KR102628990B1 - Pt-W catalyst for synthesis of hydrogen, and Method of preaparing hydrogen using the Pt-W catalyst - Google Patents
Pt-W catalyst for synthesis of hydrogen, and Method of preaparing hydrogen using the Pt-W catalyst Download PDFInfo
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- KR102628990B1 KR102628990B1 KR1020210158167A KR20210158167A KR102628990B1 KR 102628990 B1 KR102628990 B1 KR 102628990B1 KR 1020210158167 A KR1020210158167 A KR 1020210158167A KR 20210158167 A KR20210158167 A KR 20210158167A KR 102628990 B1 KR102628990 B1 KR 102628990B1
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- platinum
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- tungsten
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- dehydrogenation
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 97
- 239000001257 hydrogen Substances 0.000 title claims abstract description 96
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 150000002431 hydrogen Chemical class 0.000 title claims description 5
- 238000000034 method Methods 0.000 title description 34
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 230
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 101
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000010937 tungsten Substances 0.000 claims abstract description 85
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 claims abstract description 50
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims description 49
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- RQOCUPXJUOOIRL-UHFFFAOYSA-N 1,3-dicyclohexylpropan-2-ylbenzene Chemical group C(C1CCCCC1)C(C1=CC=CC=C1)CC1CCCCC1 RQOCUPXJUOOIRL-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 3
- 239000011232 storage material Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 14
- ZONODCCBXBRQEZ-UHFFFAOYSA-N platinum tungsten Chemical compound [W].[Pt] ZONODCCBXBRQEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 27
- 230000008569 process Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- FUUPYXUBNPJSOA-UHFFFAOYSA-N 9-ethyl-1,2,3,4,4a,4b,5,6,7,8,8a,9a-dodecahydrocarbazole Chemical compound C12CCCCC2N(CC)C2C1CCCC2 FUUPYXUBNPJSOA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical group Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical group Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- WXSRCZICDYDNRP-UHFFFAOYSA-N C(C1CCCCC1)C(C1=CC=CC=C1)CC1CCCCC1.C(C1=CC=CC=C1)C(C1=CC=CC=C1)CC1=CC=CC=C1 Chemical compound C(C1CCCCC1)C(C1=CC=CC=C1)CC1CCCCC1.C(C1=CC=CC=C1)C(C1=CC=CC=C1)CC1=CC=CC=C1 WXSRCZICDYDNRP-UHFFFAOYSA-N 0.000 description 1
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- BDPNSNXYBGIFIE-UHFFFAOYSA-J tungsten;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[W] BDPNSNXYBGIFIE-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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- Physics & Mathematics (AREA)
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- Hydrogen, Water And Hydrids (AREA)
Abstract
본 발명은 수소 제조용 백금-텅스텐 촉매 및 이를 이용하여 수소를 제조하는 방법에 관한 것으로, 본 발명에 따른 수소 제조용 촉매는 다공성 담체; 상기 다공성 담체의 세공에 담지되는 백금; 및 상기 세공에 상기 백금과 혼재되어 담지되는 텅스텐;을 포함한다.
본 발명에 따르면, 다공성 담체에 백금과 텅스텐이 혼재되어 담지됨으로써, 낮은 온도에서도 탈수소화 활성이 현저하게 향상되는바, 액상 유기물 수소저장체로부터 효과적으로 수소를 수득할 수 있다.The present invention relates to a platinum-tungsten catalyst for producing hydrogen and a method for producing hydrogen using the same. The catalyst for producing hydrogen according to the present invention includes a porous carrier; Platinum supported in the pores of the porous carrier; and tungsten mixed with the platinum and supported in the pores.
According to the present invention, by supporting a mixture of platinum and tungsten on a porous carrier, the dehydrogenation activity is significantly improved even at low temperatures, making it possible to effectively obtain hydrogen from a liquid organic hydrogen storage body.
Description
본 발명은 수소 제조용 백금-텅스텐 촉매 및 이를 이용하여 수소를 제조하는 방법에 관한 것이다.The present invention relates to a platinum-tungsten catalyst for hydrogen production and a method for producing hydrogen using the same.
화석연료의 매장량 감소, 연소 시 발생하는 오염 물질 및 이산화탄소로 인한 지구 온난화 등의 환경오염 문제가 심각하게 대두됨에 따라 대체 에너지 개발에 대한 전 세계적인 관심 및 수요가 폭발적으로 증가하고 있다.As environmental pollution problems such as decreasing reserves of fossil fuels, pollutants generated during combustion, and global warming caused by carbon dioxide are becoming more serious, global interest in and demand for the development of alternative energy is explosively increasing.
대체 에너지원으로는 풍력, 조력, 지열, 수소 에너지, 태양 에너지 등과 같은 신재생 에너지가 각광받고 있으나, 신재생 에너지는 시간 및 자연 환경에 따른 에너지원의 불안정성으로 인하여 원활한 수요 및 공급이 곤란하므로, 종래의 화석연료를 효과적으로 대체하기 위하여는 안정적으로 에너지를 공급할 수 있도록 잉여 에너지를 저장하고 공급하는 기술에 대한 개발이 요구된다.As alternative energy sources, new and renewable energy such as wind power, tidal power, geothermal energy, hydrogen energy, and solar energy are in the spotlight. However, smooth supply and demand for new and renewable energy is difficult due to the instability of energy sources depending on time and the natural environment. In order to effectively replace conventional fossil fuels, development of technology for storing and supplying surplus energy is required to ensure a stable supply of energy.
이러한 관점에서, 수소 에너지는, 단위 질량당 가장 에너지 효율이 높고, 연소 시 유해한 부산물이 없으며, 수소의 주된 소스인 물은 자연에 풍부하며 사용 후 물로 전환되므로 재사용이 유리하다는 점 등 다양한 장점으로 인해 주목받고 있다. 더욱이, 수소는 태양에너지, 풍력 등과 같은 다른 신재생 에너지를 이용하여 생산할 수 있고, 다양한 에너지원뿐만 아니라, 석유화학 분야를 비롯한 다른 산업분야에서도 광범위하게 적용될 수 있는 등, 국내외에서 미래의 핵심 에너지원으로 부상하고 있다.From this perspective, hydrogen energy has various advantages, including the highest energy efficiency per unit mass, no harmful by-products during combustion, and the fact that water, the main source of hydrogen, is abundant in nature and is converted to water after use, making it advantageous for reuse. It is attracting attention. Moreover, hydrogen can be produced using other renewable energies such as solar energy and wind power, and can be widely applied not only to various energy sources but also to other industrial fields, including the petrochemical field, and is a key energy source of the future at home and abroad. is emerging.
일반적으로 수소 에너지의 연구 개발은 크게 수소의 제조 분야, 운반(수송) 분야, 및 저장 분야로 구분되는데, 수소는 질량 대비 에너지 저장 능력이 우수한 반면, 체적 대비 에너지 저장 능력은 낮기 때문에 수소를 효율적으로 저장하는 기술이 수소 에너지의 실용화에 가장 큰 장애 요인으로 작용하고 있다. 예를 들면, 77 K 조건에서 10 중량% 이상의 질량 저장밀도를 갖는 물질이 알려졌으나, 이러한 물질들의 부피저장 밀도는 40 g/L로서 실제 수소 저장 물질로 사용하기 위하여는 체적 저장밀도가 낮은 편이다. 따라서, 최대한 가볍고 부피가 작은 저장 매체에 가급적 많은 양의 수소를 저장하는 기술에 대한 연구가 활발히 진행되고 있다.In general, research and development of hydrogen energy is largely divided into hydrogen manufacturing, transportation (transportation), and storage fields. Hydrogen has excellent energy storage ability compared to mass, but low energy storage ability compared to volume, so hydrogen can be used efficiently. Storage technology is acting as the biggest obstacle to the practical use of hydrogen energy. For example, materials with a mass storage density of more than 10% by weight at 77 K are known, but the volumetric storage density of these materials is 40 g/L, which is low for use as an actual hydrogen storage material. . Therefore, research is being actively conducted on technologies to store as much hydrogen as possible in a storage medium that is as light and compact as possible.
