KR101857187B1 - Catalyst for hydrodeoxygenating oxygenates and method of preparing deoxygenated fuels using the same - Google Patents
Catalyst for hydrodeoxygenating oxygenates and method of preparing deoxygenated fuels using the same Download PDFInfo
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- KR101857187B1 KR101857187B1 KR1020160064088A KR20160064088A KR101857187B1 KR 101857187 B1 KR101857187 B1 KR 101857187B1 KR 1020160064088 A KR1020160064088 A KR 1020160064088A KR 20160064088 A KR20160064088 A KR 20160064088A KR 101857187 B1 KR101857187 B1 KR 101857187B1
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- Prior art keywords
- catalyst
- hydrocarbon compound
- titanium
- carrier
- oxygen
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000446 fuel Substances 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 24
- 239000002923 metal particle Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002551 biofuel Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- 239000002028 Biomass Substances 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 19
- FQZKLYUUIREESH-UHFFFAOYSA-N [O-2].[Zr+4].[Ti+4].[W+4].[O-2].[O-2].[O-2].[O-2].[O-2] Chemical group [O-2].[Zr+4].[Ti+4].[W+4].[O-2].[O-2].[O-2].[O-2].[O-2] FQZKLYUUIREESH-UHFFFAOYSA-N 0.000 claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 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
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 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
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- MRSOZKFBMQILFT-UHFFFAOYSA-L diazanium;oxalate;titanium(2+) Chemical compound [NH4+].[NH4+].[Ti+2].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O MRSOZKFBMQILFT-UHFFFAOYSA-L 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000000243 solution Substances 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims 1
- 229940005991 chloric acid Drugs 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 238000006392 deoxygenation reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000003208 petroleum Substances 0.000 abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 229920002488 Hemicellulose Polymers 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- TXONVAMTMVNDJZ-UHFFFAOYSA-N [O-2].[Zr+4].[W+4].[O-2].[O-2].[O-2] Chemical compound [O-2].[Zr+4].[W+4].[O-2].[O-2].[O-2] TXONVAMTMVNDJZ-UHFFFAOYSA-N 0.000 description 1
- GMTALJIKFKYVMV-UHFFFAOYSA-N [Zr].[Ti].[W] Chemical compound [Zr].[Ti].[W] GMTALJIKFKYVMV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- -1 aromatic carbon compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G49/06—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
본 발명은 티타니아-텅스텐-지르코늄 산화물 담체; 및 상기 담체에 담지된 금속입자를 포함하는 수첨탈산소 반응용 촉매 및 이의 제조방법에 관한 것이다. 또한, 본 발명은 상기 수첨탈산소 반응용 촉매를 이용하여 함산소 화합물로부터 수소를 첨가하고 산소를 제거하여, 석유를 대체할 수 있는 바이오 연료를 제조하는 방법에 관한 것이다.The present invention relates to a titania-tungsten-zirconium oxide carrier; And metal particles supported on the support, and a process for producing the catalyst. The present invention also relates to a method for producing a biofuel that can replace petroleum by adding hydrogen from an oxygen-containing compound and removing oxygen by using the catalyst for hydrocracking reaction.
Description
본 명세서에는 수첨탈산소 반응용 촉매 및 이의 제조방법과 상기 촉매를 이용한 바이오 연료의 제조방법이 개시된다.A catalyst for hydrocracking reaction, a method for producing the same, and a method for producing a biofuel using the catalyst are disclosed in this specification.
최근 화석연료 고갈 및 유가 급등, 기후변화협약 이행 강화 등으로 인해 화석연료의 사용제한으로 재생가능한 바이오매스의 활용에 대한 관심이 급증하여, 특히, 나무, 생물 부산물 등 비식량 바이오매스의 이용에 대한 연구 개발이 활발히 진행되고 있다. 주로 셀룰로오스로 이루어진 식량 바이오매스와 구분되는 목질계 바이오매스는 전체 식물성 바이오매스의 95% 이상을 차지하고 비식량 자원 및 폐기물을 활용할 수 있어서 차세대 바이오매스로 많은 관심을 받고 있다. 목질계 바이오매스의 구성성분인 셀룰로오스, 헤미셀룰로오스, 리그닌 중 셀룰로오스, 헤미셀룰로오스는 식량성 자원처럼 활용이 가능하고 리그닌은 무작위페놀 고분자로서 석유에서 유래하는 모든 방향족 탄소 화합물을 대체할 수 있는 가능성이 있으나, 현재는 그 복잡한 구조로 인해 단순한 부산물로 인식하여 폐기되고 있어서 이를 활용할 방법을 찾는 연구 개발이 활발히 진행되고 있다. Recently, due to the depletion of fossil fuels, soaring oil prices, and the strengthening of the implementation of the Convention on Climate Change, interest in the use of renewable biomass has increased due to restrictions on the use of fossil fuels. Especially, the use of non-food biomass such as wood, Research and development are actively proceeding. Ligneous biomass, which is distinguished from food biomass consisting mainly of cellulose, accounts for more than 95% of total plant biomass and can utilize non-food resources and waste, which is attracting much attention as next generation biomass. Cellulose, hemicellulose, cellulose in cellulosic materials such as hemicellulose, hemicellulose and hemicellulose, which are constituents of woody biomass, can be used as food resources, and lignin is a random phenol polymer and is likely to replace all aromatic carbon compounds derived from petroleum. However, Has been recognized as a simple byproduct due to its complicated structure and discarded, and research and development are actively pursued to find a way to utilize it.
