WO2011129640A9 - 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물 및 이를 이용한 푸르푸랄 유도체의 제조방법 - Google Patents
목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물 및 이를 이용한 푸르푸랄 유도체의 제조방법 Download PDFInfo
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- 0 C*(C)[C@](C(CO)O[C@@](*(C1C2O)C1*(CO)OC2OC(C)(C)*)C1O)C1O Chemical compound C*(C)[C@](C(CO)O[C@@](*(C1C2O)C1*(CO)OC2OC(C)(C)*)C1O)C1O 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J23/54—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
- B01J23/6522—Chromium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
Definitions
- the present invention relates to a metal catalyst composition for producing a furfural derivative from woody biomass raw materials and a method for producing a furfural derivative using the same, and more specifically, unlike the conventional multi-step process, various metal catalysts
- furfural derivatives can be produced from wood-based biomass raw materials that can be converted to furfural derivatives in a single process without a separate monoglycosylation process, which can significantly reduce the process cost.
- It relates to a metal catalyst composition and a method for producing a furfural derivative using the same.
- biomass-derived fuels and raw materials currently being industrially produced are mainly sourced from crop-based biomass resources used for food, such as sugar-based (sugar cane, sugar beets, etc.) and starch-based (corn, potatoes, sweet potatoes, etc.).
- sugar-based biomass resources used for food such as sugar-based (sugar cane, sugar beets, etc.) and starch-based (corn, potatoes, sweet potatoes, etc.).
- cellulose and hemicellulose are carbohydrates that can be extracted from wood-based biomass, such as plants that grow spontaneously in uncultivated land with vigorous growth, remaining residues after cultivation, and waste wood resources.
- wood-based biomass such as plants that grow spontaneously in uncultivated land with vigorous growth, remaining residues after cultivation, and waste wood resources.
- sucrose and starch which are carbohydrates from starch.
- cellulose and hemicellulose which are carbohydrate polymers that can be extracted from wood-based biomass, are produced a huge amount through photosynthesis every year (1,270 billion tons / year), and currently only about 3 to 4% of them are used in the United States.
- advanced countries such as Europe, Japan, researches are being actively conducted to utilize cellulose and hemicellulose derived from woody biomass resources.
- Carbohydrate polymers obtained from wood-based biomass are polysaccharides in which hexasaccharides or pentoses are linearly or two-dimensionally linked.
- Glucose or fructose and pentose which are hexasaccharides, are generally obtained through the saccharification by hydrolysis. After conversion to in xylose, it is subjected to a separation and purification process and applied to the next step, biofermentation or catalytic chemical process.
- a general preparation method for obtaining a desired final compound from a woody biomass source includes (a) a pretreatment step for extracting a carbohydrate polymer of polysaccharides from a biomass source, (b) glucose of hexasaccharides from the extracted carbohydrate polymer Or a monoglycosylation step for obtaining fructose and pentose xylose, (c) separation and purification of the prepared monosaccharide compound, and (d) a multi-step process of biofermentation or catalytic chemistry to obtain the final compound. And, there is a problem that the production cost increases, the yield is reduced in the course of the multi-step process.
- furfural derivative compounds derived from such biomass have received a lot of attention, of which the hexasaccharide derived 5-hydroxymethyl-2-furfural and 2-pentane derived 2- Furfural is a representative core platform material, and it is widely used as eco-friendly fine chemicals such as monomers, adhesives, adhesives and coatings of next-generation biofuels or bio-based plastics through various conversion reactions. It is actively running.
- a representative technique for preparing HMF from carbohydrates derived from biomass is a method obtained by dehydration reaction under acid catalyst conditions using fructose derived from corn syrup as a starting material. This is because, unlike the hexagonal saccharide compound, it is easy to obtain a furan structure without a separate isomerization reaction.
- the Dumesic group of the University of Wisconsin Madison reported a technique for producing HMF through acid catalysis conversion in multiple solvents with fructose as a starting material [ Science , 2006 , 312 , 1933-1937.], Which is 30 wt% HMF can be obtained even at the above high concentrations, thereby achieving excellent process efficiency.
- fructose used as a starting material has a disadvantage of limited biomass source, and mainly exists only in agricultural crops, and high energy distillation process is required to remove the high boiling point of solvents that exhibit optimal performance in the above technique. Therefore, new separation process technology is required.
- Glucose a monomer of cellulose derived from wood-based biomass and more commonly present in nature than fructose, can be easily supplied, but as a hexagonal ring structure, it is a compound of furan structure on an existing acid catalyst. It was known to not switch.
- 2-furfural can be used as a fuel material itself
- furfuryl alchol and furfuryl acid which are derivatives of oxidation / reduction reactions, are used as raw materials for polymer materials.
- Hemicellulose contained mainly in woody biomass as a compound has been obtained through dehydration under acidic conditions.
- the dehydration reaction process using strong acid such as sulfuric acid has a problem in that the working conditions are poor and a large amount of waste acid and waste water are generated.
- the present invention is to solve the above problems, by mixing a plurality of metal catalysts in the optimum ratio of the production process of furfural derivatives, which had conventionally had to go through a multi-step process, such as pretreatment, mono-glycosylation process, thereby one reaction Metal catalyst composition for preparing furfural derivatives from woody biomass raw materials that can directly convert furfural derivatives from cellulose or woody biomass raw materials with a simple reaction process in the apparatus and preparation of furfural derivatives using the same It is an object to provide a method.
- An object of the present invention is to provide a metal catalyst composition for producing a furfural derivative from a mass raw material and a method for producing a furfural derivative using the same.