이를 해결하기 위하여, 각국은 수년간 많은 연구 개발비를 투자하였고, 지금까지 연구 개발된 수소의 효율적인 저장 방법은 700 bar의 압력을 이용해 수소를 압축하는 CGH2 방법 및 영하 253 ℃에서 액화시켜 액체 수소를 보관하는 LH2 방법이 있다. 그러나 이러한 가압 또는 액화 방식은 낮은 온도를 유지해야 하며, 액상 수소의 밀도 역시 712 kg/㎥으로 낮은 수준이다.To solve this problem, each country has invested a lot of money in research and development over the years, and the efficient storage methods of hydrogen that have been researched and developed so far are the CGH2 method, which compresses hydrogen using a pressure of 700 bar, and the CGH2 method, which stores liquid hydrogen by liquefying it at -253 ℃. There is an LH2 method. However, this pressurization or liquefaction method requires maintaining a low temperature, and the density of liquid hydrogen is also low at 712 kg/㎥.
이에 대한 대안으로서 수소 저장능을 갖는 물질, 예를 들면 무기-유기 골격구조체(Metal-organic frameworks; MOFs), 탄소나노튜브, 제올라이트, 활성탄 등의 다공성 유기 또는 무기 나노소재, 메탈하이드라이드 등이 수소 에너지를 효과적으로 저장하는 물질로 연구되고 있으나, MOFs, 다공성 나노 소재의 물리적 흡수에 의한 상온 기상 수소 저장 기술의 경우, 에너지 저장 밀도가 상대적으로 낮고, 수소의 저장 및 탈착 시 요구되는 에너지가 비교적 크기 때문에 소형화 및 모듈화가 곤란하다는 단점이 있다. As an alternative, materials with hydrogen storage capabilities, such as metal-organic frameworks (MOFs), carbon nanotubes, zeolites, porous organic or inorganic nanomaterials such as activated carbon, and metal hydrides, can be used to store hydrogen. Although it is being studied as a material that effectively stores energy, in the case of room temperature gas-phase hydrogen storage technology through physical absorption of MOFs and porous nanomaterials, the energy storage density is relatively low and the energy required for storage and desorption of hydrogen is relatively large. It has the disadvantage of being difficult to miniaturize and modularize.
이러한 이유로 최근에는 액체 유기 수소 운반체 (LOHCs; Liquid Organic Hydrogen Carrier)를 이용한 가역적 촉매 수소화/탈수소화 반응에 의한 수소 저장 기술이 주목받고 있으며, LOHC 기술은 미국 에너지부 (DOE)의 권고안인 5 중량% 이상의 수소를 저장할 수 있으며, 낮은 압력 가동 범위와 저장 물질의 손쉬운 재생으로 인한 기술 구현의 장점을 가지고 있다. 또한 LOHC 기술은 액상 화석 연료가 갖는 다루기 쉬운 물리적 성질과 높은 에너지 밀도로 인해 기존 액체 연료 수송 및 저장 인프라를 이용한 효율적인 이동과 저장이 가능한 에너지 저장체로 자리매김 하고 있다.For this reason, hydrogen storage technology by reversible catalytic hydrogenation/dehydrogenation reaction using liquid organic hydrogen carriers (LOHCs) has recently been attracting attention, and LOHC technology is 5% by weight as recommended by the U.S. Department of Energy (DOE). It can store more hydrogen and has the advantages of technology implementation due to a low pressure operating range and easy regeneration of the stored material. In addition, LOHC technology is positioned as an energy storage material that can be efficiently transported and stored using existing liquid fuel transportation and storage infrastructure due to the easy-to-handle physical properties and high energy density of liquid fossil fuels.
한편, LOHC는 수소를 전달하는 전달체로, 수소를 공급하는 과정에서 전혀 변질되지 않아야 한다는 단점을 가지고 있다. 고온의 촉매공정에서 LOHC가 변질되면, 그 과정에서 발생하는 부산물로 인하여 수소의 순도가 저하될 수 있으며 촉매 또한 활성을 잃어버릴 수 있다. Dibenzyltoluene은 toluene 분자 3개가 뭉쳐진 형태로, 6.3 wt.%의 수소를 분자내에 저장할 수 있는 우수한 성질을 가지고 있다. 하지만 massive molecule은 탈수소화 공정에 높은 온도를 요구하기 때문에, perhydro-dibenzyltoluene은 일반적으로 300℃ 이상의 매우 높은 온도에서 탈수소화 공정을 거치게 된다. 따라서 재활용을 거치면서 열화되거나 코크가 발생할 수 있는데, 이러한 점을 예방하기 위해서는 낮은 온도에서도 높은 탈수소화 활성을 보이는 촉매가 필요하지만, 현재 알려진 촉매들의 경우 270℃ 미만에서의 perhydro-dibenzyltoluene의 탈수소화율이 매우 낮은 수준을 나타내고 있다.On the other hand, LOHC is a carrier that delivers hydrogen, and has the disadvantage that it must not deteriorate at all during the process of supplying hydrogen. If LOHC deteriorates during a high-temperature catalyst process, the purity of hydrogen may decrease due to by-products generated in the process, and the catalyst may also lose activity. Dibenzyltoluene is a form of three toluene molecules aggregated together and has excellent properties of being able to store 6.3 wt.% of hydrogen within the molecule. However, because massive molecules require a high temperature for the dehydrogenation process, perhydro-dibenzyltoluene generally undergoes the dehydrogenation process at a very high temperature of over 300℃. Therefore, deterioration or coking may occur during recycling. To prevent this, a catalyst showing high dehydrogenation activity even at low temperatures is required. However, currently known catalysts have a low dehydrogenation rate of perhydro-dibenzyltoluene below 270°C. It represents a very low level.
본 발명은 전술한 문제점을 해결하기 위해 안출된 것으로서, 본 발명의 목적은 백금이 담지된 촉매에 텅스텐을 조촉매로 추가 도입함으로써 낮은 온도에서도 탈수소화 활성이 향상된 수소 제조용 촉매를 제공하는 것이다.The present invention was devised to solve the above-mentioned problems, and the purpose of the present invention is to provide a catalyst for hydrogen production with improved dehydrogenation activity even at low temperatures by additionally introducing tungsten as a cocatalyst to the platinum-supported catalyst.
본 발명의 다른 목적은 백금이 담지된 촉매에 텅스텐을 조촉매로 추가 도입함으로써 낮은 온도에서도 탈수소화 활성이 향상된 수소 제조용 촉매의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing a catalyst for hydrogen production with improved dehydrogenation activity even at low temperatures by additionally introducing tungsten as a cocatalyst to the platinum-supported catalyst.
본 발명의 또 다른 목적은 상기 수소 제조용 촉매를 이용하여 수소를 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing hydrogen using the catalyst for producing hydrogen.
본 발명은 상기 과제를 해결하기 위하여,In order to solve the above problems, the present invention
다공성 담체; 상기 다공성 담체의 세공에 담지되는 백금; 및 상기 세공에 상기 백금과 혼재되어 담지되는 텅스텐;을 포함하는 수소 제조용 촉매를 제공한다.porous carrier; Platinum supported in the pores of the porous carrier; and tungsten mixed with the platinum and supported in the pores.
본 발명에 따르면, 상기 다공성 담체는 활성탄(activated carbon) 또는 산화알루미늄(Al2O3)일 수 있다.According to the present invention, the porous carrier may be activated carbon or aluminum oxide (Al 2 O 3 ).
본 발명에 따르면, 상기 활성탄은 산화 그래핀, 카본블랙, Vulcan으로 이루어진 군에서 선택될 수 있다.According to the present invention, the activated carbon may be selected from the group consisting of graphene oxide, carbon black, and Vulcan.
본 발명에 따르면, 상기 텅스텐은 상기 다공성 담체의 세공에 백금이 담지된 후에 담지될 수 있다.According to the present invention, the tungsten can be supported after platinum is supported in the pores of the porous carrier.
본 발명에 따르면, 상기 백금과 상기 텅스텐은 0.9:0.1 내지 0.6:0.4의 중량비로 담지될 수 있다.According to the present invention, the platinum and the tungsten may be supported at a weight ratio of 0.9:0.1 to 0.6:0.4.