다양한 바이오매스 원료로부터 고급 연료를 생산하는 다양한 화학적, 생물학적 방법이 제시되고 있으며, 모든 종류의 탄소화합물을 원료로 사용할 수 있는 방법으로는 열분해 방법이 있다. 열분해 또는 수열분해 방법은 다양한 바이오매스 종류에 활용할 수 있다는 장점이 있으나 생성된 열분해 산물, 또는 액체 열분해 오일이 높은 산소 함량으로 인해 석유 대체 연료로 부적합하다는 단점이 있다. Various chemical and biological methods for producing high-quality fuels from various biomass feedstocks have been proposed, and pyrolysis methods are available as a method for using all kinds of carbon compounds as feedstocks. The pyrolysis or hydrothermal decomposition method has an advantage that it can be applied to various kinds of biomass, but the generated pyrolysis product or liquid pyrolysis oil is disadvantageous as an alternative petroleum fuel due to high oxygen content.
일 측면에서, 본 발명은 상기 수첨탈산소 반응에 사용하기 위한 촉매를 제공하는 것을 목적으로 한다.In one aspect, the present invention is directed to providing a catalyst for use in the hydrochemical oxygenation reaction.
일 측면에서, 본 발명은 상기 촉매를 사용하여 수첨탈산소 반응과 같이 수소를 첨가하여 산소를 제거하는 공정을 통해 바이오 연료를 생산하는 방법을 제공하는 것을 목적으로 한다. In one aspect, the present invention provides a method for producing biofuel through a process of removing oxygen by adding hydrogen such as hydrocracking oxygen using the catalyst.
상기와 같은 목적을 해결하기 위하여 본 발명의 일 관점은 티타늄-텅스텐-지르코늄 산화물(Titanium-Tungsten-Zirconium oxide, TiO2/WO3/ZrO2) 담체; 및 상기 담체에 담지된 금속입자를 포함하는 수첨탈산소 반응용 촉매를 제공한다.According to an aspect of the present invention, there is provided a titanium-tungsten-zirconium oxide (TiO 2 / WO 3 / ZrO 2 ) carrier; And a metal particle supported on the support.
본 발명의 일 관점은, 금속 전구체 수용액을 상기 티타늄-텅스텐-지르코늄 산화물 담체와 혼합하여 함침시키는 단계; 및 상기 금속 전구체 수용액을 함침시킨 담체를 공기 중에서 소성하는 단계를 포함하는 상기 수첨탈산소 반응용 촉매의 제조방법을 제공한다.In one aspect of the present invention, there is provided a method for producing a titanium-tungsten-zirconium oxide support, comprising: impregnating a metal precursor aqueous solution with the titanium-tungsten- And calcining the carrier impregnated with the metal precursor aqueous solution in air. The present invention also provides a method for producing the catalyst for hydrocracking reaction.
또한, 본 발명의 일 관점은 상기 수첨탈산소 반응용 촉매를 함산소 탄화수소 화합물을 포함하는 바이오매스에 가하여 산소 탄화수소 화합물로부터 탈산소 탄화수소 화합물을 제조하는 단계를 포함하는 바이오연료의 제조방법을 제공한다.Another aspect of the present invention provides a method for producing a biofuel comprising the step of adding a catalyst for hydrocracking reaction to a biomass containing an oxygen-containing hydrocarbon compound to prepare a deoxy-hydrocarbon compound from the oxygen-hydrocarbon compound .
본 발명의 수첨탈산소 반응용 촉매는 수첨탈산소(hydrodeoxygenation) 반응 중 코크 또는 타르의 생성을 억제하여 반응을 촉진시킬 수 있다. 따라서, 상기 촉매를 이용하면 효율적으로 함산소 화합물에 수소를 첨가하여 산소를 제거할 수 있어, 석유를 대체할 수 있는 바이오 연료를 높은 수율로 효과적으로 생산할 수 있다.The catalyst for hydrocracking reaction of the present invention can promote the reaction by inhibiting the formation of coke or tar during the hydrodeoxygenation reaction. Therefore, using the catalyst effectively removes oxygen by adding hydrogen to oxygen-containing compounds, thereby effectively producing biofuel that can replace petroleum with high yield.
