KR102613061B1 - Catalyst for Hydrodeoxygenating Oxygenated Compounds and Method for Preparing Bionaphtha from Biomass Using the Same - Google Patents
Catalyst for Hydrodeoxygenating Oxygenated Compounds and Method for Preparing Bionaphtha from Biomass Using the Same Download PDFInfo
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- KR102613061B1 KR102613061B1 KR1020210111841A KR20210111841A KR102613061B1 KR 102613061 B1 KR102613061 B1 KR 102613061B1 KR 1020210111841 A KR1020210111841 A KR 1020210111841A KR 20210111841 A KR20210111841 A KR 20210111841A KR 102613061 B1 KR102613061 B1 KR 102613061B1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000002028 Biomass Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 86
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000001301 oxygen Substances 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 47
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 46
- 238000000197 pyrolysis Methods 0.000 claims abstract description 46
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 41
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 31
- 239000010937 tungsten Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 238000010485 C−C bond formation reaction Methods 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005882 aldol condensation reaction Methods 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000003635 deoxygenating effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 38
- 229910010413 TiO 2 Inorganic materials 0.000 description 26
- 239000012071 phase Substances 0.000 description 17
- 239000002243 precursor Substances 0.000 description 7
- 239000002551 biofuel Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CDNQOMJEQKBLBN-UHFFFAOYSA-N 3-(hydroxymethyl)benzaldehyde Chemical compound OCC1=CC=CC(C=O)=C1 CDNQOMJEQKBLBN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- GBKGJMYPQZODMI-SNAWJCMRSA-N (e)-4-(furan-2-yl)but-3-en-2-one Chemical compound CC(=O)\C=C\C1=CC=CO1 GBKGJMYPQZODMI-SNAWJCMRSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001667 (E)-4-furan-2-ylbut-3-en-2-one Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002927 oxygen compounds Chemical class 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
- B01J37/02—Impregnation, coating or precipitation
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
본 발명은 금속 산화물 지지체 상에 백금(Pt) 및 텅스텐(W)이 순차적으로 담지된 촉매를 사용하여 함산소 화합물의 수소첨가 탈산소반응을 실시함으로써, 함산소 화합물로부터 탄소수 5 내지 12개의 탈산소 탄화수소 화합물을 제조하는 방법을 제공한다. 또한, 본 발명은 바이오매스로부터 바이오나프타를 제조하는 방법으로서, (a) 상기 바이오매스로부터 열분해유를 얻는 단계; (b) 상기 열분해유 중의 함산소 화합물을 탄소-탄소 결합 형성 반응에 의해 탄소수를 증가시켜 중쇄 함산소 화합물을 얻는 단계; 및 (c) 상기 중쇄 함산소 화합물을 탄소수 5 내지 12개의 탈산소 탄화수소 화합물의 제조 방법에 적용하는 단계를 포함하는, 방법이 제공된다.The present invention performs a hydrogenation deoxygenation reaction of oxygen-containing compounds using a catalyst in which platinum (Pt) and tungsten (W) are sequentially supported on a metal oxide support, thereby deoxygenating carbon atoms of 5 to 12 from oxygen-containing compounds. A method for producing a hydrocarbon compound is provided. In addition, the present invention provides a method for producing bionaphtha from biomass, comprising the steps of (a) obtaining pyrolysis oil from the biomass; (b) obtaining a medium-chain oxygenated compound by increasing the carbon number of the oxygenated compound in the pyrolysis oil through a carbon-carbon bond formation reaction; and (c) applying the medium chain oxygenated compound to a method for producing a deoxygenated hydrocarbon compound having 5 to 12 carbon atoms.
Description
본 발명은 함산소 화합물, 구체적으로는 수상 열분해유로부터 유래된 함산소 화합물의 수소 첨가 탈산소 반응용 촉매, 이를 이용한 탈산소 탄화수소 화합물의 제조 방법, 및 바이오매스로부터 바이오나프타를 제조하는 방법에 관한 것이다.The present invention relates to oxygen-containing compounds, specifically, a catalyst for hydrogenation deoxygenation reaction of oxygen-containing compounds derived from water-phase pyrolysis oil, a method for producing deoxygenated hydrocarbon compounds using the same, and a method for producing bionaphtha from biomass. will be.
전세계적으로 화석에너지에 의한 대기오염과 화석에너지 고갈로 인한 에너지 수급의 문제에 직면하면서 대체에너지에 대한 관심이 높아지고 있다. 이 중에서 바이오매스로부터 생산되는 바이오 에너지는 탄소 중립적이며 지속가능하다는 측면에서 새로운 에너지원으로 대두되고 있다. 특히, 목질계 바이오매스 는 전체 식물성 바이오매스의 95% 이상을 차지하고 비식량 자원 및 폐기물을 활용할 수 있어서 차세대 바이오매스로 많은 관심을 받고 있다. Interest in alternative energy is increasing as the world faces problems of energy supply and demand due to air pollution caused by fossil energy and depletion of fossil energy. Among these, bioenergy produced from biomass is emerging as a new energy source in that it is carbon neutral and sustainable. In particular, lignocellulosic biomass accounts for more than 95% of total plant biomass and is receiving much attention as a next-generation biomass because it can utilize non-food resources and waste.
다양한 바이오매스 원료로부터 고급 연료를 생산하는 다양한 화학적, 생물학적 방법이 제시되고 있으며, 모든 종류의 탄소화합물을 원료로 사용할 수 있는 방법으로는 열분해 방법이 있다. 열분해 공정으로 얻어지는 액상 생성물인 열분해유는 난방 및 수송을 위한 바이오 연료로 활용할 수 있다. 다만, 수상 열분해유는 유상 열분해유와 달리 탄화수소의 탄소수가 적기 때문에 액상 연료로의 사용이 제한적이라는 단점이 있다. 또한, 수상 열분해유는 물을 포함하고 있으며, 유기산, 케톤, 알데히드 등, 반응성이 큰 카보닐(CO-) 기를 포함하는 함산소 화합물을 다량으로 포함하고 있기 때문에 탄화수소계 연료와 잘 혼합되지 않으며 바이오연료의 품질 및 안정성이 떨어지게 된다. 따라서 함산소 화합물로부터 산소를 제거해야 할 필요가 있다. A variety of chemical and biological methods have been proposed to produce high-quality fuels from various biomass raw materials, and a method that can use all types of carbon compounds as raw materials includes pyrolysis. Pyrolysis oil, a liquid product obtained through the pyrolysis process, can be used as biofuel for heating and transportation. However, unlike oil-phase pyrolysis oil, water-phase pyrolysis oil has a disadvantage in that its use as a liquid fuel is limited because the hydrocarbon number is low. In addition, aqueous pyrolysis oil contains water and a large amount of oxygen-containing compounds containing highly reactive carbonyl (CO-) groups, such as organic acids, ketones, and aldehydes, so it does not mix well with hydrocarbon fuels and is not suitable for use in biotechnology. The quality and stability of fuel deteriorates. Therefore, there is a need to remove oxygen from oxygen-containing compounds.