본 발명은 또한, (a) 다공성 담체의 세공에 백금 전구체 용액과 텅스텐 전구체 용액을 담지하는 단계; 및 (b) 상기 백금 전구체 용액과 텅스텐 전구체 용액이 담지된 상기 다공성 담체를 환원시키는 단계;를 포함하고, 상기 (a) 단계는, 상기 다공성 담체의 세공에 백금 전구체 용액을 담지하는 단계; 상기 백금 전구체 용액이 담지된 상기 다공성 담체를 열처리하는 단계; 및 상기 열처리된 상기 다공성 담체의 세공에 텅스텐 전구체 용액을 담지하는 단계;를 포함하는 수소 제조용 촉매의 제조방법을 제공한다.The present invention also includes the steps of (a) supporting a platinum precursor solution and a tungsten precursor solution in the pores of a porous carrier; and (b) reducing the porous carrier on which the platinum precursor solution and the tungsten precursor solution are supported, wherein step (a) includes supporting the platinum precursor solution in the pores of the porous carrier; heat-treating the porous carrier on which the platinum precursor solution is supported; and supporting a tungsten precursor solution in the pores of the heat-treated porous carrier.
본 발명에 따르면, 상기 수소 제조용 촉매는 백금과 텅스텐이 0.9:0.1 내지 0.6:0.4의 중량비로 담지될 수 있다.According to the present invention, the catalyst for hydrogen production may contain platinum and tungsten at a weight ratio of 0.9:0.1 to 0.6:0.4.
본 발명에 따르면, 상기 (a) 단계는 초기 젖음 담지법(incipient wetness impregnation)으로 수행될 수 있다.According to the present invention, step (a) may be performed by incipient wetness impregnation.
본 발명에 따르면, 상기 (b) 단계의 환원은 수소와 질소의 혼합 가스 분위기하에서 300 내지 600℃에서 수행될 수 있다.According to the present invention, the reduction in step (b) may be performed at 300 to 600° C. in a mixed gas atmosphere of hydrogen and nitrogen.
본 발명은 또한, 상기 수소 제조용 촉매, 및 액상 유기물 수소 저장체(Liquid Organic Hydrogen Carrier, LOHC)를 혼합하는 단계; 및 상기 혼합 후 탈수소화 반응을 수행하는 단계를 포함하는 수소 제조방법을 제공한다.The present invention also includes the steps of mixing the catalyst for hydrogen production and a liquid organic hydrogen carrier (Liquid Organic Hydrogen Carrier, LOHC); and performing a dehydrogenation reaction after the mixing.
본 발명에 따르면, 상기 액상 유기물 수소 저장체는 퍼하이드로-디벤질톨루엔(perhydro-Dibenzyltoluene), 시클로헥산(cyclohexane), 메틸시클로헥산(methyl cyclohexane), 데칼린(decalin), 벤질톨루엔(benzyl toluene), 디벤질톨루엔(dibenzyl toluene), 퍼하이드로N-에틸카바졸(perhydro-N-ethylcarbazole), 2-[(N-메틸시클로헥실)메틸]피페리딘으로 이루어진 군에서 선택될 수 있다.According to the present invention, the liquid organic hydrogen storage includes perhydro-Dibenzyltoluene, cyclohexane, methyl cyclohexane, decalin, benzyl toluene, It may be selected from the group consisting of dibenzyl toluene, perhydro-N-ethylcarbazole, and 2-[(N-methylcyclohexyl)methyl]piperidine.
본 발명에 따르면, 상기 탈수소화 반응은 250 ~ 300℃의 온도에서 2 내지 4시간 동안 수행될 수 있다.According to the present invention, the dehydrogenation reaction can be performed at a temperature of 250 to 300 ° C. for 2 to 4 hours.
본 발명의 특징 및 이점들은 첨부도면에 의거한 다음의 상세한 설명으로 더욱 명백해질 것이다.The features and advantages of the present invention will become more apparent from the following detailed description based on the accompanying drawings.
이에 앞서 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이고 사전적인 의미로 해석되어서는 아니되며, 발명자가 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Prior to this, terms or words used in this specification and claims should not be interpreted in their usual, dictionary meaning, and the inventor may appropriately define the concept of the term in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.
본 발명에 따르면, 다공성 담체에 백금과 텅스텐이 혼재되어 담지됨으로써, 낮은 온도에서도 탈수소화 활성이 현저하게 향상되는바, 액상 유기물 수소저장체로부터 효과적으로 수소를 수득할 수 있다.According to the present invention, by supporting a mixture of platinum and tungsten on a porous carrier, the dehydrogenation activity is significantly improved even at low temperatures, making it possible to effectively obtain hydrogen from a liquid organic hydrogen storage body.
도 1은 본 발명의 실시예 1 내지 실시예 3 및 비교예 1 내지 비교예 3에 따라 제조된 수소 제조용 촉매의 탈수소화도를 나타내는 그래프이다.
도 2는 본 발명의 실시예 2, 비교예 1 및 비교예 4에 따라 제조된 수소 제조용 촉매의 탈수소화도를 나타내는 그래프이다.
도 3은 본 발명의 실시예 2, 비교예 1, 비교예 2 및 비교예 5에 따라 제조된 수소 제조용 촉매의 탈수소화도를 나타내는 그래프이다.
도 4는 본 발명의 실시예 1 내지 실시예 3, 비교예 1 및 비교예 3에 따라 제조된 수소 제조용 촉매의 표면에서의 전자적 특성 변화 및 이에 따른 백금 당 탈수소화 활성을 비교한 결과를 나타낸 것이다.Figure 1 is a graph showing the dehydrogenation degree of catalysts for hydrogen production prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 of the present invention.
Figure 2 is a graph showing the degree of dehydrogenation of catalysts for hydrogen production prepared according to Example 2, Comparative Example 1, and Comparative Example 4 of the present invention.
Figure 3 is a graph showing the degree of dehydrogenation of catalysts for hydrogen production prepared according to Example 2, Comparative Example 1, Comparative Example 2, and Comparative Example 5 of the present invention.
Figure 4 shows the results of comparing the change in electronic properties on the surface of catalysts for hydrogen production prepared according to Examples 1 to 3, Comparative Examples 1, and Comparative Examples 3 of the present invention and the resulting platinum sugar dehydrogenation activity. .
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술 분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술 분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.
본 발명에서는 백금이 담지된 촉매에 텅스텐을 조촉매로 추가 도입함으로써 낮은 온도에서도 탈수소화 활성이 향상된 수소 제조용 촉매, 이의 제조방법 및 이를 이용하여 수소를 제조하는 방법을 제공하고자 한다.The present invention seeks to provide a catalyst for producing hydrogen with improved dehydrogenation activity even at low temperatures by additionally introducing tungsten as a cocatalyst to a catalyst carrying platinum, a method for producing the same, and a method for producing hydrogen using the same.
이를 위해 먼저 본 발명은 다공성 담체; 상기 다공성 담체의 세공에 담지되는 백금; 및 상기 세공에 상기 백금과 혼재되어 담지되는 텅스텐;을 포함하는 수소 제조용 촉매를 제공한다.To this end, the present invention first provides a porous carrier; Platinum supported in the pores of the porous carrier; and tungsten mixed with the platinum and supported in the pores.
이때, 상기 다공성 담체는 표면에 다수의 세공을 구비한 다공성 부재로서, 백금 및 텅스텐을 수용한다. 세공은 마이크로포어(micropore), 또는 메조포어(mesopore) 크기로 형성될 수 있다. 일반적으로, 마이크로포어는 2 ㎚ 이하, 메조포어는 2 ㎚ 초과 50 ㎚ 미만 정도의 크기로 정의되는데, 본 발명에서는 반드시 이에 한정되는 것은 아니고 백금 및 텅스텐이 혼재되어 담지될 수 있는 크기이면 족하다.At this time, the porous carrier is a porous member with a large number of pores on the surface, and accommodates platinum and tungsten. Pore may be formed in the size of micropore or mesopore. Generally, micropores are defined as 2 nm or less, and mesopores are defined as having a size of more than 2 nm but less than 50 nm. However, in the present invention, this is not necessarily limited, and any size that allows a mixture of platinum and tungsten to be supported is sufficient.