도 1 은 본 발명의 일 실시예에 따른 바이오 연료 제조방법에 사용되는 연속식 수첨탈산소 반응기의 구성을 도식화한 것이다.FIG. 1 is a schematic diagram illustrating the construction of a continuous hydrocracking oxygenator used in a method for manufacturing a biofuel according to an embodiment of the present invention. Referring to FIG.
본 명세서에서, 용어 "함산소 화합물" 또는 "함산소 탄화수소 화합물"은 산소 원자를 분자 구조 내에 포함하는 탄화수소 화합물을 의미한다.In this specification, the term " oxygen-containing compound "or" oxygen-containing hydrocarbon compound "means a hydrocarbon compound containing an oxygen atom in its molecular structure.
본 명세서에서, 용어 "탈산소 탄화수소 화합물"은 "함산소 화합물"로부터 산소가 일부 또는 전부 제거된 화합물"을 의미한다.As used herein, the term "deoxygenated hydrocarbon compound" means a compound in which some or all of oxygen has been removed from " oxygenated compound ".
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 발명의 일 실시예는 담체; 및 상기 담체에 담지된 금속입자를 포함하는 수첨탈산소 반응용 촉매를 제공할 수 있다. One embodiment of the present invention includes a carrier; And a catalyst for hydrocracking reaction comprising the metal particles supported on the support.
일 실시예로서 상기 담체는 지르코니아 기반 담체일 수 있으며, 보다 구체적으로는 티타늄-텅스텐-지르코늄 산화물(Titanium-Tungsten-Zirconium oxide, TiO2/WO3/ZrO2) 담체일 수 있다. 티타늄을 첨가함으로써 촉매의 탈산소 능력을 향상시킬 수 있다.In one embodiment, the support may be a zirconia-based support, and more specifically, a titanium-tungsten-zirconium oxide (TiO 2 / WO 3 / ZrO 2 ) support. By adding titanium, the deoxidizing ability of the catalyst can be improved.
이에, 본 발명의 일 실시예는 티타늄-텅스텐-지르코늄 산화물 담체; 및 상기 담체에 담지된 금속입자를 포함하는 수첨탈산소 반응용 촉매를 제공할 수 있다.Accordingly, an embodiment of the present invention provides a titanium-tungsten-zirconium oxide carrier; And a catalyst for hydrocracking reaction comprising the metal particles supported on the support.
일 실시예로서 상기 금속 입자는 수소화 반응의 촉매로서 작용할 수 있는 금속 촉매라면 특별히 제한되지 않는다. 예를 들어 상기 금속 입자는 백금(Pt), 루테늄(Ru), 팔라듐(Pd), 로듐(Rh) 및 이리듐(Ir)으로 이루어진 군에서 선택된 하나 이상을 포함할 수 있다. 구체적으로 상기 금속 전구체는 루테늄(Ru) 및 백금(Pt) 중 하나 이상일 수 있고, 더욱 구체적으로는 루테늄(Ru)일 수 있다.In one embodiment, the metal particles are not particularly limited as long as they are metal catalysts that can act as catalysts for the hydrogenation reaction. For example, the metal particles may include at least one selected from the group consisting of platinum (Pt), ruthenium (Ru), palladium (Pd), rhodium (Rh), and iridium (Ir). Specifically, the metal precursor may be at least one of ruthenium (Ru) and platinum (Pt), and more specifically may be ruthenium (Ru).
다른 일 실시예로서, 상기 금속입자는 구리(Cu), 니켈(Ni) 및 코발트(Co)로 이루어진 군에서 선택된 하나 이상을 포함하는 전이금속일 수 있다.In another embodiment, the metal particles may be a transition metal including at least one selected from the group consisting of copper (Cu), nickel (Ni), and cobalt (Co).
본 발명의 일 실시예에서 상기 촉매는 상기 금속입자를 촉매 총 중량에 대하여 0.01 내지 10 중량%로 포함할 수 있다. 구체적으로, 상기 금속입자를 1 내지 5중량%로 포함할 수 있다. 금속의 함량이 0.01 중량% 미만이면 전환율, 수율 등으로 측정되는 촉매 반응성이 저하되고, 10 중량% 초과이면 금속 함량이 높아서 촉매 제조 비용이 높아질 수 있다.In one embodiment of the present invention, the catalyst may contain the metal particles in an amount of 0.01 to 10% by weight based on the total weight of the catalyst. Specifically, the metal particles may be contained in an amount of 1 to 5% by weight. If the content of the metal is less than 0.01% by weight, the catalytic activity measured by the conversion rate, the yield and the like is lowered. If the content of the metal is more than 10% by weight, the metal content is high.