다만, 함산소 화합물로부터 산소를 제거하기 위해 고온/고압에 노출시킬 경우, 높은 반응성으로 인해 촉매에 심각한 코크 형성 및 고분자화가 되어 촉매를 비활성시키는 문제점이 있다. 이를 해결하기 위해 2단 반응으로서 먼저 저온 수소화를 통해 산소를 -OH로 전환하는 수소화의 1단계 및 고온에서 수소첨가 탈산소반응을 통해 산소를 제거하는 2단계를 실시하는 방안이 제안되었다. 그러나 이 방법은 시간, 비용 등의 측면에서 생산 효율이 떨어지는 단점이 있었다. 이에 따라 1단계로 수소화/수소첨가 탈산소반응을 모두 진행하되 전술한 문제점을 고려하여 저온에서 반응을 진행시키고자 하였으나, 이 경우에도 원료나 반응중간체가 촉매 표면에 붙어 이론수율만큼 탄화수소 수율을 얻기 어렵다는 문제점이 있었다.However, when exposed to high temperature/high pressure to remove oxygen from oxygen-containing compounds, there is a problem of serious coke formation and polymerization in the catalyst due to high reactivity, thereby deactivating the catalyst. To solve this problem, a two-stage reaction was proposed: the first stage of hydrogenation, which first converts oxygen to -OH through low-temperature hydrogenation, and the second stage, which removes oxygen through hydrogenation deoxygenation reaction at high temperature. However, this method had the disadvantage of low production efficiency in terms of time, cost, etc. Accordingly, it was attempted to proceed with both hydrogenation/hydrogenation and deoxygenation reactions in one step, but to proceed at low temperatures in consideration of the above-mentioned problems. However, even in this case, raw materials or reaction intermediates adhere to the catalyst surface, resulting in a hydrocarbon yield equivalent to the theoretical yield. There was a problem that it was difficult.
본 발명의 일 목적은 수소화 반응을 포함하는 2단계 반응을 이용하지 않고, 저온 및 저압에서 수소첨가 탈산소반응을 수행하더라도 촉매에서의 코크 형성이 억제되고 촉매 활성이 우수하여 높은 탄소 밸런스, 전환율, 탄화수소 수율 등으로 탈산소 화합물을 생성할 수 있는, 촉매, 이를 이용한 탈산소 화합물의 제조 방법 및 바이오매스로부터 바이오나프타를 얻는 방법을 제공하는 것이다.One object of the present invention is to suppress coke formation in the catalyst and achieve excellent catalytic activity, resulting in high carbon balance, conversion rate, and The aim is to provide a catalyst capable of producing deoxygenated compounds with high hydrocarbon yield, a method for producing deoxygenated compounds using the same, and a method for obtaining bionaphtha from biomass.
상기 목적을 달성하기 위하여, 본 발명의 일 양태에 따르면, 금속 산화물 지지체 상에 백금(Pt) 및 텅스텐(W)이 순차적으로 담지된 촉매를 사용하여 함산소 화합물의 수소첨가 탈산소반응을 실시함으로써 함산소 화합물로부터 탄소수 5 내지 12개의 탈산소 탄화수소 화합물을 제조하는 방법이 제공된다.In order to achieve the above object, according to one aspect of the present invention, a hydrogenation deoxygenation reaction of an oxygen-containing compound is performed using a catalyst in which platinum (Pt) and tungsten (W) are sequentially supported on a metal oxide support. A method for producing a deoxygenated hydrocarbon compound having 5 to 12 carbon atoms from an oxygenated compound is provided.
본 발명의 일 구현예에 따르면, 상기 함산소 화합물은 함산소 헤테로고리부를 포함하는 화합물을 포함하는 것일 수 있다.According to one embodiment of the present invention, the oxygen-containing compound may include a compound containing an oxygen-containing heterocyclic group.
본 발명의 일 구현예에 따르면, 상기 함산소 화합물은 바이오매스의 수상 열분해유에서 유래된 것일 수 있다.According to one embodiment of the present invention, the oxygen-containing compound may be derived from aqueous pyrolysis oil of biomass.
본 발명의 일 구현예에 따르면, 상기 수소첨가 탈산소반응은 수소 가스를 제공하여 수소 분위기 하에서 탈산소 반응이 진행되도록 함으로써 수행될 수 있다.According to one embodiment of the present invention, the hydrogenation deoxygenation reaction can be performed by providing hydrogen gas to allow the deoxygenation reaction to proceed under a hydrogen atmosphere.
본 발명의 일 구현예에 따르면, 상기 수소첨가 탈산소 반응은 190℃ 내지 210℃의 온도 및 30 내지 70 bar의 압력에서 수소 분위기 하에 수행되어 97% 이상의 탄소 밸런스(carbon balance)(생성물 내의 탄소 몰수/반응물 내의 탄소 몰수 X 100), 97% 이상의 전환율, 및 60% 이상의 탄화수소 수율을 나타낼 수 있다.According to one embodiment of the present invention, the hydrogenation deoxygenation reaction is performed under a hydrogen atmosphere at a temperature of 190°C to 210°C and a pressure of 30 to 70 bar to achieve a carbon balance of 97% or more (number of moles of carbon in the product) / number of moles of carbon in the reactant
본 발명의 일 구현예에 따르면, 상기 금속 산화물 지지체는 티타늄 산화물 지지체일 수 있다.According to one embodiment of the present invention, the metal oxide support may be a titanium oxide support.
본 발명의 일 구현예에 따르면, 상기 백금(Pt)은 상기 지지체 중량을 기준으로 0.1 내지 5 중량%로 담지되고, 상기 텅스텐은 상기 지지체 중량을 기준으로 1 내지 20 중량%의 양으로 담지될 수 있다.According to one embodiment of the present invention, the platinum (Pt) may be supported in an amount of 0.1 to 5% by weight based on the weight of the support, and the tungsten may be supported in an amount of 1 to 20% by weight based on the weight of the support. there is.
본 발명의 다른 일 양태에 따르면, 바이오매스로부터 바이오나프타를 제조하는 방법으로서, (a) 상기 바이오매스로부터 열분해유를 얻는 단계; (b) 상기 열분해유 중의 함산소 화합물을 탄소-탄소 결합 형성 반응에 의해 탄소수를 증가시켜 중쇄 함산소 화합물을 얻는 단계; 및 (c) 상기 중쇄 함산소 화합물을 탄소수 5 내지 12개의 탈산소 탄화수소 화합물의 제조 방법에 적용하는 단계를 포함하는, 방법이 제공된다.According to another aspect of the present invention, there is a method of producing bionaphtha from biomass, comprising the steps of (a) obtaining pyrolysis oil from the biomass; (b) obtaining a medium-chain oxygenated compound by increasing the carbon number of the oxygenated compound in the pyrolysis oil through a carbon-carbon bond formation reaction; and (c) applying the medium chain oxygenated compound to a method for producing a deoxygenated hydrocarbon compound having 5 to 12 carbon atoms.