또한, 상기 다공성 담체는 활성탄(activated carbon) 또는 산화알루미늄(Al2O3)인 것이 바람직하며, 상기 활성탄은 산화 그래핀, 카본블랙, Vulcan으로 이루어진 군에서 선택될 수 있다. 또한, 상기 산화알루미늄은 θ-, δ-, γ-, α- phase를 갖는 것이 바람직하며, γ-phase를 갖는 것이 더욱 바람직하다. In addition, the porous carrier is preferably activated carbon or aluminum oxide (Al 2 O 3 ), and the activated carbon may be selected from the group consisting of graphene oxide, carbon black, and Vulcan. In addition, the aluminum oxide preferably has θ-, δ-, γ-, and α- phases, and more preferably has a γ-phase.
또한, 하기 실시예의 결과로부터 알 수 있는 바와 같이, 상기 텅스텐은 상기 다공성 담체의 세공에 백금이 담지된 후에 담지되는 것이 바람직하며, 상기 백금과 텅스텐은 상호 혼재되어 다공성 담체에 담지되며, 백금과 텅스텐의 상호작용에 의해 저온에서도 탈수소화 활성이 현저하게 향상되는바, 수소 제조에 유용하게 활용될 수 있다.In addition, as can be seen from the results of the following examples, it is preferable that the tungsten is supported after platinum is supported in the pores of the porous carrier, and the platinum and tungsten are mixed with each other and supported on the porous carrier, and platinum and tungsten Due to the interaction, the dehydrogenation activity is significantly improved even at low temperatures, so it can be usefully used in hydrogen production.
또한, 하기 실시예의 결과로부터 알 수 있는 바와 같이, 상기 백금과 상기 텅스텐은 0.9:0.1 내지 0.6:0.4의 중량비로 담지되는 것이 바람직하다. 하기 실시예의 결과로부터 알 수 있는 바와 같이, 담지되는 백금과 텅스텐의 중량비가 상기 범위를 벗어나게 되면, 본 발명에 따른 촉매의 활성이 저하될 수 있다. In addition, as can be seen from the results of the following examples, it is preferable that the platinum and the tungsten are supported at a weight ratio of 0.9:0.1 to 0.6:0.4. As can be seen from the results of the following examples, if the weight ratio of the supported platinum and tungsten is outside the above range, the activity of the catalyst according to the present invention may be reduced.
또한, 상기 백금-텅스텐은 상기 다공성 담체 총 중량에 대하여 1 내지 10 중량%로 담지되는 것이 바람직하다. In addition, the platinum-tungsten is preferably supported in an amount of 1 to 10% by weight based on the total weight of the porous carrier.
이하에서는 발명에 따른 수소 제조용 촉매의 제조방법에 대해 설명한다. 여기서 수소 제조용 촉매에 관한 내용은 상술하였는바, 중복되는 사항에 대해서는 설명을 생략하거나 간단하게만 기술한다.Hereinafter, a method for producing a catalyst for hydrogen production according to the invention will be described. Here, the details regarding the catalyst for hydrogen production have been described above, and the description of overlapping matters will be omitted or only briefly described.
본 발명에 따른 수소 제조용 촉매의 제조방법은 (a) 다공성 담체의 세공에 백금 전구체 용액과 텅스텐 전구체 용액을 담지하는 단계; 및 (b) 상기 백금 전구체 용액과 텅스텐 전구체 용액이 담지된 상기 다공성 담체를 환원시키는 단계;를 포함한다.The method for producing a catalyst for hydrogen production according to the present invention includes the steps of (a) supporting a platinum precursor solution and a tungsten precursor solution in the pores of a porous carrier; and (b) reducing the porous carrier on which the platinum precursor solution and the tungsten precursor solution are supported.
본 발명에 따른 상기 수소 제조용 촉매를 제조하기 위해서는, 먼저 (a) 다공성 담체의 세공에 백금 전구체 용액과 텅스텐 전구체 용액을 담지한다. 이때, 다공성 담체는 기공 내에 잔존하는 물분자를 제거하여 담체의 기공 내부로 백금과 텅스텐이 담지되는 효율을 높이기 위해, 100 내지 150℃의 온도에서 건조된 것을 사용하는 것이 바람직할 수 있다. 또한, 상기 백금 전구체 용액과 상기 텅스텐 전구체 용액 담지 시 백금 전구체 용액과 텅스텐 전구체 용액을 혼합하여 동시에 담지하거나, 텅스텐 전구체 용액을 담지한 후 백금 전구체 용액을 담지하거나, 백금 전구체 용액을 담지한 후 텅스텐 전구체 용액을 담지할 수 있으나, 하기 실시예의 결과로부터 알 수 있는 바와 같이, 촉매의 탈수소화도 활성 향상을 위해서는 백금 전구체 용액을 담지한 후 텅스텐 전구체 용액을 담지하는 것이 바람직하다. To prepare the catalyst for hydrogen production according to the present invention, first (a) a platinum precursor solution and a tungsten precursor solution are supported in the pores of a porous carrier. At this time, it may be desirable to use a porous carrier dried at a temperature of 100 to 150° C. in order to remove water molecules remaining in the pores and increase the efficiency of supporting platinum and tungsten inside the pores of the carrier. In addition, when supporting the platinum precursor solution and the tungsten precursor solution, the platinum precursor solution and the tungsten precursor solution are mixed and supported simultaneously, the tungsten precursor solution is supported and then the platinum precursor solution is supported, or the platinum precursor solution is supported and then the tungsten precursor is supported. A solution can be supported, but as can be seen from the results of the following examples, in order to improve the dehydrogenation activity of the catalyst, it is preferable to support the platinum precursor solution and then the tungsten precursor solution.
이를 위해, 상기 (a) 단계는, 상기 다공성 담체의 세공에 백금 전구체 용액을 담지하는 단계; 상기 백금 전구체 용액이 담지된 상기 다공성 담체를 열처리하는 단계; 및 상기 열처리된 상기 다공성 담체의 세공에 텅스텐 전구체 용액을 담지하는 단계;를 포함한다. 이때, 상기 열처리는 200 내지 400℃의 온도 범위에서 30분 내지 2시간 동안 수행될 수 있다.To this end, step (a) includes supporting a platinum precursor solution in the pores of the porous carrier; heat-treating the porous carrier on which the platinum precursor solution is supported; and supporting a tungsten precursor solution in the pores of the heat-treated porous carrier. At this time, the heat treatment may be performed for 30 minutes to 2 hours at a temperature range of 200 to 400°C.
또한, 상기 (a) 단계를 통해 상기 다공성 담체에 담지되는 백금과 텅스텐은 0.9:0.1 내지 0.6:0.4의 중량비로 담지되는 것이 바람직하다. 또한, 담지되는 상기 백금과 텅스텐의 합은 상기 다공성 담체 총 중량에 대하여 1 내지 10 중량%인 것이 바람직하다. 하기 실시예의 결과로부터 알 수 있는 바와 같이, 담지되는 백금과 텅스텐의 중량비가 상기 범위를 벗어나게 되면, 본 발명에 따른 촉매의 활성이 저하될 수 있다. In addition, platinum and tungsten supported on the porous carrier through step (a) are preferably supported at a weight ratio of 0.9:0.1 to 0.6:0.4. In addition, the sum of the platinum and tungsten supported is preferably 1 to 10% by weight based on the total weight of the porous carrier. As can be seen from the results of the following examples, if the weight ratio of the supported platinum and tungsten is outside the above range, the activity of the catalyst according to the present invention may be reduced.