- An object of the present invention is to provide a catalyst composition and a method for producing a furfural derivative using the same.
- An object of the present invention is to provide a composition and a method for producing a furfural derivative using the same.
- Metal catalyst composition for producing a furfural derivative from the wood-based biomass raw material according to the present invention for achieving the above object is characterized in that it comprises ruthenium and chromium.
- the chromium is characterized in that it comprises 300 to 500 parts by weight, further comprising a solvent, the solvent is characterized in that at least one of an ionic solvent or an aprotic polar solvent. do.
- the ionic solvent may also be in ethylmethylimidazolium chloride ([EMIM] Cl), ethylmethylimidazolium bromine ([EMIM] Br) or ethylmethylimidazolium iodine ([EMIM] I).
- the aprotic polar solvent is dimethylacetamide dimethyl sulfoxide, dimethylformamide, hexamethylphosphorotriamide, N-methylpyrrolidone, tetrahydrofuran ( THF) or ⁇ -butyrolact.
- a method for producing a furfural derivative from the woody biomass raw material may include a pretreatment step of extracting cellulose from woody biomass; And cellulose and MXn or MXn.H 2 O (M is a metal element, X is selected from a functional group consisting of a halogen element or a triflate, nonaplate, mesylate, tosylate or diazonium, n is 1 to 3). It is characterized in that it comprises a; reaction step of producing a 5-hydroxymethylfurfural by catalytic conversion reaction of the metal catalyst represented in the).
- the metal catalyst may include at least one of a metal catalyst of which the metal element (M) is Cr (II) and a metal catalyst of which the metal element (M) is Ru (III).
- the equivalent ratio of the metal catalyst containing II) and the metal catalyst containing the metal element Ru (III) is 1: 1 to 5: 1.
- the ratio of the cellulose to the solvent is characterized in that 50 to 500g / L, the equivalent weight of the metal catalyst is characterized in that 0.5 to 20 mol%.
- the reaction temperature is 100 to 150 °C
- the reaction time is characterized in that 1 to 5 hours.
- a method for producing a furfural derivative from a woody biomass raw material includes a mixing step of mixing a metal catalyst and a solvent to prepare a mixture; A heating step of heating the mixture; An addition step of preparing a reactant by adding a woody biomass raw material to the mixture; And a reaction step of heating and reacting the reactants.
- the metal catalyst is made of MXn or MXn.H 2 O, wherein M is a metal element, X is a functional group consisting of a halogen element, triflate, nona plate, mesylate, tosylate or diazonium Any one of the above, characterized in that n is 1 to 3.
- the metal element is manganese (Mn), nickel (Ni), iron (Fe), chromium (Cr), copper (Cu), cobalt (Co), ruthenium (Ru), tin (Sn) , Zinc (Zn), aluminum (Al), cerium (Ce), lanthanum (La), neodymium (Nd), scandium (Sc), ytterbium (Yb) or indium (In).
- the metal catalyst is characterized in that made of ruthenium and chromium, with respect to 100 parts by weight of the ruthenium, the chromium is characterized in that it comprises 300 to 500 parts by weight.
- the solvent is at least one of an ionic solvent or an aprotic polar solvent
- the ionic solvent is ethyl methyl imidazolium chloride ([EMIM] Cl), ethyl At least one of methylimidazolium bromine ([EMIM] Br) or ethylmethylimidazolium iodine ([EMIM] I), wherein the aprotic polar solvent is dimethylacetamide dimethyl sulfoxide. ), Dimethylformamide, hexamethylphosphorotriamide, N-methylpyrrolidone, tetrahydrofuran (THF) or ⁇ -butyrolact.
- the heating temperature is characterized in that 60 to 100 °C
- the wood-based biomass raw material is characterized in that it comprises at least one of cellulose or hemicellulose.
- the reactant based on 100 mol% of the wood-based biomass raw material, characterized in that the metal catalyst comprises 1 to 20 mol%
- the wood-based bio The mass raw material is characterized in that it comprises 50 to 500g with respect to 1L of the solvent, in the reaction step, the reaction temperature is 100 to 200 °C, the reaction time is characterized in that 1 to 4 hours.
- the crop-based biomass may be utilized by utilizing cellulose derived from the wood-based biomass.
- the process of producing furfural derivatives which had previously been subjected to a multi-step process such as pretreatment and monoglycosylation, is mixed with various metal catalysts at an optimum ratio, so that the wood-based system is simple in a single reactor.
- a multi-step process such as pretreatment and monoglycosylation
- furfural derivatives can be directly prepared from the wood-based biomass raw materials in a simple process, the process cost can be significantly reduced and the yield is high.
- FIG. 1 is a flow chart sequentially showing a first embodiment of a method for producing a furfural derivative according to the present invention
- Figure 2 is a flow chart sequentially showing a second embodiment of a method for producing a furfural derivative according to the present invention
- Figure 3 is a graph showing the high performance liquid chromatography (HPLC) of the products produced using the method for producing a furfural derivative of the present invention
- 5 is a graph comparing the yield of 2-furfural, a product produced using the method for preparing furfural derivative of the present invention, according to wood-based biomass raw materials
- the first embodiment of the metal catalyst composition for producing a furfural derivative from the wood-based biomass raw material comprises MXn or MXn.H 2 O, wherein M is a metal element, X is a halogen Element, triflate, nona plate, mesylate, tosylate or any one of the functional group consisting of diazonium, n is characterized in that 1 to 3.