본 발명의 일 실시예에서 상기 촉매는 상기 담체의 티타늄 산화물을 촉매 총 중량에 대하여 0.01 이상 10 중량%로 포함할 수 있다. 구체적으로, 상기 티타늄 산화물을 0.01 내지 4 중량%로 포함할 수 있다. 티타늄 산화물의 함량이 0.01 중량% 미만이면 티타늄 산화물의 효과가 미미하고, 10 중량% 초과이면 티타늄-텅스텐-지르코늄의 복합 효과가 잘 나타나지 않는다.In one embodiment of the present invention, the catalyst may contain titanium oxide of the carrier in an amount of 0.01 to 10 wt% based on the total weight of the catalyst. Specifically, the titanium oxide may be contained in an amount of 0.01 to 4% by weight. If the content of titanium oxide is less than 0.01 wt%, the effect of titanium oxide is insignificant. If it exceeds 10 wt%, the composite effect of titanium-tungsten-zirconium does not appear well.
일 실시예에서 상기 촉매는 상기 담체의 텅스텐 산화물을 촉매 총 중량에 대하여 5 내지 30 중량%로 포함할 수 있다. 일 실시예에서 상기 촉매는 상기 담체의 지르코늄 산화물을 촉매 총 중량에 대하여 50 내지 94 중량%로 포함할 수 있다. In one embodiment, the catalyst may comprise tungsten oxide of the carrier in an amount of 5 to 30 wt% based on the total weight of the catalyst. In one embodiment, the catalyst may comprise zirconium oxide of the carrier in an amount of 50 to 94 wt% based on the total weight of the catalyst.
또한, 본 발명의 일 실시예는 상기 수첨탈산소 반응용 촉매의 제조방법으로, 금속 전구체 수용액을 상기 티타늄-텅스텐-지르코늄 산화물 담체와 혼합하여 함침시키는 단계; 및 상기 금속 전구체 수용액을 함침시킨 담체를 공기 중에서 소성하는 단계를 포함할 수 있다.According to another embodiment of the present invention, there is provided a method of preparing the catalyst for hydrocracking reaction, comprising the steps of: mixing a metal precursor aqueous solution with the titanium-tungsten-zirconium oxide carrier; And firing the carrier impregnated with the metal precursor aqueous solution in air.
일 실시예로서 상기 금속 전구체는 예를 들어 상기 금속 전구체는 루테늄(Ru) 전구체, 백금(Pt) 전구체, 팔라듐(Pd) 전구체, 로듐(Rh) 전구체 및 이리듐(Ir) 전구체로 이루어진 군에서 선택되는 하나 이상을 포함할 수 있다. 구체적으로 상기 금속 전구체는 루테늄(Ru) 전구체 및 백금(Pt) 전구체 중 하나 이상일 수 있고, 더욱 구체적으로는 루테늄(Ru) 전구체일 수 있다. In one embodiment, the metal precursor is selected from the group consisting of, for example, a ruthenium (Ru) precursor, a platinum (Pt) precursor, a palladium (Pd) precursor, a rhodium (Rh) precursor, and an iridium And may include one or more. Specifically, the metal precursor may be at least one of a ruthenium (Ru) precursor and a platinum (Pt) precursor, and more specifically, a ruthenium (Ru) precursor.
다른 일 실시예로서, 상기 금속 전구체는 구리(Cu) 전구체, 니켈(Ni) 전구체 및 코발트(Co) 전구체로 이루어진 군에서 선택된 하나 이상의 전이금속 전구체를 포함할 수 있다.In another embodiment, the metal precursor may include at least one transition metal precursor selected from the group consisting of a copper (Cu) precursor, a nickel (Ni) precursor, and a cobalt (Co) precursor.
일 실시예로서 상기 금속 전구체는 금속 염화물 또는 금속 염소산일 수 있으나, 수소화 반응의 촉매로서 작용할 수 있는 금속 촉매의 전단계 물질이라면 특별히 제한되지 않는다.In one embodiment, the metal precursor may be a metal chloride or metal chlorate, but is not limited as long as it is a precursor of a metal catalyst that can act as a catalyst for a hydrogenation reaction.
일 실시예로서 상기 금속 전구체 수용액을 함침시킨 담체를 공기 중에서 소성하는 단계는 상기 금속 전구체 수용액을 함침시킨 담체를 공기 중에서 약 200 내지 600℃로 약 1시간 내지 3시간 동안 소성하는 것일 수 있다. 구체적으로, 상기 소성온도는 약 300 내지 500℃일 수 있으며, 소성시간은 약 30분 내지 200분일 수 있다.In one embodiment, in the step of firing the carrier impregnated with the metal precursor aqueous solution, the carrier impregnated with the metal precursor aqueous solution may be fired in the air at a temperature of about 200 to 600 ° C for about 1 hour to 3 hours. Specifically, the firing temperature may be about 300 to 500 ° C, and the firing time may be about 30 minutes to 200 minutes.
