. 이러한 한계점을 극복하기 위해 새로운 촉매 개발에 관한 연구가 활발히 진행되고 있다.There are two main methods for converting methane. The first is to convert methane to synthesis gas (H 2 , CO) through methane reforming reactions such as steam reforming, oxy-reforming, CO 2 -forming, It is a method to obtain petrochemical base materials through the reaction. This method is referred to as indirect conversion, which requires a large amount of energy in the process of obtaining syngas, and requires a large initial investment cost. The second is a direct conversion of methane to the desired hydrocarbon material without passing through intermediate products such as syngas, which is referred to as direct conversion. The direct conversion method has the advantage that the final product can be obtained through a single process, but it still has a limitation in that it is less economical than the indirect conversion method. In order to overcome these limitations, new catalysts have been actively studied.
대표적인 메탄의 직접전환방법으로는 메탄 산화이량화 반응 (oxidative coupling of methane)이 있는데, 이는 천연가스의 주원료인 메탄으로부터 C2 탄화수소를 얻을 수 있는 유용한 방법이다. 하기 반응식 1에서 메탄이 산화이량화 반응을 통해서 C2 탄화수소의 일종인 에틸렌으로 전환되는 반응식을 나타내었다:
A typical methane direct conversion method is the oxidative coupling of methane, which is a useful method for obtaining C 2 hydrocarbons from methane, the mainstream of natural gas. In the following
<반응식 1><
2CH4 + O2 → C2H4 + 2H2O 2CH 4 + O 2 → C 2 H 4 + 2H 2 O
상기와 같은 메탄 산화이량화 반응은 비교적 단순한 반응 시스템에서 추가적인 공정이나 처리과정 없이 C2 탄화수소를 얻을 수 있다는 장점이 있다. 그러나, 전술한 바와 같이, 현재까지는 메탄의 간접전환방법에 비해 경제적 가치가 낮기 때문에, C2 탄화수소의 선택도를 높일 수 있는 (예를 들어, 상기 에틸렌으로의 변환 과정에서 대부분의 메탄은 에틸렌으로 변환되기보다는, 이산화탄소로 산화되려는 경향이 있다) 촉매 개발이 필요한 실정이다. 또한, 메탄의 산화이량화 반응은 비교적 높은 온도에서 수행되기 때문에 촉매가 높은 온도에서 높은 반응활성을 유지할 수 있도록 하여야 한다.The above-described methane oxidation quantification reaction is advantageous in that C 2 hydrocarbons can be obtained in a relatively simple reaction system without any additional process or treatment. However, as described above, since it is low in economic value compared with the indirect conversion method of methane up to now, it is possible to increase the selectivity of C 2 hydrocarbons (for example, in the conversion to ethylene, Catalysts tend to be oxidized to carbon dioxide rather than being converted). Also, since the oxidation-reduction reaction of methane is performed at a relatively high temperature, the catalyst should be able to maintain a high reaction activity at a high temperature.
현재까지 메탄 산화이량화 반응에는, 소정 금속 산화물 담체에 텅스토나트륨-망간산화물을 담지한 촉매 등이 사용되고 있다. 예를 들어, 대한민국 공개특허공보 제2010-130722호에서는 실리카 에어로젤 담지 촉매 및 이를 이용한 메탄 전환 방법을 개시하고 있으며, 구체적으로는 실리카 에어로젤 담체 및 상기 담체 내에 담지된 텅스토나트륨 및 망간 산화물을 포함하는 실리카 에어로젤 담지 촉매를 개시하고 있다.To date, a catalyst containing tungstosodium-manganese oxide supported on a predetermined metal oxide support has been used for the methanation reaction of oxidizing methane. For example, Korean Patent Laid-Open Publication No. 2010-130722 discloses a silica airgel supported catalyst and a methane conversion method using the silica airgel supported catalyst. Specifically, the silica airgel supported catalyst includes a silica airgel carrier and tungstosodium and manganese oxide A silica airgel supported catalyst is disclosed.
상기와 같은 문제점을 해결하기 위하여 본 발명은 메탄 산화이량화 반응에서 높은 C2 탄화수소 수율 및 선택도를 제공하면서 고온의 반응에서 안정적으로 사용할 수 있는 메탄 산화이량화 반응촉매를 제조하고 이를 이용한 메탄 산화이량화 반응방법을 제공하는 것을 그 목적으로 한다. In order to solve the above problems, the present invention provides a methane oxidation quantification reaction catalyst which can be used stably in a high-temperature reaction while providing a high C 2 hydrocarbon yield and selectivity in the methane oxidation polymerization reaction, The present invention is directed to providing a method for providing a service to a user.
상기와 같은 목적을 해결하기 위하여 본 발명은 금속 첨가 티타늄산화물 나노와이어를 포함하는 메탄 산화이량화 반응 촉매를 제공한다. In order to solve the above-mentioned problems, the present invention provides a methane oxidation quantitative reaction catalyst comprising metal-doped titanium oxide nanowires.
본 발명의 일실시예에 있어서, 상기 금속은 망간(Mn), 바나듐(V), 크롬(Cr), 로듐(Rh), 몰리브덴(Mo) 및 코발트(Co)로 이루어진 군에서 선택되는 하나 이상일 수 있다.In one embodiment of the present invention, the metal may be at least one selected from the group consisting of manganese (Mn), vanadium (V), chromium (Cr), rhodium (Rh), molybdenum (Mo), and cobalt have.