- the functional group may include a halogen element such as Cl, Br, I, or the like, and may correspond to a functional group such as triflate, nonaplate, mesylate, ethylsulfonate, benzenesulfonate, tosylate, triisopropylbenzenesulfonate, Formate, acetate, trifluoroacetate, nitrobenzoate, halogenated arylcarboxylates, in particular fluorinated benzoate, methyl carbonate, ethyl carbonate, benzyl carbonate, t-butylcarbonate, dimethyl phospho Preference is given to using any one of nitrate, diethyl phosphonate, diphenyl phosphonate or diazonium, more preferably a functional group consisting of a halogen element, a triflate, nonaplate, mesylate, tosylate or diazonium It is most effective to use either.
- the metal element is manganese (Mn), nickel (Ni), iron (Fe), chromium (Cr), copper (Cu), cobalt (Co), ruthenium (Ru), tin (Sn), zinc (Zn) It is effective to use any one of aluminum (Al), cerium (Ce), lanthanum (La), neodymium (Nd), scandium (Sc), ytterbium (Yb) or indium (In).
- the metal catalyst composition of the present invention as described above was configured to perform the reaction that can convert the wood-based biomass raw material directly to the furfural derivative most efficiently through several experiments.
- the MXn or MXn.H 2 O preferably contains 1 to 20 mol%, more preferably 5 to 10 mol% based on 100 mol% of the wood-based biomass raw material. to be. If it is less than 1 mol%, the catalyst is difficult to exhibit the function, the conversion is almost impossible, there is a problem that the conversion rate is significantly lower, even if the conversion exceeds 20 mol%, not only economic efficiency is lowered, but rather yield there is a problem.
- a second embodiment of the metal catalyst composition for producing a furfural derivative from the wood-based biomass raw material is characterized in that it comprises ruthenium and chromium, more preferably ruthenium chloride (RuCl 3 ) And chromium chloride (CrCl 2 ).
- RuCl 3 ruthenium chloride
- CrCl 2 chromium chloride
- ruthenium serves as a Lewis acid for the hydrolysis reaction and dehydration reaction
- chromium is effective for the isomerization reaction, by mixing them, there is an advantage that can cause a number of reactions at the same time.
- the chromium preferably contains 300 to 500 parts by weight, and more preferably 350 to 450 parts by weight based on 100 parts by weight of the ruthenium of the ruthenium and chromium. If less than 300 parts by weight or more than 500 parts by weight is out of the optimum composition ratio, there is a problem that the yield of the final product is significantly reduced.
- the first and second embodiments further include a solvent, and the solvent is effectively at least one of an ionic solvent or an aprotic polar solvent. This helps in the conversion reaction.
- the ionic solvent is at least one of ethylmethylimidazolium chloride ([EMIM] Cl), ethylmethylimidazolium bromine ([EMIM] Br) or ethylmethylimidazolium iodine ([EMIM] I).
- the aprotic polar solvent is dimethylacetamide, dimethyl sulfoxide, dimethylformamide, dimethylmethylphosphorotriamide, N-methylpyrrolidone, or tetrahydrofuran. It is effective to be at least one of (THF) or ⁇ -butyrolact.
- the metal catalyst composition for producing a furfural derivative from the wood-based biomass raw material of the present invention is optimized for the second embodiment of the method for producing the furfural derivative below, and is directly converted from the wood-based biomass raw material to the fururfural derivative. It is possible to let. Therefore, although the technical characteristics are common to the metal catalyst used in the first embodiment of the method for producing a furfural derivative, the composition ratio may be slightly different.
- the pretreatment step (S10) is a step of extracting cellulose used as a starting material in the reaction step (S11) described later from the wood-based biomass called Lignocellulosic biomass.
- the wood-based biomass is spontaneously grown in nature, wood that does not share crops and arable land, waste wood in the form of urban waste, or forest by-products scattered throughout the forest, and various plants having excellent viability even in non-cultivated land. Groups (switchgrass, etc.), residues remaining after planting crops (straw straw, corn stalks, etc.), and waste wood resources (waste wood, waste paper, etc.).
- any method used in the art may be used without limitation.
- the amount of cellulose that can be obtained from the wood-based biomass resources through the pretreatment process varies depending on the plant, but on average is about 33%. Generally, about 50% wood and about 90% cotton. It is known to reach.
- the remaining major components consist of hemicellulose, a natural polymer of pentose, and lignin, an aromatic phenolic family.
- the lignin is dissolved and removed by dissolving in basic conditions, hemicellulose relatively weak in acid compared to cellulose can be separated by treating the weak acid.
- the cellulose extracted in this way is a natural polymer including D-glucose as a monomer, and forms a glucose bond at the C1 and C4 positions of glucose as shown in Chemical Formula 1 below, and ⁇ (1 ⁇ 4). It is connected by a bond.
- the reaction step (S11) is a step of preparing a furfural derivative by catalytic conversion of the cellulose and the metal catalyst in a solvent.
- the desired furfural derivative may be obtained in a single process without converting the starting cellulose into monosaccharides by hydrolysis.
- Scheme 1 as a preferred embodiment of the present invention, a process of obtaining 5-hydroxymethyl-2-furfural by a single reaction using cellulose is briefly shown.
- the inventors of the present invention use various metal catalysts to simultaneously implement (a) hydrolysis reaction (monosaccharide), (b) isomerization reaction and (c) dehydration reaction in one reactor as described above.
- various reaction conditions such as the composition ratio, temperature, time, solvent, etc. of metal catalysts, various metal catalyst combinations, and various metal catalyst combinations are changed to An attempt was made to find the metal catalyst conversion reaction conditions.