본 발명의 일 구현예에 따르면, 상기 (a) 단계는 상기 바이오매스를 열분해하여 유상 열분해유 및 수상 열분해유를 얻는 단계이고, 상기 (a) 단계에서 얻어진 유상 열분해유와 수상 열분해유를 분리하는 단계를 추가로 포함하여 상기 (b) 단계의 열분해유로서 사용할 수 있다.According to one embodiment of the present invention, step (a) is a step of pyrolyzing the biomass to obtain oil phase pyrolysis oil and water phase pyrolysis oil, and separating the oil phase pyrolysis oil and the water phase pyrolysis oil obtained in step (a). It can be used as pyrolysis oil in step (b) above by further including the step.
본 발명의 일 구현예에 따르면, 상기 (b) 단계에서 상기 탄소-탄소 결합 형성 반응은 알돌 축합 반응, 케톤화 반응, 또는 알킬화 반응일 수 있다.According to one embodiment of the present invention, the carbon-carbon bond forming reaction in step (b) may be an aldol condensation reaction, a ketonization reaction, or an alkylation reaction.
본 발명의 일 구현예에 따르면, 상기 바이오매스는 목질계 또는 초본계 바이오매스일 수 있다.According to one embodiment of the present invention, the biomass may be lignocellulosic or herbaceous biomass.
본 발명의 또다른 일 양태에 따르면, 금속 산화물 지지체 상에 백금(Pt) 및 텅스텐(W)이 순차적으로 담지된, 바이오매스의 수상 열분해유에서 유래된 함산소 화합물의 수소첨가 탈산소반응용 촉매가 제공된다.According to another aspect of the present invention, there is a catalyst for hydrogenation deoxygenation reaction of oxygenated compounds derived from aqueous pyrolysis oil of biomass, in which platinum (Pt) and tungsten (W) are sequentially supported on a metal oxide support. provided.
본 발명의 일 구현예에 따르면, 상기 촉매에서 상기 금속 산화물 지지체는 티타늄 산화물 지지체이고, 상기 백금(Pt)은 상기 지지체 중량을 기준으로 0.1 내지 5 중량%로 담지되고, 상기 백금 담지 후 상기 텅스텐은 상기 지지체 중량을 기준으로 1 내지 20 중량%의 양으로 담지될 수 있다.According to one embodiment of the present invention, in the catalyst, the metal oxide support is a titanium oxide support, the platinum (Pt) is supported in an amount of 0.1 to 5% by weight based on the weight of the support, and after the platinum is supported, the tungsten is It may be supported in an amount of 1 to 20% by weight based on the weight of the support.
본 발명에 따르면, 금속 산화물 지지체 상에 백금(Pt)과 텅스텐이 순차적으로 담지된 촉매를 사용함으로써, 수소화 반응을 포함하는 2단계 반응을 이용하지 않고, 수소첨가 탈산소반응을 1단계로, 특히 저온 및 저압에서 수행하여도 함산소 화합물로부터 탈탄소 탄화수소 화합물을 얻을 수 있다. 이에 따라 탈탄소 탄화수소 화합물을 제조하기 위한 생산 효율이 향상될 수 있다. 특히, 상기 수소첨가 탈탄소반응에서 촉매에서의 코크 형성이 억제될 수 있으며 촉매 활성이 우수하여 높은 탄소 밸런스, 전환율, 탄화수소 수율 등으로 탈산소 화합물을 생성할 수 있다. According to the present invention, by using a catalyst in which platinum (Pt) and tungsten are sequentially supported on a metal oxide support, the hydrogenation deoxygenation reaction is performed in one step, rather than using a two-step reaction including a hydrogenation reaction. Even when performed at low temperature and pressure, decarbonized hydrocarbon compounds can be obtained from oxygenated compounds. Accordingly, production efficiency for producing decarbonized hydrocarbon compounds can be improved. In particular, in the hydrogenation decarbonization reaction, coke formation in the catalyst can be suppressed, and the catalyst activity is excellent, so that deoxygenation compounds can be produced with high carbon balance, conversion rate, and hydrocarbon yield.
또한, 바이오매스로부터의 열분해유 중에서 유상 열분해유는 바이오연료로 활용될 수 있으나, 수상 열분해유는 탄화수소 화합물의 탄소수가 적어서 바이오연료로의 활용이 제한적인 단점이 있었다. 그러나, 본 발명에 따르면, 탄소-탄소 결합 형성 반응을 통해 상기 수상 열분해유 중 함산소 화합물의 탄소수를 증가시키고, 그 후, 본 발명에 따른 촉매를 사용하여 수소첨가 탈산소 반응을 실시함으로써 바이오나프타를 얻을 수 있다. 이에, 바이오연료로 활용이 곤란했던 바이오매스로부터의 수상 열분해유를 활용할 수 있는 방안이 마련될 수 있게 되었다.In addition, among pyrolysis oils from biomass, oil-phase pyrolysis oil can be used as biofuel, but water-phase pyrolysis oil has a disadvantage in that its use as biofuel is limited due to the low carbon number of hydrocarbon compounds. However, according to the present invention, the carbon number of oxygenated compounds in the water phase pyrolysis oil is increased through a carbon-carbon bond formation reaction, and then a hydrogenation deoxygenation reaction is performed using the catalyst according to the present invention to produce bionaphtha. can be obtained. Accordingly, a method could be developed to utilize aqueous pyrolysis oil from biomass, which had been difficult to utilize as biofuel.
도 1은 촉매 중의 귀금속과 텅스텐의 담지 유무, 담지 순서에 따른 수소첨가 탈산소 반응, 및 반응 온도에 따른 수소첨가 탈산소 반응을 탄소 밸런스, 전환율, 탄화수소 수율에 의해 비교한 것이다.
도 2는 촉매 중의 텅스텐 담지량에 따른 수소첨가 탈산소 반응을 비교한 것이다.
도 3은 본 발명에 따른 W/Pt/TiO2 촉매에서 텅스텐(W)을 이와 유사한 금속으로 대체한 Re/Pt/TiO2 촉매, Co/Pt/TiO2 촉매, Fe/Pt/TiO2 촉매를 사용하였을 때의 수소첨가 탈산소 반응을 비교한 것이다.Figure 1 compares the hydrogenation deoxygenation reaction according to the presence or absence of noble metal and tungsten in the catalyst, the support order, and the hydrogenation deoxygenation reaction according to the reaction temperature in terms of carbon balance, conversion rate, and hydrocarbon yield.
Figure 2 compares hydrogenation and deoxygenation reactions according to the amount of tungsten supported in the catalyst.