또한, 상기 (a) 단계는 초기 젖음 담지법(incipient wetness impregnation)으로 수행될 수 있다. 초기 젖음 담지법에 따른 담지의 경우, 백금 전구체 용액과 텅스텐 전구체 용액이 충분히 담지되도록 수차례 담지 공정을 반복하고, 담지마다 건조 과정을 거칠 수 있다. 여기서, 상기 다공성 담체는 활성탄(activated carbon) 또는 산화알루미늄(Al2O3)인 것이 바람직하며, 상기 활성탄은 산화 그래핀, 카본블랙, Vulcan으로 이루어진 군에서 선택될 수 있다. 또한, 상기 산화알루미늄은 θ-, δ-, γ-, α- phase를 갖는 것이 바람직하며, γ-phase를 갖는 것이 더욱 바람직할 수 있다. 또한, 상기 백금 전구체 용액은 백금 염화물 군 및 백금 질산화물 염을 지칭하며, 백금을 제공할 수 있는 염이라면 특별히 한정되지 않으나, 예를 들어 platinum chloride, potassium hexachloroplatinate, chloroplatinic acid 및 tetraammineplatinum nitrate로 이루어진 군에서 선택되는 것을 사용할 수 있다. 또한, 상기 텅스텐 전구체 용액은 텅스텐 염화물 군, 텅스텐 수산화물 및 텅스텐 암모늄염을 지칭하며, 텅스텐을 제공할 수 있는 염이라면 특별히 한정되지 않으나, 예를 들어 tungsten chloride, ammonium metatungstate 및 ammonium paratungstate로 이루어진 군에서 선택되는 것을 사용할 수 있다. 또한, 상기 초기 젖음 담지법을 이용한 담지의 경우에는, 백금 전구체 용액 또는 텅스텐 전구체 용액이 담지된 다공성 담체를 100 ~ 150℃에서 8 ~ 24 시간 동안 건조할 수 있다.Additionally, step (a) may be performed by incipient wetness impregnation. In the case of support according to the initial wet support method, the support process may be repeated several times to ensure that the platinum precursor solution and the tungsten precursor solution are sufficiently supported, and a drying process may be performed for each support. Here, the porous carrier is preferably activated carbon or aluminum oxide (Al 2 O 3 ), and the activated carbon may be selected from the group consisting of graphene oxide, carbon black, and Vulcan. In addition, the aluminum oxide preferably has θ-, δ-, γ-, and α- phases, and may more preferably have a γ-phase. In addition, the platinum precursor solution refers to a platinum chloride group and a platinum nitrate salt, and is not particularly limited as long as it is a salt that can provide platinum, but is, for example, selected from the group consisting of platinum chloride, potassium hexachloroplatinate, chloroplatinic acid, and tetraammineplatinum nitrate. You can use anything that works. In addition, the tungsten precursor solution refers to the tungsten chloride group, tungsten hydroxide, and tungsten ammonium salt, and is not particularly limited as long as it is a salt capable of providing tungsten, but for example, it is selected from the group consisting of tungsten chloride, ammonium metatungstate, and ammonium paratungstate. can be used. Additionally, in the case of support using the initial wet support method, the porous carrier on which the platinum precursor solution or tungsten precursor solution is supported can be dried at 100 to 150°C for 8 to 24 hours.
다음으로, 상기 (b) 단계에서는 상기 백금 전구체 용액과 텅스텐 전구체 용액이 담지된 상기 다공성 담체를 수소와 질소의 혼합가스를 이용하여 환원시키며, 구체적으로는 5~20% 부피비의 H2/N2 기체 분위기 하, 300 내지 600℃에서 30분 내지 3시간 동안 수행하는 것이 바람직하다. 상기 환원 단계를 거쳐 최종적으로 본 발명에 따른 수소 제조용 백금-텅스텐 촉매가 제조된다. Next, in step (b), the porous carrier on which the platinum precursor solution and the tungsten precursor solution are supported is reduced using a mixed gas of hydrogen and nitrogen, specifically, H 2 /N 2 at a volume ratio of 5 to 20%. It is preferably carried out at 300 to 600°C for 30 minutes to 3 hours under a gas atmosphere. Through the above reduction step, the platinum-tungsten catalyst for hydrogen production according to the present invention is finally manufactured.
본 발명은 또한, 상기 수소 제조용 촉매, 및 액상 유기물 수소 저장체(Liquid Organic Hydrogen Carrier, LOHC)를 혼합하는 단계; 및 상기 혼합 후 탈수소화 반응을 수행하는 단계를 포함하는 수소 제조방법을 제공한다.The present invention also includes the steps of mixing the catalyst for hydrogen production and a liquid organic hydrogen carrier (Liquid Organic Hydrogen Carrier, LOHC); and performing a dehydrogenation reaction after the mixing.
이때, 상기 액상 유기물 수소 저장체는 퍼하이드로-디벤질톨루엔(perhydro-Dibenzyltoluene), 시클로헥산(cyclohexane), 메틸시클로헥산(methyl cyclohexane), 데칼린(decalin), 벤질톨루엔(benzyl toluene), 디벤질톨루엔(dibenzyl toluene), 퍼하이드로N-에틸카바졸(perhydro-N-ethylcarbazole), 2-[(N-메틸시클로헥실)메틸]피페리딘으로 이루어진 군에서 선택될 수 있으며, 바람직하게는 퍼하이드로-디벤질톨루엔(perhydro-Dibenzyltoluene)일 수 있다.At this time, the liquid organic hydrogen storage is perhydro-Dibenzyltoluene, cyclohexane, methyl cyclohexane, decalin, benzyl toluene, and dibenzyltoluene. (dibenzyl toluene), perhydro-N-ethylcarbazole, and 2-[(N-methylcyclohexyl)methyl]piperidine, preferably perhydro- It may be dibenzyltoluene (perhydro-Dibenzyltoluene).
본 발명에 따르면, 상기 탈수소화 반응은 250 ~ 300℃의 온도에서 2 내지 4시간 동안 수행하는 것이 바람직하다.According to the present invention, the dehydrogenation reaction is preferably performed at a temperature of 250 to 300°C for 2 to 4 hours.
[실시예][Example]
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. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as limited by these examples. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
실시예Example 1. 백금 담지 후 텅스텐을 1. After depositing platinum, tungsten 담지한supported PtPt 00 .9.9 WW 0.10.1 // AlAl 22 OO 33 촉매의 제조 Preparation of catalyst
(1) 백금 및 텅스텐 전구체 용액 제조(1) Preparation of platinum and tungsten precursor solution
5 ml 바이알에 증류수 1.302 ml, tetraammineplatinum nitrate 0.0898 g 을 함께 섞은 후 초음파 분산기를 이용하여 10분간 교반하여 백금 전구체 용액을 제조하였고, 5 ml 바이알에 증류수 0.434 ml, ammonium metatungstate hydrate 0.00655 g 을 함께 섞은 후 초음파 분산기를 이용하여 10분간 교반하여 텅스텐 전구체 용액을 제조하였다.A platinum precursor solution was prepared by mixing 1.302 ml of distilled water and 0.0898 g of tetraammineplatinum nitrate in a 5 ml vial and stirring for 10 minutes using an ultrasonic disperser. Then, 0.434 ml of distilled water and 0.00655 g of ammonium metatungstate hydrate were mixed in a 5 ml vial and then ultrasonicated. A tungsten precursor solution was prepared by stirring for 10 minutes using a disperser.
(2) γ상 알루미나 제조(2) Production of γ-phase alumina
Boehmite(AlOOH) 1 내지 20 g을 공기 분위기하에서 650 ℃, 5시간 동안 소성시켜 γ상 알루미나를 제조하였다.γ-phase alumina was prepared by calcining 1 to 20 g of boehmite (AlOOH) at 650°C for 5 hours in an air atmosphere.
(3) 백금이 담지된 γ상 알루미나 제조(3) Production of γ-phase alumina loaded with platinum
상기 백금 전구체 용액을 상기 알루미나 1g에 초기 젖음 담지법(incipient wetness impregnation)을 이용하여 담지하였다. 이후 120℃에서 12시간 동안 건조 후 소성로에서 공기 분위기하에 300℃, 1시간 동안 열처리하였다. The platinum precursor solution was supported on 1 g of the alumina using an initial wetness impregnation method. Afterwards, it was dried at 120°C for 12 hours and then heat treated at 300°C for 1 hour in an air atmosphere in a kiln.
(4) 텅스텐이 조촉매로 첨가된 Pt0 .9W0.1/Al2O3 촉매 제조(4) Preparation of Pt 0.9 W 0.1 /Al 2 O 3 catalyst with tungsten added as cocatalyst
상기 백금이 담지된 γ상 알루미나에 상기 텅스텐 전구체 용액을 초기 젖음 담지법으로 담지하였다. 이후 120℃에서 12시간 동안 건조 후 10% H2/N2 기체 분위기 하, 450℃에서 1시간 동안 환원시켜, 본 발명에 따른 수소 제조용 백금-텅스텐 촉매(Pt0.9W0.1/Al2O3)를 제조하였다. 상기 촉매는 진공 분위기하에서 보관하였다.The tungsten precursor solution was supported on the γ-phase alumina on which the platinum was supported using an initial wet deposition method. Afterwards, it was dried at 120°C for 12 hours and then reduced at 450°C for 1 hour under a 10% H 2 /N 2 gas atmosphere to produce a platinum-tungsten catalyst for hydrogen production according to the present invention (Pt 0.9 W 0.1 /Al 2 O 3 ). was manufactured. The catalyst was stored under vacuum atmosphere.