본 발명의 일 실시예에 따른 상기 제조방법은 금속 전구체 수용액을 티타늄-텅스텐-지르코늄 산화물 담체와 혼합하여 함침시키는 단계 이전에 티타늄-텅스텐-지르코늄 산화물 담체를 제조하는 단계를 더 포함할 수 있다.The method may further include a step of preparing a titanium-tungsten-zirconium oxide support before mixing the metal precursor aqueous solution with the titanium-tungsten-zirconium oxide support.
일 실시예로서 상기 티타늄-텅스텐-지르코늄 산화물 담체를 제조하는 단계는, 지르코늄 수산화물(zirconium hydroxide), 암모늄 메타텅스테이트 수화물(ammonium metatungstate hydrate)을 이온교환수와 혼합하여 반응시킨 후 소성하는 단계; 및 상기 소성물을 암모늄 티타닐 옥살레이트 일수화물(ammonium titanyl oxalate monohydrate)와 혼합한 후 소성하는 단계를 포함할 수 있다.In one embodiment, the step of preparing the titanium-tungsten-zirconium oxide support comprises mixing zirconium hydroxide and ammonium metatungstate hydrate with ion-exchanged water, reacting and mixing the mixture; And mixing the fired product with ammonium titanyl oxalate monohydrate and then firing the mixture.
본 발명의 상기 제조방법은, 일 실시예로서 상기 금속 전구체 수용액을 함침시킨 담체를 공기 중에서 소성한 후, 이를 수소 분위기에서 환원시키는 단계를 더 포함할 수 있다. 일 실시예로서 상기 환원 단계는 수소 분위기에서 약 200 내지 500℃로 약 1시간 내지 5시간 동안 진행될 수 있다. 또는, 보다 구체적으로 약 300 내지 450℃에서 약 1시간 내지 3시간 동안 진행될 수 있다.The method of the present invention may further include a step of calcining a carrier impregnated with the metal precursor aqueous solution in air and reducing the metal precursor in a hydrogen atmosphere. In one embodiment, the reducing step may be conducted at about 200 to 500 ° C in a hydrogen atmosphere for about 1 hour to 5 hours. Or more specifically about 300 to 450 < 0 > C for about 1 hour to 3 hours.
본 발명의 일 실시예들에서 상기 촉매는 수첨탈산소 반응에서 산촉매로서 산소 원자를 끌어당겨서 제거하는 역할을 한다. 이때 티타니아가 산소 원자를 더 효율적으로 끌어당기게 해줌으로써 촉매의 탈산소 효율을 높일 수 있다.In one embodiment of the present invention, the catalyst serves to withdraw oxygen atoms as acid catalysts in the hydrocracking reaction. At this time, the efficiency of the deoxidation of the catalyst can be increased by allowing the titania to draw oxygen atoms more efficiently.
이에, 본 발명의 일 실시예는 상기 수첨탈산소 반응용 촉매를 함산소 탄화수소 화합물을 포함하는 바이오매스에 가하여 산소 탄화수소 화합물로부터 탈산소 탄화수소 화합물을 제조하는 단계를 포함하는 바이오연료의 제조방법을 제공할 수 있다.Accordingly, an embodiment of the present invention provides a method for producing a biofuel comprising the step of adding a catalyst for hydrocracking reaction to a biomass containing an oxygen-containing hydrocarbon compound to prepare a deoxy-hydrocarbon compound from the oxygen-hydrocarbon compound can do.
상기 제조방법은, 일 실시예로서 반응기 내에 함산소 탄화수소 화합물을 포함하는 바이오매스를 투입하는 단계; 및 상기 반응기 내에 상기 수첨탈산소 반응용 촉매를 가하여 수첨탈산소 반응을 통해 탈산소 탄화수소 화합물을 제조하는 단계를 포함할 수 있다.In one embodiment, the method comprises the steps of injecting a biomass containing an oxygen-containing hydrocarbon compound into a reactor; And adding the catalyst for hydrocracking to the reactor to produce a deoxy-hydrocarbon compound through a hydrocracking reaction.
일 실시예로서, 상기 함산소 탄화수소 화합물을 포함하는 바이오매스는 함산소 탄화수소 화합물을 포함하는 바이오매스라면 제한되지 않으며, 상기 바이오매스 유래 증기, 기체, 액체 등을 모두 포함할 수 있다. 상기 함산소 탄화수소 화합물을 포함하는 바이오매스는 예를 들어 바이오매스 열분해 오일을 포함할 수 있다.In one embodiment, the biomass including the oxygen-containing hydrocarbon compound is not limited as long as it is a biomass including an oxygen-containing hydrocarbon compound, and may include all of the biomass-derived vapor, gas, and liquid. The biomass including the oxygen-containing hydrocarbon compound may include, for example, a biomass pyrolysis oil.