Figure 3 shows the Re/Pt/TiO 2 catalyst, Co/Pt/TiO 2 catalyst, and Fe/Pt/TiO 2 catalyst in which tungsten (W) is replaced with a similar metal in the W/Pt/TiO 2 catalyst according to the present invention. This compares the hydrogenation and deoxygenation reactions when used.
이하, 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 출원에서 사용한 용어는 단지 특정한 구현예를 설명하기 위해 사용된 것으로서 본 발명을 한정하려는 의도가 아니다. 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. The terms used in this application are merely used to describe specific embodiments and are not intended to limit the invention. Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the technical field to which the present invention pertains.
명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다, "함유"한다, "가지다"라고 할 때, 이는 특별히 달리 정의되지 않는 한, 다른 구성 요소를 더 포함할 수 있다는 것을 의미한다.Throughout the specification, when a part is said to “include”, “contain”, or “have” a certain component, this means that it may further include other components, unless specifically defined otherwise.
본 발명의 일 구현예에 따르면, 금속 산화물 지지체 상에 백금(Pt) 및 텅스텐(W)이 순차적으로 담지된 촉매는 함산소 화합물의 수소첨가 탈산소 반응, 특히 바이오매스의 수상 열분해유에서 유래된 함산소 화합물의 수소첨가 탈산소 반응에 사용될 수 있다. 또한, 상기 촉매는 함산소 화합물의 수소첨가 탈산소반응을 실시함으로써 함산소 화합물로부터 탄소수 5 내지 12개의 탈산소 탄화수소 화합물을 제조하는 방법 또는 바이오매스로부터 바이오나프타를 제조하는 방법에 사용될 수 있다. 이에, 상기 촉매에 대해 보다 구체적으로 설명하면 다음과 같다.According to one embodiment of the present invention, a catalyst in which platinum (Pt) and tungsten (W) are sequentially supported on a metal oxide support is used for the hydrogenation deoxygenation reaction of oxygenated compounds, especially those derived from aqueous pyrolysis oil of biomass. It can be used in the hydrogenation-deoxygenation reaction of oxygen-containing compounds. In addition, the catalyst can be used in a method of producing a deoxygenated hydrocarbon compound having 5 to 12 carbon atoms from an oxygen-containing compound by performing a hydrogenation deoxygenation reaction of the oxygen-containing compound or a method of producing bionaphtha from biomass. Accordingly, the catalyst will be described in more detail as follows.
본 발명의 일 구현예에 따른 촉매는 금속 산화물 지지체 상에 백금(Pt)이 먼저 담지되고 그 후 텅스텐(W)이 담지된 구성의 촉매이다. 이와 같이 백금(Pt) 과 텅스텐을 사용하되 순차로 담지함으로써 함산소 화합물의 수소첨가 탈산소 반응에서 우수한 촉매 활성, 예를 들어 탄소 밸런스, 전환율, 및 탄화수소 수율을 나타낼 수 있다. The catalyst according to one embodiment of the present invention is a catalyst in which platinum (Pt) is first supported on a metal oxide support and then tungsten (W) is supported. In this way, by using platinum (Pt) and tungsten and sequentially supporting them, excellent catalytic activity, such as carbon balance, conversion rate, and hydrocarbon yield, can be exhibited in the hydrogenation-deoxygenation reaction of oxygen-containing compounds.
본 발명의 일 구현예에 따르면, 상기 금속 산화물 지지체는 지르코늄 산화물, 텅스텐 산화물, 티타늄 산화물 등이 사용될 수 있으나, 바람직하게는 티타늄 산화물 지지체이다.According to one embodiment of the present invention, the metal oxide support may be zirconium oxide, tungsten oxide, titanium oxide, etc., but is preferably a titanium oxide support.
또한, 본 발명의 일 구현예에 따르면, 상기 백금(Pt)은 상기 지지체 중량을 기준으로 0.1 내지 5 중량%로 담지될 수 있다. 또한, 본 발명의 일 구현예에 따르면, 상기 텅스텐은 상기 지지체 중량을 기준으로 1 내지 20 중량%의 양으로, 예를 들어 5 내지 20 중량% 또는 10 내지 17 중량%의 양으로 담지될 수 있다.Additionally, according to one embodiment of the present invention, platinum (Pt) may be supported in an amount of 0.1 to 5% by weight based on the weight of the support. In addition, according to one embodiment of the present invention, the tungsten may be supported in an amount of 1 to 20% by weight, for example, 5 to 20% by weight or 10 to 17% by weight, based on the weight of the support. .
본 발명의 일 구현예에 따르면, 상기 촉매는 함침법, 예를 들어 초기 습식법 (wetness incipient method)에 따라 제조될 수 있다. 본 발명의 일 구현예에 따르면, 상기 촉매의 제조 방법은, 금속 산화물 지지체를 백금(Pt) 전구체 용액과 혼합하여 함침하여 백금(Pt)을 담지시키는 단계; 상기 백금(Pt)이 담지된 지지체를 소성하는 단계; 상기 소성된 지지체를 텅스텐 전구체 용액과 혼합하여 텅스텐을 담지시키는 단계; 및 상기 텅스텐이 담지된 지지체를 소성하는 단계를 포함할 수 있다. According to one embodiment of the present invention, the catalyst may be prepared according to an impregnation method, for example, an initial wet method (wetness incipient method). According to one embodiment of the present invention, the method for producing the catalyst includes the steps of impregnating a metal oxide support by mixing it with a platinum (Pt) precursor solution to support platinum (Pt); Calcining the support on which platinum (Pt) is supported; mixing the fired support with a tungsten precursor solution to support tungsten; And it may include the step of firing the support on which the tungsten is supported.
본 발명의 일 구현예에 따르면, 상기 백금(Pt) 전구체 및 상기 텅스텐 전구체는 염의 형태일 수 있으며, 예를 들어 염화물, 염소산염, 암모늄염 등의 형태일 수 있다.According to one embodiment of the present invention, the platinum (Pt) precursor and the tungsten precursor may be in the form of a salt, for example, chloride, chlorate, ammonium salt, etc.
본 발명의 일 구현예에 따르면, 상기 소성은 공기 중에서 실시될 수 있다. 또한, 상기 소성 온도 및 시간은 특별히 제한되지 않고 촉매의 조성이나 상태 등에 따라 적절히 조절될 수 있으나, 통상적으로는 200 내지 600℃의 온도에서 1 내지 5시간 동안 수행될 수 있다.According to one embodiment of the present invention, the firing may be carried out in air. In addition, the calcination temperature and time are not particularly limited and can be appropriately adjusted depending on the composition or state of the catalyst, but can typically be performed at a temperature of 200 to 600°C for 1 to 5 hours.