실시예Example 2. 백금 담지 후 텅스텐을 2. After depositing platinum, tungsten 담지한supported PtPt 00 .8.8 WW 0.20.2 // AlAl 22 OO 33 촉매의 제조 Preparation of catalyst
tetraammineplatinum nitrate 0.0803g을 사용하고, ammonium metatungstate hydrate 0.0132g을 사용하였다는 점을 제외하고는 실시예 1과 동일한 방법을 이용하여 본 발명에 따른 수소 제조용 백금-텅스텐 촉매(Pt0.8W0.2/Al2O3)를 제조하였다. A platinum-tungsten catalyst for hydrogen production according to the present invention was prepared using the same method as Example 1, except that 0.0803 g of tetraammineplatinum nitrate and 0.0132 g of ammonium metatungstate hydrate were used. 3 ) was prepared.
실시예Example 3. 백금 담지 후 텅스텐을 3. After depositing platinum, tungsten 담지한supported PtPt 00 .6.6 WW 0.40.4 // AlAl 22 OO 33 촉매의 제조 Preparation of catalyst
tetraammineplatinum nitrate 0.0610g을 사용하고, ammonium metatungstate hydrate 0.0266g을 사용하였다는 점을 제외하고는 실시예 1과 동일한 방법을 이용하여 본 발명에 따른 수소 제조용 백금-텅스텐 촉매(Pt0.6W0.4/Al2O3)를 제조하였다.A platinum-tungsten catalyst for hydrogen production according to the present invention was prepared using the same method as Example 1, except that 0.0610 g of tetraammineplatinum nitrate and 0.0266 g of ammonium metatungstate hydrate were used. 3 ) was prepared.
비교예Comparative example 1. Pt/ 1.Pt/ AlAl 22 OO 33 촉매의 제조 Preparation of catalyst
tetraammineplatinum nitrate 0.0992g을 사용하고, 텅스텐 전구체 용액 ammonium metatungstate hydrate을 사용하지 않은 점을 제외하고는 실시예 1과 동일한 방법을 이용하여 텅스텐이 담지되지 않은 백금 담지 수소 제조용 촉매(Pt/Al2O3)를 제조하였다.A platinum-supported hydrogen production catalyst (Pt/Al 2 O 3 ) without tungsten was prepared using the same method as in Example 1, except that 0.0992 g of tetraammineplatinum nitrate was used and the tungsten precursor solution ammonium metatungstate hydrate was not used. was manufactured.
비교예Comparative example 2. W/ 2.W/ AlAl 22 OO 33 촉매의 제조 Preparation of catalyst
ammonium metatungstate 0.0691g 사용하고, 백금 전구체 용액 tetraammineplatinum nitrate을 사용하지 않은 점을 제외하고는 실시예 1과 동일한 방법을 이용하여 백금이 담지되지 않은 텅스텐 담지 수소 제조용 촉매(W/Al2O3)를 제조하였다.A tungsten-supported hydrogen production catalyst (W/Al 2 O 3 ) without platinum was prepared using the same method as Example 1, except that 0.0691 g of ammonium metatungstate was used and the platinum precursor solution tetraammineplatinum nitrate was not used. did.
비교예 3. 백금 담지 후 텅스텐을 담지한 PtComparative Example 3. Pt loaded with platinum and then tungsten 0.20.2 WW 0.80.8 /Al/Al 22 OO 33 촉매의 제조 Preparation of catalyst
tetraammineplatinum nitrate 0.0208g을 사용하고, Ammonium metatungstate hydrate 0.0546g을 사용하였다는 점을 제외하고는 실시예 1과 동일한 방법을 이용하여 수소 제조용 백금-텅스텐 촉매(Pt0.2W0.8/Al2O3)를 제조하였다.A platinum-tungsten catalyst (Pt 0.2 W 0.8 /Al 2 O 3 ) for hydrogen production was prepared using the same method as Example 1, except that 0.0208 g of tetraammineplatinum nitrate and 0.0546 g of ammonium metatungstate hydrate were used. did.
비교예Comparative example 4. 백금 담지 시 열처리 공정을 수행하지 않고 텅스텐을 4. When depositing platinum, tungsten is used without performing a heat treatment process. 담지한supported Pt Pt 0.80.8 WW 0.20.2 /Al/Al 22 OO 33 (without calcination) 촉매의 제조(without calcination) Preparation of catalyst
tetraammineplatinum nitrate 0.0803g을 사용하고, ammonium metatungstate hydrate 0.0132g을 사용하되, 실시예 1의 (3)의 300℃, 1시간 동안 열처리하는 공정을 수행하지 않은 점을 제외하고는 실시예 1과 동일한 방법을 이용하여 수소 제조용 백금-텅스텐 촉매(Pt0.8W0.2/Al2O3, without calcination)를 제조하였다.The same method as Example 1 was used except that 0.0803 g of tetraammineplatinum nitrate and 0.0132 g of ammonium metatungstate hydrate were used, but the heat treatment process at 300°C for 1 hour in (3) of Example 1 was not performed. A platinum-tungsten catalyst for hydrogen production (Pt 0.8 W 0.2 /Al 2 O 3 , without calcination) was prepared.
비교예Comparative example 5. 텅스텐 담지 후 백금을 5. After depositing tungsten, platinum 담지한supported W W 0.0. 22 PtPt 00 .8.8 // AlAl 22 OO 33 촉매의 제조 Preparation of catalyst
tetraammineplatinum nitrate 0.0803g을 사용하고, ammonium metatungstate hydrate 0.0132g을 사용하되, 상기 실시예 1의 (3)과 (4)의 공정 순서를 바꾸어서, 텅스텐이 담지된 γ상 알루미나를 제조한 후, 백금 전구체 용액을 초기 젖음법으로 담지한 것을 제외하고는 실시예 1과 동일한 방법을 이용하여 텅스텐 담지 후 백금을 담지한 수소 제조용 텅스텐-백금 촉매(W0.2Pt0.8/Al2O3)를 제조하였다.0.0803 g of tetraammineplatinum nitrate and 0.0132 g of ammonium metatungstate hydrate were used, but the process order of (3) and (4) of Example 1 was changed to prepare tungsten-supported γ-phase alumina, and then platinum precursor solution. A tungsten-platinum catalyst for hydrogen production (W 0.2 Pt 0.8 /Al 2 O 3 ) was prepared by supporting tungsten and then supporting platinum using the same method as in Example 1, except that it was supported by the initial wetting method.
실험예Experiment example 1. 백금과 텅스텐의 담지 비율에 따른 촉매의 탈수소화 능력 측정 1. Measurement of dehydrogenation ability of catalyst according to the supporting ratio of platinum and tungsten
백금과 텅스텐의 담지 비율에 따른 촉매 성능 확인을 위해, 상기 실시예 1 내지 실시예 3 및 비교예 1 내지 비교예 3에 따라 제조된 수소 제조용 촉매의 탈수소화 능력을 측정하였다. In order to confirm the catalyst performance according to the supporting ratio of platinum and tungsten, the dehydrogenation ability of the catalyst for hydrogen production prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 was measured.