- the metal catalyst used in the reaction step (S11) of the present invention as a Lewis acid to promote the hydrolysis reaction and dehydration reaction, isomeric reaction for converting the hexahex ring structure of cellulose into a pentagonal ring structure It played a role of mediating.
- the metal catalyst used in the embodiment of the present invention may be used without particular limitation as long as it is a substance represented by MXn or MXn ⁇ H 2 O.
- M is a metal element
- X is a halogen element or a functional group containing or corresponding to a halogen element
- n is 1-3.
- halogen element Cl, Br, I and the like trifunctional, nona plate, mesylate, ethylsulfonate, benzenesulfonate, tosylate, triisopropylbenzenesulfonate, containing or equivalent functional groups of halogen, Formate, acetate, trifluoroacetate, nitrobenzoate, halogenated arylcarboxylates, in particular fluorinated benzoate, methyl carbonate, ethyl carbonate, benzyl carbonate, t-butylcarbonate, dimethyl phospho Nitrate, diethyl phosphonate, diphenyl phosphonate or diazonium.
- the element that can be preferably applied as the metal element (M) is selected from the group consisting of Mn, Ni, Fe, Cr, Cu, Co, Ru, Zn, Al, Ce, La, Nd, Sc, Yb,
- a metal catalyst containing Cr (II) as the metal element (M) for example, CrCl 2 , CrCl 2 H 2 O, CrBr 2 , Chromium triplates, chromium acetate and / or metal catalysts containing Ru (III) as metal element (M), for example RuCl 3 , RuCl 3 H 2 O, RuBr 3 ,
- RuCl 3 RuCl 3 H 2 O, RuBr 3
- a combination of ruthenium tosylate and the like exhibited particularly desirable properties in terms of yield.
- the solvent used in the reaction step (S11) of the present invention is ethyl methyl imidazolium chloride ([EMIM] Cl), ethyl methyl imidazolium bromine ([EMIM] Br), ethyl methyl imidazolium iodine Ionic solvents such as ([EMIM] I) or DMA (dimethylacetamide) DMSO (dimethyl sulfoxide), DMF (Dimethylformamide), hexamethylphosphorotriamide, N-methylpyrrolidone, tetrahydrofuran (THF) and ⁇ - It is preferable that it is an aprotic polar solvent, such as butyrolactone. Especially preferably, an ionic solvent is used as a solvent.
- a preferable ratio of the solvent and the cellulose added thereto is 50 to 500 g / L, more preferably 100 to 300 g / L (wt / V), and shows excellent yield when applied in the above ratio.
- the total equivalent weight of the metal catalyst for maximizing the yield is 0.5 to 20 mol%, more preferably 5 to 10 mol%.
- Ru (III) is preferably used as the metal catalyst for the Lewis acid role for the hydrolysis and dehydration reaction
- Cr (II) as the metal catalyst for the isomerization reaction.
- composition ratio between the various metal catalysts also affects the yield of the final product, so it is important to obtain an optimum composition ratio.
- a desirable composition ratio between the Cr (II) metal catalyst and the Ru (III) metal catalyst Cr (II): Ru (III), equivalent ratio, molar ratio was found to be 1: 1 to 5: 1, particularly preferably 4: 1.
- the preferred reaction temperature of the reaction step (S11) is 100 °C or more, more preferably 100 to 150 °C, the reaction time is 1 to 5 hours.
- the mixing step (S20) is a step of preparing a mixture by mixing the metal catalyst and the solvent. This is a process of effectively mixing the metal catalyst and the solvent to facilitate the reaction.
- the metal catalyst is made of MXn or MXn ⁇ H 2 O, wherein M is a metal element, X is a halogen element, triflate, nona plate, mesylate, tosylate or diazonium Any one of the functional groups consisting of, n is characterized in that 1 to 3.
- the metal element is manganese (Mn), nickel (Ni), iron (Fe), chromium (Cr), copper (Cu), cobalt (Co), ruthenium (Ru), tin (Sn), zinc (Zn) , Aluminum (Al), cerium (Ce), lanthanum (La), neodymium (Nd), scandium (Sc), ytterbium (Yb) or indium (In).
- the metal catalyst is characterized in that consisting of ruthenium (RuCl 2 ) and chromium chloride (CrCl 2 ), with respect to 100 parts by weight of the ruthenium chloride (RuCl 2 ), the chromium chloride (CrCl 2 ) is 300 to 500 It is preferred to include parts by weight.
- the solvent is preferably at least one of an ionic solvent or an aprotic polar solvent
- the ionic solvent is ethyl methyl imidazolium chloride ([EMIM] Cl) , Ethylmethylimidazolium bromine ([EMIM] Br) or ethylmethylimidazolium iodine ([EMIM] I)
- the aprotic polar solvent is dimethylacetamide dimethyl sulfoxide ( dimethyl sulfoxide), dimethylformamide, hexamethylphosphorotriamide, N-methylpyrrolidone, tetrahydrofuran (THF) or ⁇ -butyrolact.
- the heating step S21 is a step of heating the mixture. This is a process of mixing the solvent and the metal catalyst effectively to facilitate the reaction.
- the heating temperature is preferably 60 to 100 °C, more preferably 80 to 90 °C effective. If the temperature is less than 60 ° C., the metal catalyst is difficult to effectively disperse in the solvent, and if it exceeds 100 ° C., there is a problem of low economic efficiency.
- the heating and stirring time is preferably 20 minutes to 50 minutes, more preferably 30 minutes is effective. If it is less than 20 minutes, the metal catalyst is not sufficiently dispersed in the solvent, and if it exceeds 50 minutes, there is a problem in that the economy is inferior.