또한, 본 발명의 일 구현예에 따르면, 상기 촉매의 제조방법은 상기 소성 단계 이후, 수소 분위기에서 환원시키는 단계를 더 포함할 수 있다. 상기 환원 단계는 수소 분위기에서 약 200 내지 500℃로 약 1시간 내지 5시간 동안 진행될 수 있다.Additionally, according to one embodiment of the present invention, the method for producing the catalyst may further include a step of reduction in a hydrogen atmosphere after the calcination step. The reduction step may be carried out in a hydrogen atmosphere at about 200 to 500° C. for about 1 hour to 5 hours.
본 발명의 일 양태에 따르면, 금속 산화물 지지체 상에 백금(Pt) 및 텅스텐(W)이 순차적으로 담지된 촉매는 함산소 화합물의 수소첨가 탈산소 반응을 통해 탈탄소 탄화수소 화합물을 제조하는데 적합하게 사용될 수 있다. 이에, 본 발명의 일 양태에 따르면, 금속 산화물 지지체 상에 백금(Pt) 및 텅스텐(W)이 순차적으로 담지된 촉매를 사용하여 함산소 화합물의 수소첨가 탈산소반응을 실시함으로써 함산소 화합물로부터 탄소수 5 내지 12개의 탈산소 탄화수소 화합물을 제조하는 방법이 제공된다. According to one aspect of the present invention, a catalyst in which platinum (Pt) and tungsten (W) are sequentially supported on a metal oxide support can be suitably used to produce decarbonized hydrocarbon compounds through hydrogenation deoxygenation reaction of oxygenated compounds. You can. Accordingly, according to one aspect of the present invention, a hydrogenation deoxygenation reaction of an oxygen-containing compound is performed using a catalyst in which platinum (Pt) and tungsten (W) are sequentially supported on a metal oxide support, thereby converting carbon numbers from the oxygen-containing compound. A method for producing 5 to 12 deoxygenated hydrocarbon compounds is provided.
본 명세서에서, 함산소 화합물은 산소 원자를 분자 구조 내에 포함하는 화합물을 의미한다. 본 발명의 일 구현예에 따르면, 상기 함산소 화합물은 탄소수 5 내지 13개, 예를 들어 탄소수 5 내지 12개의 함산소 화합물일 수 있으며, 여기서. 탄소수는 함산소부의 탄소까지 모두 합하여 전체 탄소수가 5 내지 13개, 예를 들어 5 내지 12개일 수 있다. 또한 상기 함산소 화합물은 함산소 헤테로고리부, 예를 들어 퓨란(furan)을 포함하는 화합물일 수 있으며, 함산소 헤테로고리부 이외에도 카르보닐기를 추가로 더 포함하는 화합물일 수도 있다. 또한, 상기 함산소 화합물은 상기 함산소부를 제외하고는 나머지 골격은 탄화수소 형태인, 함산소 탄화수소 화합물일 수 있다.In this specification, an oxygen-containing compound refers to a compound containing an oxygen atom in its molecular structure. According to one embodiment of the present invention, the oxygen-containing compound may be an oxygen-containing compound having 5 to 13 carbon atoms, for example, 5 to 12 carbon atoms. The total number of carbons, including the carbons of the oxygen-containing portion, may be 5 to 13, for example, 5 to 12. In addition, the oxygen-containing compound may be a compound containing an oxygen-containing heterocyclic group, for example, furan, and may be a compound further containing a carbonyl group in addition to the oxygen-containing heterocyclic group. Additionally, the oxygen-containing compound may be an oxygen-containing hydrocarbon compound in which, except for the oxygen-containing portion, the remaining skeleton is in the form of a hydrocarbon.
또한, 본 발명의 일 구현예에 따르면, 상기 함산소 화합물은 바이오매스의 열분해유, 특히 수상 열분해유에서 유래된 것일 수 있다. 본 발명의 일 구현예에 따르면, 상기 함산소 화합물은 수상 열분해유 중의 함산소 화합물을 탄소-탄소 형성 반응을 통해 탄소수를 증가시켜 얻은 함산소 화합물일 수 있다. 여기서, 상기 바이오매스는 목질계 또는 초본계 바이오매스일 수 있다. 이에, 상기 수상 열분해유의 구성성분은 목재 구성성분인 셀룰로오스와 헤미셀룰로오스의 열분해로부터 주로 생성된 것일 수 있다.In addition, according to one embodiment of the present invention, the oxygen-containing compound may be derived from pyrolysis oil of biomass, especially aqueous pyrolysis oil. According to one embodiment of the present invention, the oxygen-containing compound may be an oxygen-containing compound obtained by increasing the carbon number of an oxygen-containing compound in water-phase pyrolysis oil through a carbon-carbon formation reaction. Here, the biomass may be lignocellulosic or herbaceous biomass. Accordingly, the components of the water-phase pyrolysis oil may be mainly produced from the thermal decomposition of cellulose and hemicellulose, which are components of wood.
본 명세서에서 탈산소 탄화수소 화합물은 전술한 함산소 화합물로부터 산소가 일부 또는 전부 제거된 탄화수소 화합물을 의미한다. 이에, 탈탄소 탄화수소 화합물은 출발 물질인 함산소 화합물의 전체 탄소수와 동일한 탄소수를 갖는 탄화수소 화합물을 포함한다. 또한, 상기 탈탄소 탄화수소 화합물은 함산소 화합물의 전체 탄소수보다 탄소수가 더 적은 화합물도 추가로 포함할 수 있다. 이에, 본 발명의 일 구현예에 따르면, 상기 탈산소 탄화수소 화합물은 탄소수 5 내지 12개의 탄화수소 또는 이의 혼합물일 수 있다.As used herein, a deoxygenated hydrocarbon compound refers to a hydrocarbon compound from which some or all of the oxygen has been removed from the oxygen-containing compound described above. Accordingly, the decarbonized hydrocarbon compound includes a hydrocarbon compound having the same number of carbon atoms as the total carbon number of the oxygen-containing compound that is the starting material. In addition, the decarbonated hydrocarbon compound may further include a compound having fewer carbon atoms than the total carbon number of the oxygen-containing compound. Therefore, according to one embodiment of the present invention, the deoxygenated hydrocarbon compound may be a hydrocarbon having 5 to 12 carbon atoms or a mixture thereof.
본 발명의 일 구현예에 따르면, 상기 수소첨가 탈산소반응에서 수소첨가는 수소 가스를 투입함으로써 이루어질 수 있다. 예를 들어, 상기 수소첨가 탈산소반응은 수소 가스를 제공하여 수소 분위기 하에서 탈산소 반응이 진행되도록 함으로써 수행될 수 있다. According to one embodiment of the present invention, hydrogen addition in the hydrogenation-deoxygenation reaction can be performed by introducing hydrogen gas. For example, the hydrogenation deoxygenation reaction can be performed by providing hydrogen gas and allowing the deoxygenation reaction to proceed under a hydrogen atmosphere.