본 발명의 일실시예에 있어서, 상기 금속 첨가 티타늄산화물은 금속과 티타늄이 원자 수준에서 균일하게 혼합된 혼합산화물일 수 있다.In one embodiment of the present invention, the metal-added titanium oxide may be a mixed oxide in which metal and titanium are uniformly mixed at an atomic level.
본 발명의 일실시예에 있어서, 상기 금속 첨가 티타늄산화물은 금속과 티타늄산화물이 공비혼합된 고체 상태로 존재하는 것일 수 있다.In one embodiment of the present invention, the metal-added titanium oxide may be a solid state in which a metal and titanium oxide are mixed together in an azeotropic state.
본 발명의 일실시예에 있어서, 상기 금속 첨가 티타늄산화물은 금속/티타늄(Ti)의 원자비가 0.01 내지 0.03일 수 있다.In one embodiment of the present invention, the metal-added titanium oxide may have an atomic ratio of metal to titanium (Ti) of 0.01 to 0.03.
또한, 본 발명은 상기 메탄 산화이량화 반응 촉매의 제조방법으로서, 티타니아(TiO2)에 금속의 염화물, 질소화물 및 산화물 중 하나인 금속 전구체를 첨가하여 금속/티타늄(Ti)의 원자비가 0.01 내지 0.03가 되도록 한 후 분쇄 및 소성시키는 단계를 포함하는 메탄 산화이량화 반응 촉매의 제조방법을 제공한다.Further, the present invention provides a method for producing the above-mentioned methane oxidation quantitative reaction catalyst, which comprises adding a metal precursor, which is one of chloride, nitrogen and oxides of metals, to titanium (TiO 2 ), so that the atomic ratio of metal / titanium (Ti) , Followed by pulverization and calcination. The present invention also provides a method for producing a methane oxidation quantitative reaction catalyst.
본 발명의 일실시예에 있어서, 상기 제조방법은 티타니아(TiO2), 염화나트륨 및 나트륨 인화물을 혼합한 혼합물에, 금속의 염화물, 질소화물 및 산화물 중 하나인 금속 전구체를 첨가하여 금속/티타늄(Ti)의 원자비가 0.01 내지 0.03가 되도록 하는 단계; 및 상기 단계에서 얻어진 혼합물을 분말로 분쇄하고 700 내지 900oC에서 소성시키는 단계; 를 포함할 수 있다.In one embodiment of the present invention, the method comprises the steps of adding a metal precursor, which is one of chloride, nitrogen and oxide of a metal, to a mixture of titania (TiO 2 ), sodium chloride and sodium phosphite to form a metal / titanium ) Is in the range of 0.01 to 0.03; And pulverizing the mixture obtained in the above step into powder and calcining at 700 to 900 ° C; . ≪ / RTI >
또한, 본 발명은 상기 메탄 산화이량화 반응 촉매를 이용하여 메탄을 산화이량화시키는 메탄 산화이량화 반응방법을 제공한다.Also, the present invention provides a methane oxidation quantification reaction method for oxidizing methane using the methane oxidation quantification reaction catalyst.
본 발명의 일실시예에 있어서, 상기 반응방법은 상기 메탄 산화이량화 반응 촉매를 반응기에 충진하는 단계; 및 메탄, 산소 및 비활성가스를 포함하는 혼합가스를 상기 반응기 내부로 도입하여 메탄의 산화이량화 반응을 수행하는 단계를 포함할 수 있다.In one embodiment of the present invention, the reaction method comprises the steps of: charging the reactor with the methanation catalyst; And introducing a mixed gas containing methane, oxygen, and an inert gas into the reactor to perform the oxidation-reduction reaction of methane.
본 발명의 일실시예에 있어서, 상기 반응기 내부 온도는 750 내지 850 oC일 수 있다.In one embodiment of the present invention, the internal temperature of the reactor may be 750 to 850 ° C.
본 발명의 일실시예에 있어서, 상기 혼합가스 중 상기 산소 : 메탄의 부피비는 1 : 1 내지 1 : 10일 수 있다.In one embodiment of the present invention, the volume ratio of oxygen to methane in the mixed gas may be 1: 1 to 1:10.
본 발명의 일실시예에 있어서, 상기 비활성가스는 질소 또는 헬륨일 수 있다.In one embodiment of the present invention, the inert gas may be nitrogen or helium.
본 발명의 일실시예에 있어서, 상기 혼합가스의 상기 반응기 내부에서의 기체공간속도 (gas hourly space velocity, GHSV)는 10,000 h-1 내지 30,000 h-1일 수 있다.In one embodiment of the present invention, the gas hourly space velocity (GHSV) of the mixed gas within the reactor may be 10,000 h -1 to 30,000 h -1 .
본 발명에 따르면, 금속이 첨가된 티타늄산화물 나노와이어 촉매를 메탄의 산화이량화 반응에 사용함으로써 촉매의 반응활성 및 C2 탄화수소의 수율, 선택도를 높이고, 높은 반응온도에서도 안정적인 촉매를 제공할 수 있다.According to the present invention, by using a titanium oxide nanowire catalyst to which a metal is added, the reaction activity of the catalyst, the yield and selectivity of C 2 hydrocarbons can be increased, and a stable catalyst can be provided even at a high reaction temperature .
도 1 은 본 발명의 일실시예에 따른 금속 첨가 티타늄산화물 나노와이어 촉매를 이용한 메탄의 산화이량화 반응 공정을 도식화한 것이다.