- the addition step (S22) is a step of preparing a reactant by adding the wood-based biomass raw material to the mixture. This is a reaction preparation process for preparing a final reactant for the reaction by inputting the biomass raw material.
- the wood-based biomass raw material may be any wood-based biomass, it is preferable to include at least one of cellulose or hemicellulose in the present invention in order to achieve the optimum effect.
- Cellulose the main component of the wood-based biomass used in the present invention, is a linear natural polymer containing D-glucose as a monomer, and hemicellulose includes D-xylose as the main monomer. It is a natural polymer.
- cellulose forms glycosidic bonds at C1 and C4 positions of D-glucose and is connected by ß (1 ⁇ 4) linkage, and hemicellulose is bonded at C1 and C4 positions of D-xylose. consist of.
- ß (1 ⁇ 4) linkage hemicellulose is bonded at C1 and C4 positions of D-xylose. consist of.
- hemocellulose unlike cellulose, which is a linear polymer, hemocellulose has a two-dimensional chemical structure with some branches.
- wood-based biomass is most effective to contain 20 to 70% of carbohydrate polymers, that is, at least one of cellulose or hemicellulose.
- the metal catalyst preferably comprises 1 to 20 mol%, more preferably 5 to 10 mol Including% is effective. The description is as described above.
- the wood-based biomass raw material it is preferable to contain 50 to 500g, more preferably 100 to 300g with respect to 1L of the solvent. If the amount is less than 50g or more than 500g, there is a problem that the yield is significantly lowered. In the present invention, it is possible to maximize the yield to include the content ratio of the above range.
- the temperature in the addition step (S22) is reduced in the heating step (S21), it is preferable to maintain at 15 to 30 °C, more preferably it is effective to maintain at 20 to 25 °C. If the temperature is less than 15 °C, there is a problem that the mixture and the wood-based biomass raw material may be damaged at a low temperature, and if it exceeds 30 °C, some reaction may occur as the wood-based biomass raw material is added, Not only does the quality of the furfural derivatives deteriorate, but also the yields deteriorate.
- reaction step (S23) is a step of reacting by heating the reactant. This is a process for producing a furfural derivative finally through a conversion reaction.
- the reaction temperature is preferably 100 to 200 °C, more preferably 120 to 150 °C effective. If the temperature is less than 100 ° C., there is a problem that a sufficient reaction does not occur. If the temperature exceeds 200 ° C., not only excessive energy is consumed, but also the reaction rate is excessively accelerated, and thus the quality of the furfural derivative, which is a product, is degraded. There is also the problem of falling.
- the reaction time is preferably 1 to 4 hours, more preferably 2 to 3 hours is effective. If less than 1 hour does not occur a sufficient conversion reaction, if more than 4 hours not only economic efficiency is lowered, there is a problem that further reaction of the product and by-products occurs, rather the quality of the product.
- reaction step (S23) it is preferable to react by stirring at 500 to 1000 RPM using a stirrer. By stirring, each substance can react evenly, resulting in the effect of improving reactivity and yield.
- the stirring speed of the stirrer is 500 to 1000 RPM, which can bring about the reactivity and the yield.
- the conversion reaction of the present invention is (a) a dissolution process for extracting a carbohydrate polymer of polysaccharides from a biomass source, (b) a hydrolysis process for obtaining a monosaccharide glucose or xylose from cellulose or hemicellulose as a polysaccharide, (c) isomerization process to convert glucose of hexagonal structure into pentagonal structure, and (d) dehydration process to obtain furan structure can be simultaneously implemented in one reactor.
- the various metal catalysts of the present invention used in the conversion reaction play a role of mediating the isomer reaction of converting the hexagonal ring structure into the pentagonal structure together with the role of Lewis acid to promote the hydrolysis reaction and the dehydration reaction. Done.
- Starting materials are wood-based biomass containing cellulose and hemicellulose, which are carbohydrate polymers, and various plant groups (such as silver grass and reeds) with excellent self-sustainability even in non-cultivated lands, and residues remaining after planting crops (straw straw, barley straw). , Straw, corn rapeseed, rapeseed, etc.) and waste wood resources (waste wood, waste paper, coffee residues, etc.).
- a metal catalyst (10 mol% of the substrate), an ionic liquid as a solvent, and [EMIM] Cl (500 mg) were added to a 6 mL vial, and the mixed solution was heated to 60 ° C. and stirred for 40 minutes. After the mixture was cooled to room temperature, cellulose (50 mg) was added to the mixture, reheated to 90 to 120 ° C., and stirred at 700 rpm for 2 to 4 hours. After completion of the reaction, each vial was allowed to warm to room temperature, diluted with HPLC grade distilled water (5 mL) and stirred for 40 minutes. Each sample was diluted 100 times further and then subjected to HPLC analysis to determine the yield. Each sample was separated through a C18 reversed phase column on HPLC (Varian Pro Star 310), and the peak area was measured using a UV detector (280 nm), and the yield was inverted through a previously obtained HMF response factor.
- the reaction temperature was 120 ° C., and the reaction time was increased to 4 hours to measure the yield of HMF.
- the yield was found to increase from 19.1% to 27.1%, but in other metal catalysts, the yield was found to be equivalent or rather decreased. It is believed that this is due to further dehydration of the produced HMF resulting in the production of levulinic acid.
- the effect of reaction time on HMF yield is summarized in ⁇ Table 2>.
- HMF can be produced in high yield directly from cellulose extracted from wood-based biomass through a metal catalyst conversion reaction.
- a metal catalyst of Cr (II): Ru (III) 4: 1 composition in a [EMIM] Cl ionic solvent, and the reaction for 2 hours at a reaction temperature of 120 °C, HMF in a yield of 59.1% could be manufactured.
