KR20120094364A - Method for manufacturing of particle external additive for e-paper using carbon black and particle external additive for e-paper using carbon black prepared by using the method - Google Patents

Abstract

PURPOSE: A metal catalytic composition for directly manufacturing furfural derivatives based on wood-based biomass materials and a method for directly manufacturing the furfural derivatives from the wood-based biomass materials using the same are provided to reduce costs required for raw materials and to raise yield. CONSTITUTION: A metal catalytic composition for directly manufacturing furfural derivatives based on wood-based biomass materials includes MXn or MXn·H_2O. In MXn or MXn·H_2O, M is a metal element; X is one of a halogen element, triflate, nonaflate, mesylate, tosylate, or diazonium-based function group; and n is 1 to 3. The content of MXn or MXn·H_2O is 1 to 20 mol% based on 100 mol% of the wood-based biomass materials. The metal element is one of manganese(Mn), nickel(Ni), iron(Fe), chrome(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).

Description

Metal catalyst composition for producing furfural derivatives directly from woody biomass raw materials and methods for producing furfural derivatives directly from woody biomass raw materials using the same {METHOD FOR MANUFACTURING OF PARTICLE EXTERNAL ADDITIVE FOR E-PAPER USING CARBON BLACK AND PARTICLE EXTERNAL ADDITIVE FOR E-PAPER USING CARBON BLACK PREPARED BY USING THE METHOD}

The present invention relates to a metal catalyst composition for directly preparing furfural derivatives from woody biomass raw materials and a method for directly producing furfural derivatives from woody biomass raw materials using the same. Unlike the process, which requires the use of various metal catalysts under the optimum reaction conditions, it is possible to directly convert to furfural derivatives in one reactor without the need for a separate monoglycosylation process, thereby significantly reducing the process cost. The present invention relates to a metal catalyst composition for directly preparing furfural derivatives from woody biomass raw materials, and a method for directly producing furfural derivatives from woody biomass raw materials using the same.

The rapid decline in oil reserves and the rapid growth of emerging developing countries, such as BRICs, have led to an imbalance in supply and demand, leading to high oil prices. Moreover, the irreversible use of petroleum, a non-cyclic resource, causes irreversible amounts of greenhouse gases, causing serious environmental problems such as global warming, and the world has established strong regulations that charge for greenhouse gas emissions. Strong sanctions on the use of noncyclic resources such as oil.

Many efforts have already been made to replace petroleum resources through renewable and sustainable use such as biomass, especially in advanced countries.Lactic acid, a raw material of polymer materials, as well as biofuels such as bioethanol and biodiesel It also produces industrially produced biomass-derived chemicals such as propanediol.

 However, 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.). This has led to a rise in grain prices through the reduction of existing farmland, and there is serious controversy over the world food problem from the international community.

To solve this problem, cellulose and hemicellulose are carbohydrates that can be extracted from wood-based biomass, such as plants that grow spontaneously with non-cultivated growth power, residues remaining after cultivation, and waste wood resources. In addition, it is attracting attention as an alternative to sucrose and starch, which are carbohydrates from starch.

In particular, cellulose and hemicellulose, which are carbohydrate polymers that can be extracted from wood-based biomass, generate huge amounts through photosynthesis every year (1,270 billion tons / year), and currently only about 3-4% of them are used in the United States. In 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 linked linearly or two-dimensionally. 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.

Specifically, 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.

On the other hand, recently, furfural derivative compounds derived from such biomass (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.

Structural Formula of Hydroxymethyl-2-furfural (HMF)

또는

or

[Structure of 2-Furfural]

또는

or

First, a representative technique for preparing HMF from carbohydrates derived from biomass is a method obtained by dehydration 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.

However, 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.

In addition, there is a problem that a monosaccharide process that can efficiently obtain glucose from cellulose which is a polysaccharide is required.

On the other hand, 2-furfural can be used as a fuel material itself, and 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. However, 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.

Therefore, there is a need for development of a method for directly producing furfural derivatives without complex and costly pretreatment and monoglycosylation from woody biomass raw materials.

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 directly preparing furfural derivatives from woody biomass raw materials that can directly convert furfural derivatives from woody biomass raw materials with a simple reaction process in the apparatus, and woody biomass raw materials using the same It is an object to provide a method for producing furfural derivatives directly from a substance.