도 2는 본 발명의 일실시예에 따른 금속 첨가 티타늄산화물 나노와이어 촉매의 SEM 이미지를 나타낸 것이다. FIG. 1 is a diagram illustrating a process for quantifying methane oxidation using a metal-added titanium oxide nanowire catalyst according to an embodiment of the present invention.
2 is an SEM image of a metal-doped titanium oxide nanowire catalyst according to an embodiment of the present invention.
이하에서는, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명을 용이하게 실시할 수 있도록 하기 위하여, 본 발명의 바람직한 실시예들에 관하여 상세히 설명하기로 한다.
Hereinafter, preferred embodiments of the present invention will be described in detail in order to facilitate the present invention by those skilled in the art.
본 발명에서 'C2 탄화수소' 또는 'C2 화합물'이라 함은 탄소수가 2개인 탄화수소를 총칭하는 개념으로서, 이에 제한되는 것은 아니나 에탄, 에틸렌 또는 아세틸렌 등의 탄화수소를 포함하는 개념이다.
In the present invention, the term "C 2 hydrocarbon" or "C 2 compound" refers to a concept including generically refers to a hydrocarbon having two carbon atoms, including, but not limited to, hydrocarbons such as ethane, ethylene or acetylene.
본 발명은 금속 첨가 티타늄산화물 나노와이어를 포함하는 메탄 산화이량화 반응 촉매를 제공한다. 즉, 본 발명의 금속 첨가 티타늄산화물 나노와이어 촉매는 메탄의 산화이량화 반응을 위한 촉매로서, 티타니아(TiO2) 입자로부터 제조되는 것이다.
The present invention provides a methane oxidation quantification reaction catalyst comprising metal-doped titanium oxide nanowires. That is, the metal-added titanium oxide nanowire catalyst of the present invention is a catalyst for quantitatively oxidizing methane, which is produced from titania (TiO 2 ) particles.
본 발명에서, 상기 금속은 망간(Mn), 바나듐(V), 크롬(Cr), 로듐(Rh), 몰리브덴(Mo) 및 코발트(Co)로 이루어진 군에서 선택되는 하나 또는 둘 이상의 합금일 수 있고, 바람직하게 망간(Mn)을 사용할 수 있다.
In the present invention, the metal may be one or more alloys selected from the group consisting of manganese (Mn), vanadium (V), chromium (Cr), rhodium (Rh), molybdenum (Mo) and cobalt , Preferably manganese (Mn) can be used.
본 발명에서, 상기 금속 첨가 티타늄산화물은 금속과 티타늄이 원자 수준에서 균일하게 혼합된 혼합산화물로, 티타늄산화물에 금속 원자가 균일하게 분산되어 있는 것일 수 있다.In the present invention, the metal-added titanium oxide may be a mixed oxide in which metal and titanium are uniformly mixed at an atomic level, and metal atoms are uniformly dispersed in titanium oxide.
또한 상기 금속 첨가 티타늄산화물은 금속과 티타늄산화물이 공비혼합된 고체 상태로 존재하는 것일 수 있다.
The metal-doped titanium oxide may be a solid state in which the metal and the titanium oxide are mixed together in an azeotropic state.
본 발명에서, 상기 금속 첨가 티타늄산화물은 금속/티타늄(Ti)의 원자비가 0.01 내지 0.03일 수 있다. 즉, 첨가된 금속과 티타늄의 함량비는 원자수(몰수) 기준 금속/티타늄(Ti)= 0.01 내지 0.03이고, 바람직하게 0.015 내지 0.025, 더욱 바람직하게 0.02일 수 있다. 첨가 금속의 함량이 상기 범위보다 적으면 낮은 활성을 가지는 촉매 특성을 보이고, 상기 범위보다 많으면 티타늄산화물에 금속이 원자 상태로 첨가되는 외에 금속첨가물이 티타늄산화물 외부에서 입자형태로 생성되어 촉매 특성을 떨어뜨릴 수 있다.
In the present invention, the metal-added titanium oxide may have an atomic ratio of metal to titanium (Ti) of 0.01 to 0.03. That is, the content ratio of the added metal to titanium can be 0.01 to 0.03, preferably 0.015 to 0.025, and more preferably 0.02 based on the number of atoms (molar amount) of the metal / titanium (Ti). When the content of the additive metal is less than the above range, the catalyst exhibits a low activity. If the additive metal content is higher than the above range, the metal is added to the titanium oxide in an atomic state and the metal additive is formed in the form of particles outside the titanium oxide, You can knock.
본 발명에 따른 금속 첨가 티타늄산화물 나노와이어 촉매는, 티타니아(TiO2)에 금속의 염화물, 질소화물 및 산화물 중 하나인 금속 전구체를 첨가하여 금속/티타늄(Ti)의 원자비가 0.01 내지 0.03가 되도록 한 후 분쇄 및 소성시키는 단계를 포함하는 메탄 산화이량화 반응 촉매의 제조방법에 의하여 제조될 수 있다.
The metal-added titanium oxide nanowire catalyst according to the present invention can be produced by adding a metal precursor, which is one of metal chloride, nitrogen oxide and oxide, to titanium oxide (TiO 2 ) so that the atomic ratio of metal / titanium (Ti) is 0.01 to 0.03 Followed by pulverizing and firing the mixture.