- a metal catalyst RuCl 3 and CrCl 2 (equivalent ratio 1: 4, equivalent weight: 10 mol% of the substrate), an ionic liquid as a solvent, and [EMIM] Cl (500 mg) were added. It was heated to ⁇ ⁇ and stirred for 30 minutes. After the mixture was cooled to room temperature, the wood-based biomass raw materials (50 mg) shown in Table I were added to the mixture, and then reheated to 120 ° C. and stirred at 700 rpm for 2 hours. After completion of the reaction, each reactor was cooled to room temperature, diluted with HPLC grade distilled water, and then HPLC analysis was performed to determine the yield.
- HPLC high performance liquid chromatography
- the present invention is a wood-based biomass raw material that can be converted to a furfural derivative in a single process by using a variety of metal catalysts under optimum reaction conditions, without a separate monoglycosylation process, etc.
- the present invention relates to a metal catalyst composition for producing a furfural derivative from a substance and to a method for producing a furfural derivative using the same, which can be used industrially.
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Abstract
Description
순번 | 금속촉매 | 용매 | 온도 (℃) | 시간 (h) | 수율 (%) |
1 | CrCl2 | [EMIM]Cl | 90 | 2 | 7.4 |
2 | CrCl2 | [EMIM]Cl | 120 | 2 | 19.1 |
3 | MnCl2 | [EMIM]Cl | 90 | 2 | 6.6 |
4 | MnCl2 | [EMIM]Cl | 120 | 2 | 9.1 |
5 | FeCl2 | [EMIM]Cl | 90 | 2 | 9.0 |
6 | FeCl2 | [EMIM]Cl | 120 | 2 | 12.6 |
7 | FeCl3 | [EMIM]Cl | 90 | 2 | 12.8 |
8 | FeCl3 | [EMIM]Cl | 120 | 2 | 10.8 |
9 | CoCl26H2O | [EMIM]Cl | 90 | 2 | 5.8 |
10 | CoCl26H2O | [EMIM]Cl | 120 | 2 | 9.8 |
11 | NiCl2 | [EMIM]Cl | 90 | 2 | 5.4 |
12 | NiCl2 | [EMIM]Cl | 120 | 2 | 6.5 |
13 | CuCl2 | [EMIM]Cl | 90 | 2 | 13.1 |
14 | CuCl2 | [EMIM]Cl | 120 | 2 | 12.8 |
15 | ZnCl2 | [EMIM]Cl | 90 | 2 | 6.7 |
16 | ZnCl2 | [EMIM]Cl | 120 | 2 | 14.8 |
순번 | 금속촉매 | 용매 | 온도 (℃) | 시간 (h) | 수율 (%) |
1 | CrCl2 | [EMIM]Cl | 120 | 2 | 19.1 |
2 | CrCl2 | [EMIM]Cl | 120 | 4 | 27.1 |
3 | MnCl2 | [EMIM]Cl | 120 | 2 | 9.1 |
4 | MnCl2 | [EMIM]Cl | 120 | 4 | 10.9 |
5 | FeCl2 | [EMIM]Cl | 120 | 2 | 12.6 |
6 | FeCl2 | [EMIM]Cl | 120 | 4 | 9.2 |
7 | FeCl3 | [EMIM]Cl | 120 | 2 | 10.8 |
8 | FeCl3 | [EMIM]Cl | 120 | 4 | 6.8 |
9 | CoCl26H2O | [EMIM]Cl | 120 | 2 | 9.8 |
10 | CoCl26H2O | [EMIM]Cl | 120 | 4 | 9.6 |
11 | NiCl2 | [EMIM]Cl | 120 | 2 | 6.5 |
12 | NiCl2 | [EMIM]Cl | 120 | 4 | 6.1 |
13 | CuCl2 | [EMIM]Cl | 120 | 2 | 12.8 |
14 | CuCl2 | [EMIM]Cl | 120 | 4 | 9.5 |
15 | ZnCl2 | [EMIM]Cl | 120 | 2 | 14.8 |
16 | ZnCl2 | [EMIM]Cl | 120 | 4 | 6.0 |
순번 | 금속촉매 1 | 금속촉매 2 | 용매 | 온도 (℃) | 시간 (h) | 수율 (%) |
1 | CrCl2 | FeCl2 | [EMIM]Cl | 120 | 2 | 48.0 |
2 | CrCl2 | FeCl2 | [EMIM]Cl | 120 | 4 | 40.2 |
3 | CrCl2 | FeCl3 | [EMIM]Cl | 120 | 2 | 43.3 |
4 | CrCl2 | FeCl3 | [EMIM]Cl | 120 | 4 | 32.0 |
5 | CrCl2 | CuCl2 | [EMIM]Cl | 120 | 2 | 37.1 |
6 | CrCl2 | CuCl2 | [EMIM]Cl | 120 | 4 | 39.8 |
7 | CrCl2 | RuCl3 | [EMIM]Cl | 120 | 2 | 59.1 |
8 | CrCl2 | RuCl3 | [EMIM]Cl | 120 | 4 | 35.0 |
순번 | 금속촉매 1 | 금속촉매 2 | 조성비 | 용매 | 온도 (℃) | 시간 (h) | 수율 (%) |
1 | CrCl2 | RuCl3 | 10:1 | [EMIM]Cl | 120 | 2 | 37.6 |
2 | CrCl2 | RuCl3 | 6:1 | [EMIM]Cl | 120 | 2 | 51.3 |