In addition, by using wood-based biomass that does not cause food problems as a raw material, not only the raw material cost is significantly reduced, but also wood-based biomass that can be effectively converted to furfural derivatives by applying a process optimized for wood-based biomass. An object of the present invention is to provide a metal catalyst composition for directly preparing furfural derivatives from a mass raw material and a method for directly producing furfural derivatives from a woody biomass raw material using the same.

In addition, since furfural derivatives can be directly produced from woody biomass raw materials in a simple process, the process cost can be significantly reduced, and furfural derivatives can be directly produced from woody biomass raw materials with high yield. An object of the present invention is to provide a metal catalyst composition and a method for directly preparing furfural derivatives from woody biomass raw materials.

In addition, it is possible to prevent the generation of waste acid and wastewater generated in the pre-treatment and mono-glycosylation process, and to significantly reduce energy consumption, metal catalyst composition for producing furfural derivatives directly from environmentally friendly wood-based biomass raw materials and use thereof An object of the present invention is to provide a method for directly preparing furfural derivatives from woody biomass raw materials.

In addition, it is not necessary to separately extract cellulose from woody biomass raw materials, and to directly prepare furfural derivatives from woody biomass raw materials that can directly utilize hemicellulose, which is a useful component in woody biomass raw materials. It is an object of the present invention to provide a catalyst composition and a method for directly preparing furfural derivatives from woody biomass raw materials.

In addition, it has been optimized to directly convert hydroxymethyl-2-furfural and 2-furfural from woody biomass raw materials, and these products are representative core platform materials and are widely used in various fields through various conversion reactions. A metal catalyst composition for directly preparing furfural derivatives from wood based biomass raw materials, which can be used, and a method for producing furfural derivatives directly from wooden based biomass raw materials using the same. It is done.

The metal catalyst composition for directly preparing furfural derivatives from the wood-based biomass raw materials according to the present invention for achieving the above object is a metal catalyst composition for directly preparing furfural derivatives from the wood-based biomass raw materials. In the above, MXn or MXn? H ₂ O, and M is a metal element, X is any one of the functional group consisting of a halogen element, triflate, nona plate, mesylate, tosylate or diazonium , N is 1 to 3 characterized in that.

With respect to 100 mol% of the wood-based biomass raw material, the MXn or MXnH ₂ O is characterized in that it contains 1 to 20 mol%, 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).

Metal catalyst composition for directly preparing furfural derivatives from woody biomass raw materials Another embodiment is characterized in that it comprises ruthenium chloride (RuCl ₃ ) and chromium chloride (CrCl ₂ ), the ruthenium chloride (RuCl ₃ ) Based on 100 parts by weight, the chromium chloride (CrCl ₂ ) is characterized in that it comprises 300 to 500 parts by weight.

In addition, the metal catalyst composition for directly preparing a furfural derivative from the wood-based biomass raw material further comprises a solvent, wherein the solvent is any one of an ionic liquid or an aprotic polar solvent. do.

The ionic liquid can be any 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, tetrahydro It is characterized in that it is either furan (THF) or γ-butyrolact.

Next, a method for directly producing a furfural derivative from the wood-based biomass raw material according to the present invention,

A method of directly producing furfural derivatives from woody biomass raw materials, the method comprising: 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 the woody biomass raw material to the mixture; It characterized in that it comprises a; reaction step of heating and reacting the reactant.

In the mixing step, 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.

In addition, in the mixing step, 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), characterized in that The metal catalyst is characterized by consisting of ruthenium chloride (RuCl ₃ ) and chromium chloride (CrCl ₂ ).

To 100 parts by weight of the ruthenium chloride (RuCl ₃ ), the chromium chloride (CrCl ₂ ) is characterized in that it comprises 300 to 500 parts by weight, in the mixing step, the solvent is an ionic liquid or aprotic (aprotic) It is characterized by any one of the polar solvent.

The ionic liquid can be any one of 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 γ-butyrolact.

In addition, in the heating step, the heating temperature is characterized in that 60 to 100 ℃, in the addition step, the wood-based biomass raw material is characterized in that it comprises at least one of cellulose or hemicellulose.

In the addition step, the reactant, with respect to 100 mol% of the wood-based biomass raw material, characterized in that the metal catalyst comprises 1 to 20 mol%, the wood-based biomass raw material, the solvent It is characterized by containing 50 to 500g per 1L.