구체적으로, 먼저 티타니아(TiO2), 염화나트륨 및 나트륨 인화물을 혼합한 혼합물에, 금속의 염화물, 질소화물 및 산화물 중 하나인 금속 전구체를 첨가하여 금속/티탄(Ti)의 원자비가 0.01 내지 0.03가 되도록 한다. Specifically, a metal precursor, which is one of a chloride, a nitrogen and an oxide of a metal, is added to a mixture of titania (TiO 2 ), sodium chloride and sodium phosphite to obtain a metal / titanium (Ti) atomic ratio of 0.01 to 0.03 do.
상기 나트륨 인화물은 특별히 한정되는 것은 아니나, 바람직하게 Na2HPO4일 수 있다. 상기 티타니아(TiO2), 염화나트륨 및 나트륨 인화물의 혼합물은, 티타니아(TiO2): 염화나트륨: 나트륨 인화물의 중량비가 0.5~1.5: 3~5: 0.5~1.5인 것이 바람직하고, 더욱 바람직하게 1:4:1일 수 있다.The sodium phosphide is not particularly limited, but may preferably be Na 2 HPO 4 . The mixture of titania (TiO 2 ), sodium chloride and sodium phosphite preferably has a weight ratio of titania (TiO 2 ): sodium chloride: sodium phosphide of 0.5: 1.5-3: 5: 0.5-1.5, more preferably 1: 4 : May be one.
상기 금속 전구체는 첨가 금속의 전구체로서, 첨가 금속의 염화물, 질소화물 및 산화물 중 하나일 수 있다. 첨가 금속은 상술한 바와 같이 망간(Mn), 바나듐(V), 크롬(Cr), 로듐(Rh), 몰리브덴(Mo) 및 코발트(Co)로 이루어진 군에서 선택되는 하나 또는 둘 이상의 합금일 수 있고, 바람직하게 망간(Mn)일 수 있다. 이러한 첨가 금속의 전구체는 예를 들어 V2O5, Cr(NO3)3, Mn(NO3)2, Co(NO3)2, (NH4)6Mo7O24, Rh(NO3)3일 수 있다. The metal precursor is a precursor of the additive metal, and may be one of chloride, nitrogen, and oxides of the additive metal. The additive metal may be one or more alloys selected from the group consisting of manganese (Mn), vanadium (V), chromium (Cr), rhodium (Rh), molybdenum (Mo) and cobalt , Preferably manganese (Mn). Precursors of these additive metals, for example V 2 O 5, Cr (NO 3) 3, Mn (NO 3) 2, Co (NO 3) 2, (NH 4) 6 Mo 7 O 24, Rh (NO 3 ) 3 .
그 다음 상기 단계에서 얻어진 혼합물을 분말로 분쇄하고 700 내지 900oC에서 소성시킨다. 그 후 상온(약 20 내지 25oC)으로 냉각시킨 후, 대량의 끓는 이온교환수(Deionized water)로 세척하고 건조시킨다. The mixture obtained in the above step is then pulverized into powder and calcined at 700 to 900 ° C. It is then cooled to room temperature (about 20 to 25 ° C), then washed with a large amount of boiling deionized water and dried.
상기 제조방법에 의하면 티타늄산화물에 금속 원자가 균일하게 분산된 나노와이어 구조의 촉매가 제조된다. 본 발명의 나노와이어는 1 내지 40㎛ 길이와 50 내지 200nm 두께를 가지는 실린더형 구조일 수 있다.
According to the above production method, a nanowire-structured catalyst in which metal atoms are uniformly dispersed in titanium oxide is produced. The nanowire of the present invention may be a cylindrical structure having a length of 1 to 40 mu m and a thickness of 50 to 200 nm.
또한, 본 발명은 상기 메탄 산화이량화 반응 촉매를 이용하여 메탄을 산화이량화시키는 메탄 산화이량화 반응방법을 제공한다.Also, the present invention provides a methane oxidation quantification reaction method for oxidizing methane using the methane oxidation quantification reaction catalyst.
구체적으로 본 발명의 메탄 산화이량화 반응방법은 본 발명에 따른 메탄 산화이량화 반응 촉매를 반응기에 충진하는 단계; 및 메탄, 산소 및 비활성가스를 포함하는 혼합가스를 상기 반응기 내부로 도입하여 메탄의 산화이량화 반응을 수행하는 단계를 포함할 수 있다.Specifically, the methane oxidation quantification reaction method of the present invention comprises the steps of: filling a methane oxidation quantification reaction catalyst according to the present invention into a reactor; And introducing a mixed gas containing methane, oxygen, and an inert gas into the reactor to perform the oxidation-reduction reaction of methane.
예를 들어, 적당한 내경 및 길이를 갖는 석영 반응기 등에 비활성 충진 물질과 본 발명에 따른 메탄 산화이량화 반응 촉매를 적재할 수 있다. 상기 반응촉매는 촉매 중에 포함된 수분 및 불순물 등을 제거하기 위해서 고온에서 전처리를 해줄 수 있는데, 이러한 전처리는, 예를 들어, 600 내지 900℃의 온도에서 질소, 헬륨 등과 같은 비활성가스로 1시간 정도 전처리를 해줄 수 있다.For example, an inert fill material and a methane oxidation quantification reaction catalyst according to the present invention may be loaded into a quartz reactor having a suitable inner diameter and length. The reaction catalyst may be pretreated at a high temperature in order to remove moisture and impurities contained in the catalyst. The pretreatment may be performed at a temperature of 600 to 900 ° C. for about 1 hour with an inert gas such as nitrogen or helium You can do preprocessing.