3 | CrCl2 | RuCl3 | 5:1 | [EMIM]Cl | 120 | 2 | 53.1 |
4 | CrCl2 | RuCl3 | 4:1 | [EMIM]Cl | 120 | 2 | 59.6 |
5 | CrCl2 | RuCl3 | 3:1 | [EMIM]Cl | 120 | 2 | 54.6 |
6 | CrCl2 | RuCl3 | 2:1 | [EMIM]Cl | 120 | 2 | 53.6 |
7 | CrCl2 | RuCl3 | 1:1 | [EMIM]Cl | 120 | 2 | 54.2 |
8 | CrCl2 | RuCl3 | 1:2 | [EMIM]Cl | 120 | 2 | 34.1 |
9 | CrCl2 | RuCl3 | 1:3 | [EMIM]Cl | 120 | 2 | 31.2 |
10 | CrCl2 | RuCl3 | 1:4 | [EMIM]Cl | 120 | 2 | 28.5 |
순번 | 금속촉매 1 | 금속촉매 2 | 금속촉매 3 | 용매 | 온도 (℃) | 시간 (h) | 수율 (%) |
1 | CrCl2 | FeCl2 | MnCl2 | [EMIM]Cl | 120 | 2 | 38.0 |
2 | CrCl2 | FeCl2 | CuCl2 | [EMIM]Cl | 120 | 2 | 31.1 |
3 | CrCl2 | FeCl2 | ZnCl2 | [EMIM]Cl | 120 | 2 | 37.3 |
4 | CrCl2 | CuCl2 | MnCl2 | [EMIM]Cl | 120 | 2 | 31.5 |
5 | CrCl2 | CuCl2 | ZnCl2 | [EMIM]Cl | 120 | 2 | 29.4 |
6 | CrCl2 | RuCl3 | FeCl2 | [EMIM]Cl | 120 | 2 | 32.7 |
7 | CrCl2 | RuCl3 | MnCl2 | [EMIM]Cl | 120 | 2 | 33.3 |
8 | CrCl2 | RuCl3 | CuCl2 | [EMIM]Cl | 120 | 2 | 22.7 |
9 | CrCl2 | RuCl3 | ZnCl2 | [EMIM]Cl | 120 | 2 | 32.8 |
목질계 바이오매스 공급원 | 영문명 | 구성성분 | |||
셀룰로오스 | 헤미셀룰로오스 | 리그닌 | 재 | ||
볏짚 | rice straw | 35.0 | 25.0 | 12.0 | - |
보리짚 | barley straw | 37.0 | 22.2 | - | - |
밀짚 | wheat straw | 38.2 | 21.2 | 23.4 | - |
트리티케일 | triticale | 35.8 | 24.3 | 21.9 | 7.4 |
유채대 | rape stem | 31.2 | 17.2 | 20.5 | 6.5 |
억새 | grass | 39.7 | 26.4 | 24.3 | 2.4 |
갈대 | reed | 40.0 | 22.0 | 26.1 | 5.2 |
파티클보드 | MDF board | 33.2 | 12.1 | 32.2 | 1.1 |
폐지 | waste paper | 63.9 | 10.4 | 1.5 | 11.5 |
커피빈 잔유물 | coffee bean residue | 5.9 | 37.4 | 41.6 | 0.4 |
Claims (24)
- 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 직접 제조하기 위한 금속촉매조성물에 있어서,MXn 또는 MXn·H2O를 포함하여 이루어지며,상기 M은 금속원소이고, 상기 X는 할로겐 원소, 트리플레이트, 노나플레이트, 메실레이트, 토실레이트 또는 디아조늄으로 이루어진 작용기 중 어느 하나이며, 상기 n은 1 내지 3인 것을 특징으로 하는 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물
- 제 1항에 있어서,상기 목질계 바이오매스 원료물질 100몰%에 대하여, 상기 MXn 또는 MXn·H2O는 1 내지 20몰%를 포함하는 것을 특징으로 하는 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물
- 제 1항에 있어서,상기 금속원소는 망간(Mn), 니켈(Ni), 철(Fe), 크롬(Cr), 구리(Cu), 코발트(Co), 루테늄(Ru), 주석(Sn), 아연(Zn), 알루미늄(Al), 세륨(Ce), 란탄(La), 네오디뮴(Nd), 스칸듐(Sc), 이테르븀(Yb) 또는 인듐(In) 중 어느 하나인 것을 특징으로 하는 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물
- 루테늄 및 크롬을 포함하여 이루어지는 것을 특징으로 하는 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물
- 제 4항에 있어서,상기 루테늄 100중량부에 대하여, 상기 크롬은 300 내지 500중량부를 포함하는 것을 특징으로 하는 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물
- 제 1항 또는 제 4항에 있어서,용매를 더 포함하며, 상기 용매는 이온성 용매 또는 비양자성(aprotic) 극성용매 중 적어도 하나인 것을 특징으로 하는 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물
- 제 6항에 있어서,상기 이온성 용매는 에틸메틸이미다졸리엄 클로라이드([EMIM]Cl), 에틸메틸이미다졸리엄 브로민([EMIM]Br) 또는 에틸메틸이미다졸리엄 요오드([EMIM]I) 중 적어도 하나이며, 상기 비양자성 극성용매는 디메틸아세트아미드 (dimethylacetamide) 디메틸술폭시드 (dimethyl sulfoxide), 다이메틸폼아마이드 (Dimethylformamide), 헥사메틸포스포로트리아미드, N-메틸피롤리돈, 테트라히드로퓨란(THF) 또는 γ-부티로락 중 적어도 하나인 것을 특징으로 하는 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 제조하기 위한 금속촉매조성물