일 실시예로서, 상기 탈산소 탄화수소 화합물은 함산소 탄화수소 화합물로부터 산소가 일부 또는 전부 제거된 화합물을 의미하며, 사이클로헥산(C6H12), 메틸사이클로헥산(CH3C6H11), 벤젠(C5H10) 및 메틸사이클로펜탄(CH3C5H9)으로 이루어진 군에서 선택되는 하나 이상의 화합물을 포함할 수 있다. In one embodiment, the deoxy-hydrocarbon compound means a compound in which oxygen is partially or completely removed from an oxygen-containing hydrocarbon compound. The deoxidized hydrocarbon compound may be a compound selected from the group consisting of cyclohexane (C 6 H 12 ), methylcyclohexane (CH 3 C 6 H 11 ) (C 5 H 10 ), and methylcyclopentane (CH 3 C 5 H 9 ).
또한, 상기 탈산소 탄화수소 화합물을 제조하는 단계는 일 실시예로서 수소 기체를 투입하는 단계를 포함할 수 있다.Also, the step of preparing the deoxygenated hydrocarbon compound may include a step of introducing hydrogen gas as one embodiment.
일 실시예로서 상기 탈산소 탄화수소 화합물을 제조하는 단계는 반응기를 일정 반응온도, 반응압력으로 높여 수첨탈산소 반응을 진행하는 것일 수 있으며, 그 결과 산소 원자가 일부 또는 전부 제거된 탈산소 탄화수소 화합물이 생성될 수 있다.In one embodiment, the step of preparing the deoxygenated hydrocarbon compound may be carried out by raising the temperature of the reactor to a certain reaction temperature and a reaction pressure to conduct a hydrocracking reaction. As a result, a deoxygenated hydrocarbon compound in which oxygen atoms are partially or completely removed .
일 실시예에 따르면, 상기 탈산소 탄화수소 화합물을 제조하는 단계에서 상기 수첨탈산소 반응은 200 내지 450℃의 온도에서 진행되는 것일 수 있고, 구체적으로는 250 내지 400℃의 온도일 수 있다. 온도가 200℃ 미만이면 수첨탈산소 반응 활성이 거의 없으며, 450℃ 초과이면 높은 온도로 인해 반응기 운전이 어려워진다.According to one embodiment, in the step of producing the deoxygenated hydrocarbon compound, the hydrocracking reaction may be carried out at a temperature of 200 to 450 ° C, and more specifically, a temperature of 250 to 400 ° C. If the temperature is lower than 200 ° C, there is almost no hydrocracking activity. If the temperature is higher than 450 ° C, the reactor is difficult to operate due to the high temperature.
또한 일 실시예에 따르면, 상기 탈산소 탄화수소 화합물을 제조하는 단계에서 상기 수첨탈산소 반응은 20 내지 150 bar의 압력에서 진행되는 것일 수 있고, 구체적으로는 30 내지 60 bar의 압력일 수 있다. 압력이 20 bar 미만이면 수소 농도 부족으로 촉매 반응성이 낮아지고, 150 bar 초과이면 높은 압력 때문에 반응기 제작 비용이 높아진다.According to one embodiment, in the step of preparing the deoxygenated hydrocarbon compound, the hydrocracking reaction may be carried out at a pressure of 20 to 150 bar, and more specifically, a pressure of 30 to 60 bar. If the pressure is less than 20 bar, the catalytic reactivity is lowered due to the lack of hydrogen concentration. If the pressure is more than 150 bar, the reactor cost is increased due to the high pressure.
본 발명의 일 실시예에서 사용되는 상기 반응기는 특별히 제한되지 않으나, 예를 들어 고온에서 작동하는 고압 반응기 일 수 있으며, 대량생산을 위한 연속식 반응기일 수도 있고, 회분식 반응기일 수도 있다. 도 1에 본 발명의 일실시예로 사용될 수 있는 연속식 반응기를 나타내었다. The reactor used in one embodiment of the present invention is not particularly limited, but may be, for example, a high-pressure reactor operating at a high temperature, a continuous reactor for mass production, or a batch reactor. Figure 1 shows a continuous reactor which can be used as an embodiment of the present invention.
도 1을 참조로 설명하면, 상기 연속식 반응기는 백프레셔레귤레이터(Back pressure regulator)와 가열 장치가 연결된 고압반응기(30), 함산소화합물 원료 주입용 용기(10), 수소 가스 주입용 고압 실린더(20), 반응후 생성물의 냉각 및 포집을 위한 냉각 장치(40), 최종 생성물을 저장하는 저장 장치(50)를 포함할 수 있다.1, the continuous reactor includes a high-
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.