전처리가 종료되면 상기 반응기 내부로 메탄, 산소 및 비활성가스를 포함하는 혼합가스를 도입시켜 준다. Upon completion of the pretreatment, a mixed gas containing methane, oxygen, and an inert gas is introduced into the reactor.
상기 메탄, 산소 및 비활성가스를 포함하는 혼합가스 중 상기 산소 : 메탄의 부피비는 1 : 1 내지 1 : 10일 수 있고, 바람직하게 1:3 내지 1:7, 더욱 바람직하게 1:5일 수 있고, 상기 범위일 때 촉매 활성 및 C2 탄화수소 수율이 가장 높은 것을 알아내었다. 이때, 총 반응물 유량 중 메탄과 산소를 제외한 유량은 비활성 가스, 예를 들어 질소 또는 헬륨 가스로 보충해 주는데, 이는 반응의 안정성을 기하기 위함이며, 구체적으로, 상기 비활성 가스는 상기 혼합가스 중 10 부피% 내지 30 부피%인 것이 바람직하다. 본 발명에서, 상기 비활성가스는 바람직하게 질소일 수 있다.The volume ratio of oxygen to methane in the mixed gas containing methane, oxygen and inert gas may be 1: 1 to 1:10, preferably 1: 3 to 1: 7, more preferably 1: 5 , The catalyst activity and the C 2 hydrocarbon yield were the highest in the above range. At this time, the flow rate except the methane and oxygen in the total reactant flow rate is supplemented with an inert gas, for example, nitrogen or helium gas, in order to ensure the stability of the reaction. Specifically, By volume to 30% by volume. In the present invention, the inert gas may preferably be nitrogen.
상기 반응기 내부 온도는 750 내지 850℃일 수 있다. 이러한 고온의 반응에서 본 발명에 따른 촉매는 안정적으로 사용될 수 있다.The internal temperature of the reactor may be 750 to 850 ° C. In this high temperature reaction, the catalyst according to the present invention can be used stably.
또한, 본 발명에서 상기 혼합가스의 상기 반응기 내부에서의 기체공간속도 (gas hourly space velocity, GHSV)는 10,000 h-1 내지 30,000 h-1인 것이 바람직한데, 기체공간속도는 유량과 촉매 층의 부피의 비율로서, 기체공간속도가 클수록 반응물이 촉매 층 내부에 체류하는 시간이 작아진다. 또한, 본 발명에 따른 촉매의 상기 반응기 내 적재량은, 촉매마다 밀도가 상이하기 때문에 적재량이 달라질 수 있으며, 반응물인 상기 혼합가스의 기체공간속도와 반응물 유량을 토대로 하여 산정될 수 있다.
In the present invention, it is preferable that the gas hourly space velocity (GHSV) of the mixed gas in the reactor is in the range of 10,000 h -1 to 30,000 h -1 , and the gas space velocity is the volume of the catalyst layer The larger the gas space velocity, the smaller the time during which the reactant stays in the catalyst layer. The loading amount of the catalyst according to the present invention in the reactor may be varied based on the density of catalysts, and may be calculated based on the gas space velocity of the mixed gas as the reactant and the reactant flow rate.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.
[실시예 1] 금속이 첨가된 티타늄산화물 나노와이어 촉매의 제조[Example 1] Production of metal-added titanium oxide nanowire catalyst
금속 첨가 티타늄산화물 나노와이어 촉매를 제조하고, 비교예로서 금속 무첨가 티타늄산화물 나노와이어를 제조하였다. 먼저, 비교예로서 금속 무첨가 티타늄산화물 나노와이어를 제조하기 위해 P25 TiO2, 염화나트륨(NaCl, Sodium chloride), 나트륨 인화물(Na2HPO4, sodium phosphate dibasic)을 중량비 1:4:1로 혼합한 후 고운 분말로 분쇄하고 825℃에서 8시간동안 공기분위기에서 소성시켰다. 상온으로 냉각시킨 후, 대량의 끓는 이온교환수(Deionized water)로 세척하고 건조시켜 티타늄산화물(TiO2) 나노와이어 촉매를 제조하였다.A metal-added titanium oxide nanowire catalyst was prepared, and as a comparative example, a metal-free titanium oxide nanowire was prepared. First, P25 TiO 2, in order, as a comparative example the production of metal-free titanium oxide nanowires sodium chloride (NaCl, Sodium chloride), sodium phosphite (Na 2 HPO 4, sodium phosphate dibasic) a weight ratio of 1: then a solution of 1: 4 Crushed into fine powder and fired at 825 DEG C for 8 hours in an air atmosphere. After cooling to room temperature, the titanium oxide (TiO 2 ) nanowire catalyst was prepared by washing with a large amount of boiling ion-exchanged water (Deionized water) and drying.
금속 첨가 티타늄산화물 나노와이어를 제조하기 위해 P25 TiO2, 염화나트륨(NaCl, Sodium chloride), 나트륨 인화물(Na2HPO4, sodium phosphate dibasic)을 중량비 1:4:1로 혼합한 후, 첨가 금속의 전구체로서 V2O5, Cr(NO3)3, Mn(NO3)2, Co(NO3)2, (NH4)6Mo7O24, Rh(NO3)3 각각을 (첨가 금속)/(Ti)의 원자비가 0.02가되도록 첨가한 후 고운 분말로 분쇄하고 825 oC에서 8시간동안 공기분위기에서 소성시켰다. 상온으로 냉각시킨 후, 대량의 끓는 이온교환수(Deionized water)로 세척하고 건조시켜 금속 첨가 티타늄산화물(V-TiO2, Cr-TiO2, Mn-TiO2, Co-TiO2, Mo-TiO2, Rh-TiO2) 나노와이어 촉매를 제조하였다. 제조된 나노와이어 촉매의 SEM 사진을 도 2에 나타내었다.