또한, 본 발명의 일 구현예에 따르면, 상기 수소첨가 탈산소 반응은 190℃ 내지 500℃의 온도, 예를 들어 200℃ 내지 400℃의 온도, 및 20 내지 150 bar의 압력, 예를 들어 30 내지 100 bar의 압력에서 수행될 수 있다. 상기 온도 및 압력 범위에서 수소첨가 탈산소 반응의 효율이 우수하다. 여기서 상기 압력은 반응 시작시의 수소 압력이다.In addition, according to one embodiment of the present invention, the hydrogenation deoxygenation reaction is performed at a temperature of 190°C to 500°C, for example, a temperature of 200°C to 400°C, and a pressure of 20 to 150 bar, for example, 30 to 150 bar. It can be performed at a pressure of 100 bar. The efficiency of hydrogenation deoxygenation reaction is excellent in the above temperature and pressure range. Here, the pressure is the hydrogen pressure at the start of the reaction.
본 발명의 수소첨가 탈산소반응은 본 발명의 촉매를 사용함으로써 저온, 저압에서도 우수하게 진행될 수 있다. 또한, 별도의 수소화 처리 단계를 추가로 수행하지 않고 수소첨가 탈산소반응의 1단계만 수행하여도 함산소 화합물이 탈산소 탄화수소 화합물로 전환될 수 있다. 더욱이, 탄소 밸런스, 전환율, 탄화수소 수율 등의 성능이 우수하다. 이에 본 발명의 일 구현예에 따르면, 상기 수소첨가 탈산소 반응은 190℃ 내지 210℃의 온도 및 30 내지 70 bar의 압력에서 수소 분위기 하에 수행되어 97% 이상, 예를 들어 100%의 탄소 밸런스(carbon balance)(생성물 내의 탄소 몰수/반응물 내의 탄소 몰수Ⅹ100), 97% 이상, 예를 들어 99% 내지 100%의 전환율, 및 60% 이상의 탄화수소 수율을 나타낼 수 있다. 또한, 이론상 수율에 대비한 탄화수소 수율도 70% 이상, 예를 들어 대략 96%일 수 있다.The hydrogenation deoxygenation reaction of the present invention can proceed excellently even at low temperature and low pressure by using the catalyst of the present invention. In addition, oxygenated compounds can be converted to deoxygenated hydrocarbon compounds by performing only one step of the hydrogenation deoxygenation reaction without additionally performing a separate hydrogenation treatment step. Moreover, the performance of carbon balance, conversion rate, and hydrocarbon yield is excellent. Accordingly, according to one embodiment of the present invention, the hydrogenation deoxygenation reaction is performed under a hydrogen atmosphere at a temperature of 190°C to 210°C and a pressure of 30 to 70 bar to achieve a carbon balance of 97% or more, for example, 100%. carbon balance) (number of moles of carbon in the product/number of moles of carbon in the reactant Ⅹ100), a conversion rate of 97% or more, for example, 99% to 100%, and a hydrocarbon yield of 60% or more. Additionally, the hydrocarbon yield compared to the theoretical yield may be 70% or more, for example, approximately 96%.
또한, 본 발명의 일 양태에 따르면, 바이오매스로부터 바이오나프타를 제조하는 방법으로서, (a) 상기 바이오매스로부터 열분해유를 얻는 단계; (b) 상기 열분해유 중의 함산소 화합물을 탄소-탄소 결합 형성 반응에 의해 탄소수를 증가시켜 중쇄 함산소 화합물을 얻는 단계; 및 (c) 상기 중쇄 함산소 화합물을 탄소수 5 내지 12개의 탈산소 탄화수소 화합물의 제조 방법에 적용하는 단계를 포함하는, 방법이 제공된다.Additionally, according to one aspect of the present invention, there is a method for producing bionaphtha from biomass, comprising: (a) obtaining pyrolysis oil from the biomass; (b) obtaining a medium-chain oxygenated compound by increasing the carbon number of the oxygenated compound in the pyrolysis oil through a carbon-carbon bond formation reaction; and (c) applying the medium chain oxygenated compound to a method for producing a deoxygenated hydrocarbon compound having 5 to 12 carbon atoms.
바이오나프타는 일반적으로, 바이오매스와 같은 재생가능한 공급원으로부터 생성된 나프타를 의미한다. 나프타는 수송용 연료로 사용될 수 있을 뿐만 아니라 고부가가치의 석유화학제품으로 전환될 수 있어서 그 활용도가 우수하다. 나프타는 통상적으로 탄소수가 5 내지 12개 사이인 혼합물로 구성된다. 본원에서 "탄소수 5 내지 12개의 탈산소 탄화수소 화합물"은 상기 바이오나프타일 수 있다.Bionaphtha generally refers to naphtha produced from renewable sources such as biomass. Naphtha has excellent utility because it can not only be used as a transportation fuel, but can also be converted into high value-added petrochemical products. Naphtha typically consists of a mixture containing between 5 and 12 carbon atoms. As used herein, “deoxygenated hydrocarbon compound having 5 to 12 carbon atoms” may be the bionaphtha.
본 발명의 일 구현예에 따르면, 상기 (a) 단계는 상기 바이오매스를 열분해하여 유상 열분해유 및 수상 열분해유를 얻는 단계일 수 있다. 이에 따라, 본 발명의 방법은 상기 (a) 단계에서 얻어진 유상 열분해유와 수상 열분해유를 분리하는 단계를 추가로 포함할 수 있다. 상기 유상 열분해유의 경우에는 필요에 따라 수소첨가 탈산소 반응을 통해 화합물 구조 내의 산소를 제거한 후에 바이오연료로 사용될 수 있으며, 이 때 상기 수소첨가 탈산소 반응은 본 발명에 따른 촉매를 사용하여 수행될 수 있다. 다만, 상기 수상 열분해유의 경우에는 탄소수가 적어서 바이오연료로의 사용이 제한적이다. 이에, 본 발명의 상기 (b) 단계에 투입되어 탄소-탄소 결합 형성 반응을 통해 탄소수를 증가시켜서 활용할 수 있다. 본 발명의 일 구현예에 따르면, 상기 (b) 단계에서 상기 탄소-탄소 결합 형성 반응은 특별히 제한되지는 않으나, 예를 들어 알돌 축합 반응, 케톤화 반응, 또는 알킬화 반응일 수 있다. 상기 (c) 단계에 대한 상세한 사항은 전술한 수소첨가 탈산소 반응에 대해 기재한 바를 참고한다.According to one embodiment of the present invention, step (a) may be a step of obtaining oil phase pyrolysis oil and aqueous phase pyrolysis oil by pyrolyzing the biomass. Accordingly, the method of the present invention may further include the step of separating the oil phase pyrolysis oil and the water phase pyrolysis oil obtained in step (a). In the case of the oil phase pyrolysis oil, it can be used as biofuel after removing oxygen in the compound structure through a hydrogenation deoxygenation reaction, if necessary. In this case, the hydrogenation deoxygenation reaction can be performed using the catalyst according to the present invention. there is. However, in the case of the water-based pyrolysis oil, its use as biofuel is limited due to its low carbon count. Accordingly, it can be used by adding it to step (b) of the present invention to increase the number of carbon atoms through a carbon-carbon bond formation reaction. According to one embodiment of the present invention, the carbon-carbon bond forming reaction in step (b) is not particularly limited, but may be, for example, an aldol condensation reaction, a ketonization reaction, or an alkylation reaction. For details on step (c), refer to the description of the hydrogenation deoxygenation reaction described above.