구체적으로, 100 ml 3-neck flask에 반응물인 perhydro-dibenzyltoluene을 5 g 충진하고, 상기 실시예 1 내지 실시예 3 및 비교예 1 내지 비교예 3에 따른 촉매 각각을 반응물 대비 활성금속의 비율이 0.15% 몰 비율이 되도록 충진하였다. 반응장비 내부는 초고순도 질소를 이용해 30분간 퍼징(purging) 과정을 진행하였다. 반응 온도를 270℃에 맞추기 위해 30분 동안 700 rpm으로 교반하며 가열하였고, 정상 상태(steady state)에 도달한 뒤 3시간 동안 유지하며 탈수소화 반응을 진행하였다. 탈수소화 반응 중에 발생하는 수소의 양은 2개의 냉각기를 거쳐 25℃로 냉각된 후 mass flow meter를 이용하여 실시간으로 기록하였다. 반응 종료 후, 반응기는 자연냉각 방식을 이용하여 상온까지 냉각하였다. mass flow meter로 기록된 수소의 부피는 반데르발스 방정식을 이용하여 몰 수로 정량화하였으며, perhydro-dibenzyltoluene이 생성 가능한 수소의 총량에 대조하여 탈수소화도 수치를 계산하였고, 그 결과를 하기 도 1 및 표 1에 나타내었다. Specifically, 5 g of perhydro-dibenzyltoluene as a reactant was charged into a 100 ml 3-neck flask, and each of the catalysts according to Examples 1 to 3 and Comparative Examples 1 to 3 was added at a ratio of active metal to reactant of 0.15. It was filled to a % molar ratio. The inside of the reaction equipment was purged using ultra-high purity nitrogen for 30 minutes. To adjust the reaction temperature to 270°C, it was heated with stirring at 700 rpm for 30 minutes, and after reaching a steady state, it was maintained for 3 hours and the dehydrogenation reaction was performed. The amount of hydrogen generated during the dehydrogenation reaction was cooled to 25°C through two coolers and then recorded in real time using a mass flow meter. After completion of the reaction, the reactor was cooled to room temperature using a natural cooling method. The volume of hydrogen recorded by the mass flow meter was quantified in moles using the van der Waals equation, and the degree of dehydrogenation was calculated by comparing it to the total amount of hydrogen that can be produced by perhydro-dibenzyltoluene, and the results are shown in Figure 1 and Table below. It is shown in 1.
/Al2O3 Pt 0.9 W 0.1
/Al 2 O 3
/Al2O3 Pt 0.8 W 0.2
/Al 2 O 3
/Al2O3 Pt 0.6 W 0.4
/Al 2 O 3
/Al2O3 Pt 0.2 W 0.8
/Al 2 O 3
상기 표 1 및 하기 도 1에 나타난 바와 같이, 다공성 담체에 백금과 텅스텐을 0.9:0.1 내지 0.6:0.4의 중량비로 담지할 경우(실시예 1 내지 실시예 3), 백금 또는 텅스텐이 담지되지 않거나(비교예 1 내지 비교예 2), 텅스텐이 담지되더라도 상기 함량 범위를 벗어날 경우(비교예 3) 대비 촉매의 탈수소화도가 현저하게 향상되는 것을 확인하였으며, 그 중에서도 실시예 2 즉 백금과 텅스텐이 0.8:0.2의 중량비로 담지될 경우 촉매의 탈수소화도가 가장 우수함을 확인하였다. 상기 결과를 통해, 본 발명에 따라 다공성 담체에 백금과 텅스텐이 0.9:0.1 내지 0.6:0.4의 중량비로 담지된 실시예 1 내지 실시예 3의 촉매는 다른 촉매들 대비 수소 제조용 촉매로 유용하게 활용될 수 있음을 확인하였다. As shown in Table 1 and Figure 1 below, when platinum and tungsten are supported on a porous carrier at a weight ratio of 0.9:0.1 to 0.6:0.4 (Examples 1 to 3), platinum or tungsten is not supported ( In Comparative Examples 1 to 2), it was confirmed that even when tungsten was supported, the dehydrogenation degree of the catalyst was significantly improved compared to when the content exceeded the above range (Comparative Example 3). Among them, Example 2, that is, platinum and tungsten were 0.8: It was confirmed that the dehydrogenation degree of the catalyst was the best when supported at a weight ratio of 0.2. Through the above results, the catalysts of Examples 1 to 3, in which platinum and tungsten were supported on a porous carrier at a weight ratio of 0.9:0.1 to 0.6:0.4 according to the present invention, can be usefully used as a catalyst for hydrogen production compared to other catalysts. It was confirmed that it was possible.
실험예Experiment example 2. 백금 담지 시 열처리 공정 여부에 따른 촉매의 탈수소화 능력 측정 2. Measurement of dehydrogenation ability of catalyst according to heat treatment process when carrying platinum
백금 담지 시 열처리 공정 여부에 따른 촉매 성능 확인을 위해, 상기 실시예 2, 비교예 1 및 비교예 4에 따라 제조된 수소 제조용 촉매의 탈수소화 능력을 측정하였다. 측정은 상기 실험예 1과 동일한 방법으로 진행하였으며, 측정 결과는 하기 도 2에 나타내었다.In order to confirm catalyst performance depending on whether a heat treatment process was carried out when carrying platinum, the dehydrogenation ability of the catalyst for hydrogen production prepared according to Example 2, Comparative Example 1, and Comparative Example 4 was measured. The measurement was conducted in the same manner as in Experimental Example 1, and the measurement results are shown in Figure 2 below.
도 2의 결과를 통해, 촉매 제조 시 동일하게 백금 담지 후에 텅스텐을 담지하더라도, 백금 담지 후에 열처리 공정을 수행하지 않은 촉매의 경우(비교예 4), 백금 담지 후에 열처리 공정을 수행한 촉매(실시예 2) 대비 탈수소화 능력이 현저하게 저하됨을 확인하였다. 이는 백금 담지 후에 열처리 공정 수행시에는 백금의 형상이 고정되어 텅스텐이 백금 입자 외부에 위치하지만, 백금 담지 후 열처리 공정을 수행하지 않은 촉매의 경우 환원과정에서 백금과 텅스텐이 혼합되어 촉매 표면의 구조가 달라지기 때문이다. 또한, 텅스텐이 담지되지 않은 백금 촉매(비교예 1)에 비해서도 탈수소화 능력이 현저하게 감소됨을 확인할 수 있었는바, 이러한 결과를 통해, 백금 담지 후에 수행되는 열처리 공정이 필요함을 확인하였다. Through the results of FIG. 2, even if tungsten was supported after platinum support during catalyst production, in the case of a catalyst in which a heat treatment process was not performed after platinum support (Comparative Example 4), a catalyst in which a heat treatment process was performed after platinum support (Example 2) It was confirmed that the dehydrogenation ability was significantly reduced. This means that when the heat treatment process is performed after platinum deposition, the shape of the platinum is fixed and the tungsten is located outside the platinum particles. However, in the case of catalysts in which the heat treatment process is not performed after platinum deposition, the structure of the catalyst surface is changed due to the mixing of platinum and tungsten during the reduction process. Because it changes. In addition, it was confirmed that the dehydrogenation ability was significantly reduced compared to the platinum catalyst on which tungsten was not supported (Comparative Example 1). These results confirmed that a heat treatment process performed after platinum support was necessary.
실험예Experiment example 3. 백금과 텅스텐의 담지 순서에 따른 촉매의 탈수소화 능력 측정 3. Measurement of catalyst dehydrogenation ability according to the loading order of platinum and tungsten
백금과 텅스텐의 담지 순서에 따른 촉매의 성능 확인을 위해, 상기 실시예 2, 비교예 1, 비교예 2 및 비교예 5에 따라 제조된 수소 제조용 촉매의 탈수소화 능력을 측정하였다. 측정은 상기 실험예 1과 동일한 방법으로 진행하였으며, 측정 결과는 하기 도 3에 나타내었다.In order to confirm the performance of the catalyst according to the loading order of platinum and tungsten, the dehydrogenation ability of the catalyst for hydrogen production prepared according to Example 2, Comparative Example 1, Comparative Example 2, and Comparative Example 5 was measured. The measurement was conducted in the same manner as in Experimental Example 1, and the measurement results are shown in Figure 3 below.
도 3에 나타난 바와 같이, 백금과 텅스텐의 담지 순서를 달리하였을 때 동일한 백금과 텅스텐 함량을 가짐에도 탈수소화도 결과가 상이하게 관찰되었다. 구체적으로, 촉매 제조 시 동일한 함량의 백금과 텅스텐을 담지하더라도, 텅스텐을 먼저 담지한 후에 백금을 담지한 촉매의 경우(비교예 5), 백금을 먼저 담지하고 텅스텐을 담지한 촉매(실시예 2) 대비 탈수소화 능력이 현저하게 저하됨을 확인하였으며, 텅스텐이 담지되지 않은 백금 촉매(비교예 1)에 비해서도 탈수소화 능력이 현저하게 감소됨을 확인할 수 있었는바, 이러한 결과를 통해, 촉매 제조 시 백금을 먼저 담지하고 텅스텐을 담지하는 것이 바람직함을 확인하였다. As shown in Figure 3, when the loading order of platinum and tungsten was changed, different dehydrogenation results were observed even though the platinum and tungsten contents were the same. Specifically, even if the same amounts of platinum and tungsten are supported during catalyst production, in the case of a catalyst first supported with tungsten and then supported with platinum (Comparative Example 5), a catalyst supported with platinum first and then with tungsten (Example 2) It was confirmed that the dehydrogenation ability was significantly reduced compared to the platinum catalyst on which tungsten was not supported (Comparative Example 1). These results showed that platinum was used first when manufacturing the catalyst. It was confirmed that it is desirable to support tungsten.