For the production of metal added titanium oxide nanowires P25 TiO 2, sodium chloride (NaCl, Sodium chloride), sodium phosphite (Na 2 HPO 4, sodium phosphate dibasic) a weight ratio of 1: 4: then a solution of 1, a precursor of an additive metal as a V 2 O 5, Cr (NO 3) 3, Mn (NO 3) 2, Co (NO 3) 2, (NH 4) 6 Mo 7 O 24, Rh (NO 3 ) 3 was added so that the atomic ratio of (additive metal) / (Ti) became 0.02, and then crushed into fine powder and fired in air atmosphere at 825 ° C for 8 hours. Cr-TiO 2 , Mn-TiO 2 , Co-TiO 2 , and Mo-TiO 2 (TiO 2 ) were added to the mixture, and the mixture was cooled to room temperature, washed with a large amount of deionized water, , Rh-TiO 2 ) nanowire catalysts. SEM photographs of the prepared nanowire catalyst are shown in FIG.
[실험예 1] 금속 첨가 티타늄산화물 나노와이어 촉매를 이용한 메탄의 산화이량화 반응[Experimental Example 1] Oxidation quantification reaction of methane using metal-added titanium oxide nanowire catalyst
상기 실시예 1에서 제조된 금속 첨가 티타늄산화물 나노와이어 촉매 분말 및 비교예인 금속 무첨가 티타늄산화물 나노와이어 촉매 분말 각각 0.09 mL를 1/4-in 실린더형 석영(quartz) 반응기에 넣고 700℃에서 1시간동안 질소 기체를 30 mL/min의 유량으로 흘려주었다. 이후 질소 기체 10.8 mL/min, 메탄 기체 16 mL/min, 산소 기체 3.2 mL/min으로 구성된 혼합 기체를 흘려주고 반응 온도를 각각 750, 775, 800, 825, 850℃를 유지하면서 반응을 수행하였다. 반응유량과 촉매양에 따라 GHSV는 20,000 h-1로 유지하였다. 반응 후 생성물은 -2℃의 트랩을 통과시켜 물을 제거한 후 기상 반응 생성물을 GC-FID와 GC-TCD로 분석하였다. 분석 결과는 하기 표 1에 나타내었다.
0.09 mL of each of the metal-added titanium oxide nanowire catalyst powder prepared in Example 1 and the metal-free titanium oxide nanowire catalyst powder as a comparative example were placed in a 1/4-in cylindrical quartz reactor and heated at 700 ° C. for 1 hour Nitrogen gas was flowed at a flow rate of 30 mL / min. Then, a mixed gas composed of nitrogen gas at 10.8 mL / min, methane gas at 16 mL / min and oxygen gas at 3.2 mL / min was flowed and the reaction was carried out at reaction temperatures of 750, 775, 800, 825 and 850 ° C., respectively. GHSV was maintained at 20,000 h -1 depending on the reaction flow rate and amount of catalyst. After the reaction, the product was passed through a trap at -2 ° C to remove water, and the gas phase reaction products were analyzed by GC-FID and GC-TCD. The results of the analysis are shown in Table 1 below.
상기 나타난 결과를 참조하면, Mn이 첨가된 Mn-TiO2 나노와이어 촉매가 가장 높은 메탄전환율(13.5 - 20.1%)과 높은 C2 탄화수소(에틸렌, 에탄, 아세틸렌) 수율(4.8 - 10.9%)을 보였음을 알 수 있다.The Mn-TiO 2 nanowire catalyst with Mn added showed the highest methane conversion (13.5 - 20.1%) and high C 2 hydrocarbon (ethylene, ethane, acetylene) yields (4.8 - 10.9%). .
1: 메탄, 질소, 산소 실린더
2: MFC (질량유량계)
3: 연속식 기상 반응기
4: 전기가열로
5: 물 트랩
6: GC-FID/TCD1: Methane, nitrogen, oxygen cylinder
2: MFC (mass flowmeter)
3: Continuous gas phase reactor
4: Electric heating furnace
5: Water trap
6: GC-FID / TCD
Claims (13)
상기 금속은 망간(Mn), 바나듐(V), 크롬(Cr), 로듐(Rh), 몰리브덴(Mo) 및 코발트(Co)로 이루어진 군에서 선택되는 하나 이상인 메탄 산화이량화 반응 촉매.The method according to claim 1,
Wherein the metal is at least one selected from the group consisting of manganese (Mn), vanadium (V), chromium (Cr), rhodium (Rh), molybdenum (Mo), and cobalt (Co).
상기 금속 첨가 티타늄산화물은 금속과 티타늄이 원자 수준에서 균일하게 혼합된 혼합산화물인 메탄 산화이량화 반응 촉매.The method according to claim 1,
Wherein the metal-doped titanium oxide is a mixed oxide in which metal and titanium are uniformly mixed at an atomic level.