[제조예 1] 티타늄-텅스텐-지르코늄 산화물 담체에 담지된 Ru 나노입자 촉매 제조[Preparation Example 1] Preparation of Ru nanoparticle catalyst supported on titanium-tungsten-zirconium oxide carrier
지르코늄 수산화물 (zirconium hydroxide) 4 g, 암모늄 메타텅스테이트 수화물(ammonium metatungstate hydrate) 0.5 g을 이온교환수 50 g과 혼합하고 고압 반응기에서 180℃에서 12시간 동안 처리하였다. 이후 고체 생성물을 2시간 동안 800 ℃에서 소성하였다. 소성후 암모늄 티타닐 옥살레이트 일수화물(ammonium titanyl oxalate monohydrate)를 비율대로 혼합하고 60℃에서 건조하고 550℃에서 2시간 동안 소성하여 각각 0, 2, 4 및 6 중량%의 Ti가 첨가된 티타늄-텅스텐-지르코늄 산화물 담체를 생성하였다. 생성된 담체에 루테늄 전구체(Ruthenium chloride hydrate) 0.35 g을 이온교환수 60 g에 용해시킨 수용액을 함침시키고 소성하여 3 중량%의 Ru가 담지된 촉매를 제조하였다.4 g of zirconium hydroxide and 0.5 g of ammonium metatungstate hydrate were mixed with 50 g of ion-exchanged water and treated at 180 ° C. for 12 hours in a high-pressure reactor. The solid product was then calcined at 800 DEG C for 2 hours. After the calcination, ammonium titanyl oxalate monohydrate was mixed in proportions, dried at 60 ° C. and calcined at 550 ° C. for 2 hours to obtain titanium-boron-doped TiO 2 doped with 0, 2, 4 and 6 wt% Tungsten-zirconium oxide support. An aqueous solution in which 0.35 g of a ruthenium chloride hydrate was dissolved in 60 g of ion exchange water was impregnated into the resulting support and fired to prepare a catalyst carrying 3% by weight of Ru.
상기 각 0, 2, 4 및 6 중량%의 Ti가 첨가된 티타늄-텅스텐-지르코늄 산화물 담체에 Ru가 담지된 촉매를 350℃에서 2시간 동안 수소 분위기에서 환원하였다.The catalyst carrying Ru on the titanium-tungsten-zirconium oxide support to which 0, 2, 4 and 6 wt% Ti was added was reduced in a hydrogen atmosphere at 350 ° C for 2 hours.
[제조예 2] 바이오매스 열분해 오일의 수첨탈산소 반응[Production Example 2] Hydrophobic reaction of biomass pyrolysis oil
고정층 반응기(내부 지름 1.8 cm, 길이 14 cm)를 사용하여 바이오매스 열분해 오일의 수첨탈산소 반응을 수행하였다. 반응기내 압력은 back-pressure regulator (BPR)로 조절하였다. 반응 온도는 300 - 350℃, 반응 압력은 100 bar로 유지하였다. 반응 후 얻어진 액체, 고체 혼합물을 따로 수거하여 무게를 측정하고 분석하였다.The hydrocracking reaction of the biomass pyrolysis oil was carried out using a fixed bed reactor (inner diameter 1.8 cm, length 14 cm). The pressure in the reactor was controlled by a back-pressure regulator (BPR). The reaction temperature was maintained at 300 - 350 ℃ and the reaction pressure was maintained at 100 bar. The liquid and solid mixture obtained after the reaction were collected separately and weighed and analyzed.
아래 표 1은 본 발명의 비교예인 다양한 촉매들에 대한 350℃에서 반응 결과이다. Table 1 below shows the reaction results at 350 ° C for various catalysts which are comparative examples of the present invention.
아래 표 2는 본 발명의 일 실시예로서 상기 [제조예 1]에서 제조된 티타니아가 첨가된 텅스텐-지르코니아 담체에 담지된 Ru 촉매를 각각 300℃에서 반응시킨 결과이다. Table 2 below shows the results of reaction of the Ru catalyst supported on the titania-added tungsten-zirconia carrier prepared in [Preparation Example 1] at 300 ° C as one embodiment of the present invention.
본 발명의 일 실시예에 따른 티타늄-텅스텐-지르코늄 산화물 담체에 담지된 금속 입자 촉매가 촉매 총 중량에 대하여 3중량%의 Ru가 텅스텐-지르코니아 담체에 담지된 촉매(비교예 2)보다 낮은 O/C비 또는 높은 산소 제거 효율을 나타내었다. 실시예 1 내지 3 중 티타늄이 2 중량% 첨가된 실시예 1의 경우 가장 낮은 산소 함량에 도달하여, 수첨탈산소 반응이 효과적으로 진행하였음을 확인할 수 있다.The metal particle catalyst supported on the titanium-tungsten-zirconium oxide support according to an embodiment of the present invention has a lower O / N ratio than that of the catalyst in which 3 wt% of Ru is supported on the tungsten-zirconia carrier relative to the total weight of the catalyst (Comparative Example 2) C ratio or high oxygen removal efficiency. In the case of Example 1 in which 2% by weight of titanium was added in Examples 1 to 3, the lowest oxygen content was reached, and it was confirmed that the hydrocracking reaction proceeded effectively.