- 목질계 바이오매스로부터 셀룰로오스를 추출하는 전처리단계; 및상기 셀룰로오스와, MXn 또는 MXn·H2O(M은 금속원소이고, X는 할로겐 원소 또는 트리플레이트, 노나플레이트, 메실레이트, 토실레이트 또는 디아조늄으로 이루어진 작용기 중에서 선택되며, n은 1 내지 3이다)로 표현되는 금속촉매를 용매 내에서 촉매전환반응시켜 푸르푸랄 유도체를 제조하는 반응단계;를 포함하는 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 8항에 있어서,상기 금속촉매는, 상기 금속원소(M)가 Cr(Ⅱ)인 금속촉매와 상기 금속원소(M)가 Ru(Ⅲ)인 금속촉매 중 적어도 하나를 포함하는 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 9항에 있어서,상기 금속원소 Cr(Ⅱ)을 포함하는 금속촉매와, 상기 금속원소 Ru(Ⅲ)을 포함하는 금속촉매의 당량비는, 1:1 내지 5:1인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 8항에 있어서,상기 용매에 대한 상기 셀룰로오스의 비율은, 50 내지 500g/L인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 8항에 있어서,상기 반응단계에서, 반응온도는, 100 내지 150℃이며, 반응시간은 1 내지 5시간인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 금속촉매와 용매를 혼합하여 혼합물을 제조하는 혼합단계;상기 혼합물을 가열하는 가열단계;상기 혼합물에 목질계 바이오매스 원료물질을 첨가하여 반응물을 제조하는 첨가단계; 및상기 반응물을 가열하여 반응시키는 반응단계;를 포함하여 이루어지는 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 13항에 있어서,상기 혼합단계에서, 상기 금속촉매는 MXn 또는 MXn·H2O로 이루어지며, 상기 M은 금속원소이고, 상기 X는 할로겐 원소, 트리플레이트, 노나플레이트, 메실레이트, 토실레이트 또는 디아조늄으로 이루어진 작용기 중 어느 하나이며, 상기 n은 1 내지 3인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 14항에 있어서,상기 혼합단계에서, 상기 금속원소는 망간(Mn), 니켈(Ni), 철(Fe), 크롬(Cr), 구리(Cu), 코발트(Co), 루테늄(Ru), 주석(Sn), 아연(Zn), 알루미늄(Al), 세륨(Ce), 란탄(La), 네오디뮴(Nd), 스칸듐(Sc), 이테르븀(Yb) 또는 인듐(In) 중 어느 하나인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 13항에 있어서,상기 혼합단계에서, 상기 금속촉매는 루테늄 및 크롬을 포함하여 이루어지는 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 16항에 있어서,상기 루테늄 100중량부에 대하여, 상기 크롬은 300 내지 500중량부를 포함하는 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 16항에 있어서,상기 혼합단계에서, 상기 용매는 이온성 용매 또는 비양자성(aprotic) 극성용매 중 적어도 하나인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 18항에 있어서,상기 이온성 용매는 에틸메틸이미다졸리엄 클로라이드([EMIM]Cl), 에틸메틸이미다졸리엄 브로민([EMIM]Br) 또는 에틸메틸이미다졸리엄 요오드([EMIM]I) 중 적어도 하나이며, 상기 비양자성 극성용매는 디메틸아세트아미드 (dimethylacetamide) 디메틸술폭시드 (dimethyl sulfoxide), 다이메틸폼아마이드 (Dimethylformamide), 헥사메틸포스포로트리아미드, N-메틸피롤리돈, 테트라히드로퓨란(THF) 또는 γ-부티로락 중 적어도 하나인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 13항에 있어서,상기 가열단계에서, 가열온도는 60 내지 100℃인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 13항에 있어서,상기 첨가단계에서, 상기 목질계 바이오매스 원료물질은 셀룰로오스 또는 헤미셀룰로오스 중 적어도 하나를 포함하는 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 13항에 있어서,상기 첨가단계에서, 상기 반응물은, 상기 목질계 바이오매스 원료물질 100몰%에 대하여, 상기 금속촉매는 1 내지 20몰%를 포함하는 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 13항에 있어서,상기 첨가단계에서, 상기 목질계 바이오매스 원료물질은, 상기 용매 1L에 대하여, 50 내지 500g을 포함하는 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
- 제 13항에 있어서,상기 반응단계에서, 반응온도는 100 내지 200℃이며, 반응시간은 1 내지 4시간인 것을 특징으로 하는 푸르푸랄 유도체의 제조방법
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CN201180019103.7A CN102844114B (zh) | 2010-04-15 | 2011-04-14 | 用于从木质类生物质原料物质制备糠醛衍生物的金属催化剂组合物及利用该金属催化剂组合物的糠醛衍生物的制备方法 |
US13/640,764 US8871957B2 (en) | 2010-04-15 | 2011-04-14 | Metal catalyst composition for producing furfural derivatives from raw materials of lignocellulosic biomass, and method for producing furfural derivatives using the composition |
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KR1020100034646A KR101186503B1 (ko) | 2010-04-15 | 2010-04-15 | 목질계 바이오매스 유래 셀룰로오스를 이용한 5-히드록시메틸-2-푸르푸랄의 제조방법 |
KR10-2010-0034646 | 2010-04-15 | ||
KR1020110013821A KR101252819B1 (ko) | 2011-02-16 | 2011-02-16 | 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 직접 제조하기 위한 금속촉매조성물 및 이를 이용하여 목질계 바이오매스 원료물질로부터 푸르푸랄 유도체를 직접 제조하는 방법 |
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