이하에서는 본 발명의 실시예를 참조하여 발명을 더욱 구체적으로 설명하겠다. 실시예는 발명의 설명을 위해 제시되는 것이므로, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the invention will be described in more detail with reference to embodiments of the invention. Since the examples are presented to explain the invention, the invention is not limited thereto.
실시예 1: 촉매의 제조Example 1: Preparation of catalyst
TiO2 지지체를 백금 또는 다른 귀금속 전구체 용액 (8 중량% in H2O)에 함침함으로써 백금 또는 다른 귀금속이 2 중량%가 담지된 Pt/TiO2 또는 Ru/TiO2, Rh/TiO2, Pd/TiO2 촉매를 제조하였다. 상기 담지 촉매를 105℃에서 하룻밤동안 건조한 후, 450℃에서 4 시간 동안 공기 중에서 소성하였다. 텅스텐 전구체로서 텅스텐 암모늄염(ammonium tungstate)을 적당량의 옥살산 수용액에 용해시킨 후, 상기 텅스텐 전구체 용액에 상기 제조한 Pt/TiO2 또는 Rh/TiO2 촉매를 함침시켜 텅스텐을 담지시켜 W/Pt/TiO2 또는 W/Rh/TiO2 촉매를 얻었다. 상기 담지 촉매를 105℃에서 하룻밤동안 건조한 후, 450℃에서 4 시간 동안 공기 중에서 소성하였다. 후술하는 수소첨가 탈산소 반응에 사용하기 전에 상기 촉매를 330℃에서 수소로 1시간 동안 환원 처리하였다.By impregnating the TiO 2 support in a platinum or other noble metal precursor solution (8% by weight in H 2 O), Pt/TiO 2 or Ru/TiO 2 , Rh/TiO 2 , Pd/ on which 2% by weight of platinum or other noble metals are supported. A TiO 2 catalyst was prepared. The supported catalyst was dried at 105°C overnight and then calcined in air at 450°C for 4 hours. After dissolving tungsten ammonium salt (ammonium tungstate) as a tungsten precursor in an appropriate amount of oxalic acid aqueous solution, the tungsten precursor solution is impregnated with the prepared Pt/TiO 2 or Rh/TiO 2 catalyst to support tungsten to produce W/Pt/TiO 2 Alternatively, a W/Rh/TiO 2 catalyst was obtained. The supported catalyst was dried at 105°C overnight and then calcined in air at 450°C for 4 hours. Before being used in the hydrogenation deoxygenation reaction described later, the catalyst was reduced with hydrogen at 330°C for 1 hour.
실시예 2: 수소첨가 탈산소 반응Example 2: Hydrogenation deoxygenation reaction
수상 열분해유에 포함된 함산소 화합물인 아세톤을 furfural과 알돌 축합 반응시켜서 수득한 4-(푸란-2-일)부트-3-엔-2-온 (C8H8O2, 퍼푸랄아세톤(furfuralacetone))을 중쇄 함산소 화합물로 하고 상기 실시예 1에서 제조한 촉매를 사용하여 수소첨가 탈산소 반응을 실시하였다. Parr 반응기(배치반응기, 100ml)를 이용하여, 반응조건 대로 실험한 이후, 내부표준물질을 넣고 액상 회수하여 GC-FID/GC-MS 분석하였다. Heavy chaining of 4-(furan-2-yl)but-3-en-2-one (C8H8O2, furfuralacetone) obtained by aldol condensation of acetone, an oxygen-containing compound contained in water-phase pyrolysis oil, with furfural. A hydrogenation deoxygenation reaction was performed using an oxygen compound and the catalyst prepared in Example 1 above. After experimenting according to the reaction conditions using a Parr reactor (batch reactor, 100ml), an internal standard was added, the liquid phase was recovered, and GC-FID/GC-MS analysis was performed.
실시예 3: 촉매 및 반응조건에 따른 수소첨가 탈산소 반응의 비교/평가Example 3: Comparison/evaluation of hydrogenation deoxygenation reaction according to catalyst and reaction conditions
도 1은 촉매 중의 귀금속과 텅스텐의 담지 유무, 담지 순서에 따른 수소첨가 탈산소 반응, 및 반응 온도에 따른 수소첨가 탈산소 반응을 탄소 밸런스, 전환율, 탄화수소 수율에 의해 비교한 것이다. 도 1로부터 동일한 반응 조건에서 Rh/TiO2 촉매가 Pt/TiO2 촉매보다 좋은 탄화수소 수율을 얻었으며, 다른 귀금속 담지 촉매의 경우 낮은 탄화수소 수율을 얻었다. 그러나, Rh/TiO2와 Pt/TiO2 촉매에 텅스텐을 추가 담지하였을 때, Pt/W/TiO2 촉매에서 높은 수율의 탄화수소 및 탄소밸란스를 얻었다. 또한 Pt/TiO2 촉매 및 Pt/W/TiO2 촉매에 비해, 본 발명의 W/Pt/TiO2 촉매가 특히 탄소 밸런스 및 탄화수소 수율 측면에서 현저히 더 우수하다는 것을 확인할 수 있다. 또한, 도 1로부터 본 발명의 W/Pt/TiO2 촉매를 200℃, 150℃, 및 250℃의 반응 온도에서 사용하였을 때, 150℃에서는 반응이 거의 일어나지 않았으나, 200℃ 이상에서는 다른 촉매에 비하여 현저히 우수한 성능을 나타낸다는 것을 확인할 수 있다.Figure 1 compares the hydrogenation deoxygenation reaction according to the presence or absence of noble metal and tungsten in the catalyst, the support order, and the hydrogenation deoxygenation reaction according to the reaction temperature in terms of carbon balance, conversion rate, and hydrocarbon yield. From Figure 1, under the same reaction conditions, the Rh/TiO 2 catalyst obtained a better hydrocarbon yield than the Pt/TiO 2 catalyst, and in the case of other noble metal-supported catalysts, a lower hydrocarbon yield was obtained. However, when tungsten was additionally supported on the Rh/TiO 2 and Pt/TiO 2 catalysts, high yields of hydrocarbon and carbon balance were obtained from the Pt/W/TiO 2 catalyst. In addition, it can be seen that compared to the Pt/TiO 2 catalyst and the Pt/W/TiO 2 catalyst, the W/Pt/TiO 2 catalyst of the present invention is significantly superior, especially in terms of carbon balance and hydrocarbon yield. In addition, from Figure 1, when the W/Pt/TiO 2 catalyst of the present invention was used at reaction temperatures of 200°C, 150°C, and 250°C, almost no reaction occurred at 150°C, but above 200°C, compared to other catalysts, It can be confirmed that it shows remarkably excellent performance.