상기 금속 첨가 티타늄산화물은 금속과 티타늄산화물이 공비혼합된 고체 상태로 존재하는 것인 메탄 산화이량화 반응 촉매.The method according to claim 1,
Wherein the metal-added titanium oxide is present in a solid state in which a metal and titanium oxide are mixed together in an azeotropic state.
상기 금속 첨가 티타늄산화물은 금속/티탄(Ti)의 원자비가 0.01 내지 0.03인 메탄 산화이량화 반응 촉매.The method according to claim 1,
Wherein the metal-added titanium oxide has a metal / titanium (Ti) atomic ratio of 0.01 to 0.03.
티타니아(TiO2)에 금속의 염화물, 질소화물 및 산화물 중 하나인 금속 전구체를 첨가하여 금속/티탄(Ti)의 원자비가 0.01 내지 0.03가 되도록 한 후 분쇄 및 소성시키는 단계를 포함하는 메탄 산화이량화 반응 촉매의 제조방법.A process for producing a methane oxidation polymerization reaction catalyst according to any one of claims 1 to 5,
A step of adding a metal precursor, which is one of chloride, nitrogen and oxides of metal, to the titania (TiO 2 ) so that the atomic ratio of the metal / titanium (Ti) becomes 0.01 to 0.03 and then pulverizing and firing. Gt;
상기 제조방법은 티타니아(TiO2), 염화나트륨 및 나트륨 인화물을 혼합한 혼합물에, 금속의 염화물, 질소화물 및 산화물 중 하나인 금속 전구체를 첨가하여 금속/티탄(Ti)의 원자비가 0.01 내지 0.03가 되도록 하는 단계; 및
상기 단계에서 얻어진 혼합물을 분말로 분쇄하고 700 내지 900℃에서 소성시키는 단계;를 포함하는 메탄 산화이량화 반응 촉매의 제조방법.The method according to claim 6,
In this method, a metal precursor, which is one of a chloride, a nitrogen and an oxide of a metal, is added to a mixture of titania (TiO 2 ), sodium chloride and sodium phosphate so that the atomic ratio of metal / titanium (Ti) is 0.01 to 0.03 ; And
And pulverizing the mixture obtained in the above step into powder and calcining the mixture at 700 to 900 ° C.
상기 반응방법은 제1항 내지 제5항 중 어느 한 항에 따른 메탄 산화이량화 반응 촉매를 반응기에 충진하는 단계; 및
메탄, 산소 및 비활성가스를 포함하는 혼합가스를 상기 반응기 내부로 도입하여 메탄의 산화이량화 반응을 수행하는 단계를 포함하는 메탄 산화이량화 반응방법.9. The method of claim 8,
The reaction method comprises the steps of: charging the reactor with the methanation catalyst according to any one of claims 1 to 5; And
Introducing a mixed gas containing methane, oxygen, and an inert gas into the reactor to perform the oxidation-reduction reaction of methane.
상기 반응기 내부 온도는 750 내지 850℃인 메탄 산화이량화 반응방법.9. The method of claim 8,
Wherein the internal temperature of the reactor is in the range of 750 to 850 占 폚.
상기 혼합가스 중 상기 산소 : 메탄의 부피비는 1 : 1 내지 1 : 10인 메탄 산화이량화 반응방법.9. The method of claim 8,
Wherein the volume ratio of oxygen to methane in the mixed gas is 1: 1 to 1:10.
상기 비활성가스는 질소 또는 헬륨인 메탄 산화이량화 반응방법.9. The method of claim 8,
Wherein the inert gas is nitrogen or helium.
상기 혼합가스의 상기 반응기 내부에서의 기체공간속도(gas hourly space velocity, GHSV)는 10,000 h-1 내지 30,000 h-1인 메탄 산화이량화 반응방법.9. The method of claim 8,
Wherein the gas hourly space velocity (GHSV) of the mixed gas in the reactor is in the range of 10,000 h -1 to 30,000 h -1 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140007653A KR20150087557A (en) | 2014-01-22 | 2014-01-22 | Metal-doped titanium oxide nanowire catalyst, preparing method of the same and method for oxidative coupling reaction of methane using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140007653A KR20150087557A (en) | 2014-01-22 | 2014-01-22 | Metal-doped titanium oxide nanowire catalyst, preparing method of the same and method for oxidative coupling reaction of methane using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150087557A true KR20150087557A (en) | 2015-07-30 |
Family
ID=53876747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140007653A Ceased KR20150087557A (en) | 2014-01-22 | 2014-01-22 | Metal-doped titanium oxide nanowire catalyst, preparing method of the same and method for oxidative coupling reaction of methane using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20150087557A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101865060B1 (en) | 2016-12-19 | 2018-06-07 | 한국과학기술연구원 | Catalyst comprising titanium supported by silicon oxide for oxidative coupling reaction of methane, method for preparing the same, and method for oxidative coupling raction of methane using the same |
| KR20180113448A (en) | 2017-04-06 | 2018-10-16 | 한국과학기술연구원 | Metal-added sodium tungstate catalysts supported on silica, method for preparing the same, and method for oxidative coupling raction of methane using the same |
| KR20190057752A (en) | 2017-11-20 | 2019-05-29 | 한국과학기술연구원 | Catalysts supported on modified-carrier for oxidative coupling raction of methane and method for oxidative coupling raction of methane using the same |
| KR20210075374A (en) | 2019-12-13 | 2021-06-23 | 한국과학기술연구원 | Alkaline earth metal catalyst supported on perovskite carrier and method for oxidative coupling reaction of methane using the same |
-
2014
- 2014-01-22 KR KR1020140007653A patent/KR20150087557A/en not_active Ceased
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101865060B1 (en) | 2016-12-19 | 2018-06-07 | 한국과학기술연구원 | Catalyst comprising titanium supported by silicon oxide for oxidative coupling reaction of methane, method for preparing the same, and method for oxidative coupling raction of methane using the same |