실험예Experiment example 4. 백금과 텅스텐의 담지 비율에 따른 촉매의 전자상태 측정 4. Measurement of electronic state of catalyst according to the supporting ratio of platinum and tungsten
백금과 텅스텐의 담지 비율에 따른 촉매 성능 확인을 위해, x-ray photoelectron spectroscopy(XPS) 분석 기법을 이용하여 상기 실시예 1 내지 실시예 3 및 비교예 1 내지 비교예 3에 따라 제조된 수소 제조용 촉매에 담지된 금속의 전자상태를 측정하였다. In order to confirm the catalyst performance according to the supporting ratio of platinum and tungsten, catalyst for hydrogen production prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 using x-ray photoelectron spectroscopy (XPS) analysis technique The electronic state of the metal supported on was measured.
상기 표 2의 결과를 통해, 텅스텐이 조촉매로 사용된 백금-알루미나 촉매에서는 텅스텐 종으로부터 백금으로의 전자 공여가 나타나는 것을 확인하였으며, 도입된 텅스텐 종의 비율이 증가할수록 공여되는 전자의 양이 증가하는 것 또한 확인하였다. 이렇게 전자가 풍부해진 백금은 반응성이 증가하여 촉매 활성이 증가하게 되며, 따라서 하기 도 4에 나타난 바와 같이 백금에서의 전자가 풍부해질수록 백금 당 탈수소화 활성이 크게 증가하는 것을 확인할 수 있다. 또한, 백금과 텅스텐의 담지 순서가 변경되는 경우에서는 이러한 전자 공여현상이 나타나지 않았으며, 이로 인한 활성증가 또한 일어나지 않음을 확인하였다.Through the results in Table 2, it was confirmed that electron donation from tungsten species to platinum occurred in the platinum-alumina catalyst in which tungsten was used as a cocatalyst, and as the ratio of introduced tungsten species increases, the amount of donated electrons increases. It was also confirmed that it does. Platinum, which is enriched in electrons, has increased reactivity and thus catalytic activity. Therefore, as shown in Figure 4 below, it can be seen that as the electrons in platinum become richer, the dehydrogenation activity of platinum sugar increases significantly. In addition, it was confirmed that this electron donation phenomenon did not occur when the loading order of platinum and tungsten was changed, and no increase in activity occurred due to this.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시형태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (12)
다공성 담체; 상기 다공성 담체의 세공에 담지되는 백금; 및 상기 세공에 상기 백금과 혼재되어 담지되는 텅스텐;을 포함하고,
상기 백금과 상기 텅스텐은 0.9:0.1 내지 0.6:0.4의 중량비로 담지되며,
상기 액상 유기물 수소 저장체는 퍼하이드로-디벤질톨루엔(perhydro-Dibenzyltoluene)인 것을 특징으로 하는 액상 유기물 수소 저장체 탈수소화용 촉매.As a catalyst for liquid organic hydrogen carrier (LOHC) dehydrogenation,
porous carrier; Platinum supported in the pores of the porous carrier; And tungsten mixed with the platinum and supported in the pores,
The platinum and the tungsten are supported at a weight ratio of 0.9:0.1 to 0.6:0.4,
A catalyst for dehydrogenation of a liquid organic hydrogen storage, characterized in that the liquid organic hydrogen storage is perhydro-Dibenzyltoluene.
상기 다공성 담체는 활성탄(activated carbon) 또는 산화알루미늄(Al2O3)인 것을 특징으로 하는 액상 유기물 수소 저장체 탈수소화용 촉매.According to paragraph 1,
A catalyst for dehydrogenation of liquid organic hydrogen storage, characterized in that the porous carrier is activated carbon or aluminum oxide (Al 2 O 3 ).
상기 활성탄은 산화 그래핀, 카본블랙, Vulcan으로 이루어진 군에서 선택되는 것을 특징으로 하는 액상 유기물 수소 저장체 탈수소화용 촉매.According to paragraph 2,
A catalyst for dehydrogenation of liquid organic hydrogen storage, characterized in that the activated carbon is selected from the group consisting of graphene oxide, carbon black, and Vulcan.
상기 텅스텐은 상기 다공성 담체의 세공에 백금이 담지된 후에 담지된 것을 특징으로 하는 액상 유기물 수소 저장체 탈수소화용 촉매.According to paragraph 1,
A catalyst for dehydrogenation of liquid organic hydrogen storage, characterized in that the tungsten is supported after platinum is supported in the pores of the porous carrier.
(a) 다공성 담체의 세공에 백금 전구체 용액과 텅스텐 전구체 용액을 담지하는 단계; 및
(b) 상기 백금 전구체 용액과 텅스텐 전구체 용액이 담지된 상기 다공성 담체를 환원시키는 단계;를 포함하고,
상기 (a) 단계는, 상기 다공성 담체의 세공에 백금 전구체 용액을 담지하는 단계; 상기 백금 전구체 용액이 담지된 상기 다공성 담체를 열처리하는 단계; 및 상기 열처리된 상기 다공성 담체의 세공에 텅스텐 전구체 용액을 담지하는 단계;를 포함하고,
백금과 텅스텐이 0.9:0.1 내지 0.6:0.4의 중량비로 담지된 것을 특징으로 하는 액상 유기물 수소 저장체 탈수소화용 촉매의 제조방법.A method for producing a catalyst for dehydrogenation of the liquid organic hydrogen reservoir of claim 1, comprising:
(a) supporting a platinum precursor solution and a tungsten precursor solution in the pores of a porous carrier; and
(b) reducing the porous carrier on which the platinum precursor solution and the tungsten precursor solution are supported,
Step (a) includes supporting a platinum precursor solution in the pores of the porous carrier; heat-treating the porous carrier on which the platinum precursor solution is supported; and supporting a tungsten precursor solution in the pores of the heat-treated porous carrier.
A method for producing a catalyst for dehydrogenation of liquid organic hydrogen storage, characterized in that platinum and tungsten are supported at a weight ratio of 0.9:0.1 to 0.6:0.4.
상기 (a) 단계는 초기 젖음 담지법(incipient wetness impregnation)으로 수행되는 것을 특징으로 하는 액상 유기물 수소 저장체 탈수소화용 촉매의 제조방법.According to clause 6,
A method for producing a catalyst for dehydrogenation of liquid organic hydrogen storage, characterized in that step (a) is performed by incipient wetness impregnation.
상기 (b) 단계의 환원은 수소와 질소의 혼합 가스 분위기하에서 300 내지 600℃에서 수행되는 것을 특징으로 하는 액상 유기물 수소 저장체 탈수소화용 촉매의 제조방법.According to clause 6,
A method for producing a catalyst for dehydrogenation of liquid organic hydrogen storage, characterized in that the reduction in step (b) is performed at 300 to 600 ° C. in a mixed gas atmosphere of hydrogen and nitrogen.
상기 혼합 후 탈수소화 반응을 수행하는 단계를 포함하는 수소 제조방법.Mixing the catalyst according to claim 1 and a liquid organic hydrogen carrier (LOHC); and
A method for producing hydrogen comprising performing a dehydrogenation reaction after mixing.
상기 액상 유기물 수소 저장체는 퍼하이드로-디벤질톨루엔(perhydro-Dibenzyltoluene)인 것을 특징으로 하는 수소 제조방법.According to clause 10,
A method for producing hydrogen, wherein the liquid organic hydrogen storage material is perhydro-Dibenzyltoluene.
상기 탈수소화 반응은 250 ~ 300℃의 온도에서 2 내지 4시간 동안 수행되는 것을 특징으로 하는 수소 제조방법.According to clause 10,
A method for producing hydrogen, characterized in that the dehydrogenation reaction is performed for 2 to 4 hours at a temperature of 250 to 300 ° C.
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