도 2는 촉매 중의 텅스텐 담지량에 따른 수소첨가 탈산소 반응을 비교한 것이다. 텅스텐의 담지에 의해 성능이 향상되는 것을 확인할 수 있다.Figure 2 compares hydrogenation and deoxygenation reactions according to the amount of tungsten supported in the catalyst. It can be seen that performance is improved by tungsten support.
도 3은 본 발명에 따른 W/Pt/TiO2 촉매에서 텅스텐(W)을 이와 유사한 금속으로 대체한 Re/Pt/TiO2 촉매, Co/Pt/TiO2 촉매, Fe/Pt/TiO2 촉매를 사용하였을 때의 수소첨가 탈산소 반응을 비교한 것이다. 본 발명에 따라 W을 사용하였을 때 수율이 가장 우수하다는 것을 알 수 있다.Figure 3 shows the Re/Pt/TiO 2 catalyst, Co/Pt/TiO 2 catalyst, and Fe/Pt/TiO 2 catalyst in which tungsten (W) is replaced with a similar metal in the W/Pt/TiO 2 catalyst according to the present invention. This is a comparison of the hydrogenation and deoxygenation reactions when used. It can be seen that the yield is the best when W is used according to the present invention.
상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although the present invention has been described above with reference to preferred embodiments, those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the present invention as set forth in the following patent claims. You will understand that it is possible.
Claims (13)
상기 함산소 화합물은 함산소 헤테로고리부를 포함하는 화합물을 포함하는 것을 특징으로 하는 방법.According to paragraph 1,
A method characterized in that the oxygen-containing compound includes a compound containing an oxygen-containing heterocyclic group.
상기 함산소 화합물은 바이오매스의 수상 열분해유에서 유래된 것을 특징으로 하는 방법.According to paragraph 1,
A method wherein the oxygen-containing compound is derived from aqueous pyrolysis oil of biomass.
상기 수소첨가 탈산소반응은 수소 가스를 제공하여 수소 분위기 하에서 탈산소 반응이 진행되도록 함으로써 수행되는 것을 특징으로 하는 방법.According to paragraph 1,
The method is characterized in that the hydrogenation deoxygenation reaction is performed by providing hydrogen gas to allow the deoxygenation reaction to proceed under a hydrogen atmosphere.
상기 수소첨가 탈산소 반응은 190℃ 내지 210℃의 온도 및 30 내지 70 bar의 압력에서 수소 분위기 하에 수행되어 97% 이상의 탄소 밸런스(carbon balance)(생성물 내의 탄소 몰수/반응물 내의 탄소 몰수), 97% 이상의 전환율, 및 60% 이상의 탄화수소 수율을 나타내는 것을 특징으로 하는 방법.According to paragraph 1,
The hydrogenation deoxygenation reaction is performed under a hydrogen atmosphere at a temperature of 190°C to 210°C and a pressure of 30 to 70 bar to achieve a carbon balance of 97% or more (number of moles of carbon in the product/number of moles of carbon in the reactant), 97%. A method characterized in that it exhibits a conversion rate of more than 60% and a hydrocarbon yield of more than 60%.
상기 금속 산화물 지지체는 티타늄 산화물 지지체인 것을 특징으로 하는 방법.According to paragraph 1,
A method wherein the metal oxide support is a titanium oxide support.
상기 백금은 상기 지지체 중량을 기준으로 0.1 내지 5 중량%로 담지되고, 상기 텅스텐은 상기 지지체 중량을 기준으로 1 내지 20 중량%의 양으로 담지된 것을 특징으로 하는 방법.According to paragraph 1,
A method characterized in that the platinum is supported in an amount of 0.1 to 5% by weight based on the weight of the support, and the tungsten is supported in an amount of 1 to 20% by weight based on the weight of the support.
(a) 상기 바이오매스로부터 열분해유를 얻는 단계;
(b) 상기 열분해유 중의 함산소 화합물을 탄소-탄소 결합 형성 반응에 의해 탄소수를 증가시켜 중쇄 함산소 화합물을 얻는 단계; 및
(c) 제1항 내지 제7항 중 어느 한 항에 기재된 방법에 의해 상기 중쇄 함산소 화합물로부터 탄소수 5 내지 12개의 탈산소 탄화수소 화합물을 얻는 단계를 포함하는, 방법.As a method for producing bionaphtha from biomass,
(a) obtaining pyrolysis oil from the biomass;
(b) obtaining a medium-chain oxygenated compound by increasing the carbon number of the oxygenated compound in the pyrolysis oil through a carbon-carbon bond formation reaction; and
(c) obtaining a deoxygenated hydrocarbon compound having 5 to 12 carbon atoms from the medium chain oxygenated compound by the method according to any one of claims 1 to 7.
상기 (a) 단계는 상기 바이오매스를 열분해하여 유상 열분해유 및 수상 열분해유를 얻는 단계이고, 상기 (a) 단계에서 얻어진 유상 열분해유와 수상 열분해유를 분리하는 단계를 추가로 포함하여 상기 (b) 단계의 열분해유로서 사용하는 것을 특징으로 하는 방법.According to clause 8,
The step (a) is a step of pyrolyzing the biomass to obtain oily pyrolysis oil and aqueous pyrolysis oil, and further includes the step of separating the oily pyrolysis oil and the aqueous pyrolysis oil obtained in step (a). ) A method characterized in that it is used as pyrolysis oil in the step.
상기 (b) 단계에서 상기 탄소-탄소 결합 형성 반응은 알돌 축합 반응, 케톤화 반응, 또는 알킬화 반응인 것을 특징으로 하는 방법.According to clause 8,
In step (b), the carbon-carbon bond forming reaction is an aldol condensation reaction, a ketonization reaction, or an alkylation reaction.
상기 바이오매스는 목질계 또는 초본계 바이오매스인 것을 특징으로 하는 방법.According to clause 8,
A method characterized in that the biomass is lignocellulosic or herbaceous biomass.
상기 금속 산화물 지지체는 티타늄 산화물 지지체이고, 상기 백금(Pt) 상기 지지체 중량을 기준으로 0.1 내지 5 중량%로 담지되고, 상기 백금(Pt) 담지 후 상기 텅스텐은 상기 지지체 중량을 기준으로 1 내지 20 중량%의 양으로 담지된 것을 특징으로 하는 촉매.According to clause 12,
The metal oxide support is a titanium oxide support, and the platinum (Pt) is supported at 0.1 to 5% by weight based on the weight of the support, and after the platinum (Pt) is supported, the tungsten is 1 to 20% by weight based on the weight of the support. A catalyst characterized in that it is supported in an amount of %.
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