| KR20180113448A (en) | 2017-04-06 | 2018-10-16 | 한국과학기술연구원 | Metal-added sodium tungstate catalysts supported on silica, method for preparing the same, and method for oxidative coupling raction of methane using the same |
| KR20190057752A (en) | 2017-11-20 | 2019-05-29 | 한국과학기술연구원 | Catalysts supported on modified-carrier for oxidative coupling raction of methane and method for oxidative coupling raction of methane using the same |
| US10487021B2 (en) | 2017-11-20 | 2019-11-26 | Korea Institute Of Science And Technology | Catalysts supported on modified-carrier for oxidative coupling reaction of methane and method for oxidative coupling reaction of methane using the same |
| KR20210075374A (en) | 2019-12-13 | 2021-06-23 | 한국과학기술연구원 | Alkaline earth metal catalyst supported on perovskite carrier and method for oxidative coupling reaction of methane using the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101294592B1 (en) | Catalyst for oxidative coupling reaction of methane, method for preparing the same, and method for oxidative coupling reaction of methane using the same | |
| Kang et al. | Improving syngas selectivity of Fe2O3/Al2O3 with yttrium modification in chemical looping methane conversion | |
| CN104226353B (en) | Preparation method of iron-carbide/carbon nanocomposite catalysts including potassium additives for high temperature fischer-tropsch synthesis reaction and the iron-carbide/carbon nanocomposite catalysts thereof, and manufacturing method of liquid hydrocarbon using the same and liquid hydrocarbon thereof | |
| Wang et al. | Stable Cu catalysts supported by two‐dimensional SiO2 with strong metal–support interaction | |
| Olah et al. | Single step bi-reforming and oxidative bi-reforming of methane (natural gas) with steam and carbon dioxide to metgas (CO-2H2) for methanol synthesis: self-sufficient effective and exclusive oxygenation of methane to methanol with oxygen | |
| Marquart et al. | CO2 reduction over Mo2C-based catalysts | |
| JP5493928B2 (en) | Process for producing hydrocarbons | |
| CN105728020A (en) | Preparation method for core-shell type iron carbide catalyst | |
| KR20160123477A (en) | Carbon nitride as catalytic supports for iron-based Fischer-Tropsch synthesis reaction catalysts and its fabrication method | |
| KR20150087557A (en) | Metal-doped titanium oxide nanowire catalyst, preparing method of the same and method for oxidative coupling reaction of methane using the same | |
| Song et al. | Ce-Driven Ce-MnO x/Na2WO4/SiO2 Composite Catalysts for Low-Temperature Oxidative Coupling of Methane | |
| Hosono et al. | Co–CeO2 interaction induces the Mars–van Krevelen mechanism in dehydrogenation of Ethane | |
| Saito et al. | Dehydrogenation of ethane via the Mars–van Krevelen mechanism over La0. 8Ba0. 2MnO3− δ perovskites under anaerobic conditions | |
| JP2017178885A (en) | Process for producing hydrocarbons | |
| Tian et al. | CO methanation on mesoporous Ni–VOx/FDU‐12 catalyst: effects of the VOx promoter on low‐temperature activity | |
| JP5747326B2 (en) | Propylene production method | |
| CN117396274A (en) | Methods for converting CO2 to methane | |
| WO2014182020A1 (en) | Monolith catalyst for carbon dioxide reforming reaction, production method for same, and production method for synthesis gas using same | |
| France et al. | The effect of lanthanum addition on the catalytic activity of γ-alumina supported bimetallic Co–Mo carbides for dry methane reforming | |
| KR101487387B1 (en) | Preparation Method of Metal Carbide Methane Reforming Catalyst and Methane Reforming Catalyst Prepared by the Method | |
| Liu et al. | Plasma-Assisted Chemical Looping Oxidative Coupling of Methane over LaMnO3 at 400° C | |
| CN110801828A (en) | Catalyst for preparing olefin by oxidative dehydrogenation of ethane chemical chain and application of catalyst in oxidative dehydrogenation reaction of ethane | |
| Zeng et al. | Over 90% C2+ selectivity in Kalium-doped manganese perovskite oxygen carriers for chemical looping oxidative coupling of methane with plasma assistance | |
| US11433384B2 (en) | Nitrogen-doped catalyst for oxidative coupling reaction of methane, manufacturing method of nitrogen-doped catalyst for oxidative coupling reaction of methane thereby, and method for oxidative coupling reaction of methane using the same | |
| JP6678450B2 (en) | Partial oxidation catalyst and method for producing carbon monoxide using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| PA0109 | Patent application |
Patent event code: PA01091R01D Comment text: Patent Application Patent event date: 20140122 |
|
| PA0201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 20150420 Patent event code: PE09021S01D |
|
| PG1501 | Laying open of application | ||
| E601 | Decision to refuse application | ||
| PE0601 | Decision on rejection of patent |
Patent event date: 20151020 Comment text: Decision to Refuse Application Patent event code: PE06012S01D Patent event date: 20150420 Comment text: Notification of reason for refusal Patent event code: PE06011S01I |