10: 원료 주입용 용기
20: 수소 가스 주입용 고압 실린더
30: 고압반응기
40: 냉각 장치
50: 저장 장치10: Container for raw material injection
20: High pressure cylinder for hydrogen gas injection
30: High-pressure reactor
40: cooling device
50: Storage device
Claims (17)
상기 촉매는 티타늄이 첨가제로 담체에 첨가된 티타늄-텅스텐-지르코늄 산화물(Titanium-Tungsten-Zirconium oxide, TiO2/WO3/ZrO2) 담체; 및 상기 담체에 담지된 금속입자를 포함하고,
상기 촉매는 상기 담체의 티타늄 산화물을 촉매 총 중량에 대하여 0.01 내지 4 중량%로 포함하는 수첨탈산소 반응용 촉매.As a catalyst for hydrothermal reaction,
The catalyst is a titanium-tungsten-zirconium oxide (TiO 2 / WO 3 / ZrO 2 ) carrier in which titanium is added to the carrier as an additive; And metal particles supported on the carrier,
Wherein the catalyst comprises titanium oxide of the carrier in an amount of 0.01 to 4% by weight based on the total weight of the catalyst.
금속 전구체 수용액을 티타늄-텅스텐-지르코늄 산화물(Titanium-Tungsten-Zirconium oxide, TiO2/WO3/ZrO2) 담체와 혼합하여 함침시키는 단계; 및
상기 금속 전구체 수용액을 함침시킨 담체를 공기 중에서 소성하는 단계;
를 포함하는, 수첨탈산소 반응용 촉매의 제조방법.A process for producing a catalyst for hydrothermal reaction according to any one of claims 1 to 5,
Impregnating the metal precursor aqueous solution with titanium-tungsten-zirconium oxide (TiO 2 / WO 3 / ZrO 2 ) carrier; And
Firing the carrier impregnated with the metal precursor aqueous solution in air;
And a catalyst for hydrothermal reaction.
상기 티타늄-텅스텐-지르코늄 산화물 담체를 제조하는 단계는,
지르코늄 수산화물(zirconium hydroxide), 암모늄 메타텅스테이트 수화물(ammonium metatungstate hydrate)을 이온교환수와 혼합하여 반응시킨 후 소성하는 단계; 및
상기 소성물을 암모늄 티타닐 옥살레이트 일수화물(ammonium titanyl oxalate monohydrate)와 혼합한 후 소성하는 단계;
를 포함하는, 수첨탈산소 반응용 촉매의 제조방법.The method of claim 6, further comprising the step of preparing a titanium-tungsten-zirconium oxide support before impregnating the metal precursor aqueous solution with the titanium-tungsten-zirconium oxide support,
The step of preparing the titanium-tungsten-zirconium oxide support comprises:
Zirconium hydroxide, and ammonium metatungstate hydrate are mixed with ion exchange water and reacted; And
Mixing the calcined material with ammonium titanyl oxalate monohydrate and then calcining;
And a catalyst for hydrothermal reaction.
반응기 내에 함산소 탄화수소 화합물을 포함하는 바이오매스를 투입하는 단계; 및
상기 반응기 내에 상기 제1항 내지 제5항 중 어느 한 항의 수첨탈산소 반응용 촉매를 가하여 수첨탈산소 반응을 통해 탈산소 탄화수소 화합물을 제조하는 단계;
를 포함하는 바이오 연료의 제조방법. The method according to claim 11,
Introducing a biomass containing an oxygen-containing hydrocarbon compound into the reactor; And
Adding a catalyst for hydrotreating oxygen reaction according to any one of claims 1 to 5 into the reactor to produce a deoxygenated hydrocarbon compound through a hydrocracking reaction;
≪ / RTI >
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| KR101336981B1 (en) * | 2011-10-19 | 2013-12-04 | 고려대학교 산학협력단 | The method of aromatic compounds production using tungsten oxide titania catalyst for hydrodeoxygenation of Guaiacol |
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| KR101336981B1 (en) * | 2011-10-19 | 2013-12-04 | 고려대학교 산학협력단 | The method of aromatic compounds production using tungsten oxide titania catalyst for hydrodeoxygenation of Guaiacol |
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| US11583833B2 (en) | 2018-06-18 | 2023-02-21 | Korea Institute Of Science And Technology | Calcium salts-supported metal catalyst, method for preparing the same, and method for hydrodeoxygenation reaction of oxygenates using the same |
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