In addition, the temperature of the addition step, characterized in that 15 to 30 ℃, in the reaction step, the reaction temperature is characterized in that 100 to 200 ℃, the reaction time is characterized in that 1 to 4 hours.

According to the metal catalyst composition for directly preparing furfural derivatives from the wood-based biomass raw materials of the present invention and the method for directly producing furfural derivatives from the wood-based biomass raw materials, conventionally, pretreatment and monosaccharide processes The process for producing furfural derivatives, which had to go through a multi-step process such as these, was carried out by mixing a variety of metal catalysts at an optimum ratio, thereby purifying furfural derivatives from woody biomass raw materials with a simple reaction process in one reactor. There is an advantage that can be switched immediately.

In addition, by using wood-based biomass that does not cause food problems as a raw material, not only the raw material cost is significantly reduced, but also by applying an optimized process to wood-based biomass, there is an advantage that can be effectively converted to furfural derivatives. .

In addition, since 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.

In addition, it is possible to prevent the generation of waste acid and waste water generated in the pre-treatment and mono-glycosylation process, and to significantly reduce energy consumption, there is an environmentally friendly advantage.

In addition, there is no need to extract cellulose separately from the woody biomass raw material, and there is an advantage in that hemicellulose, which is a useful component in the woody biomass raw material, can be directly used.

In addition, it has been optimized to directly convert hydroxymethyl-2-furfural and 2-furfural from woody biomass raw materials, and these products are representative core platform materials and are widely used in various fields through various conversion reactions. As it can be used, there is a very useful and effective advantage.

1 is a flow chart sequentially showing a method for producing a furfural derivative directly from the wood-based biomass raw material according to the present invention
Figure 2 is a graph showing the high performance liquid chromatography (HPLC) of the products produced using the method for producing a furfural derivative directly from the wood-based biomass raw material of the present invention
FIG. 3 compares the yield of 5-hydroxymethyl-2-furfural, a product produced using a method of directly preparing furfural derivatives, from wood based biomass raw materials of the present invention according to wood based biomass raw materials. A graph
4 is a graph comparing the yield of 2-furfural, a product produced using a method of directly preparing furfural derivatives from the wood-based biomass raw material of the present invention, according to the wood-based biomass raw material

Hereinafter, one preferred embodiment of the present invention relates to a metal catalyst composition for directly preparing furfural derivatives from wood based biomass raw materials and a method for directly producing furfural derivatives from wood based biomass raw materials using the same. An embodiment of the present invention will be described in detail with reference to the accompanying drawings. The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

First, a first embodiment of a metal catalyst composition for directly preparing furfural derivatives from woody biomass raw materials includes MXn or MXn? H ₂ O, wherein M is a metal element, and X is It is any one of a functional group consisting of a halogen element, a triflate, nona plate, mesylate, tosylate or diazonium, wherein n is 1 to 3.

Here, 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.

In addition, 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).

That is, 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.

In addition, with respect to 100 mol% of the wood-based biomass raw material, the MXn or MXn? H ₂ O preferably comprises 1 to 20 mol%, more preferably 5 to 10 mol% is effective. 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.

Next, a second embodiment of the metal catalyst composition for directly preparing furfural derivatives from woody biomass raw materials is characterized in that it comprises ruthenium chloride (RuCl ₃ ) and chromium chloride (CrCl ₂ ). This is to develop a metal catalyst that is most effective in the conversion to furfural derivatives, it is composed of a multi-type, it is possible to most effectively play a unique role in the hydrolysis reaction, dehydration reaction and isomerization reaction.

Here, ruthenium chloride (RuCl ₃ ) acts as a Lewis acid for the hydrolysis and dehydration reaction, chromium chloride (CrCl ₂ ) is effective for the isomerization reaction, by mixing them, causing a number of reactions at the same time There are advantages to it.

In addition, the chromium chloride (CrCl2) is preferably 300 to 500 parts by weight based on 100 parts by weight of the ruthenium chloride (RuCl ₃ ) and chromium chloride (CrCl ₂ ) to 100 parts by weight of the ruthenium chloride (RuCl ₂ ). Preferably it is effective to include 350 to 450 parts by weight. 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.

Next, it is preferable that the first and second embodiments further include a solvent, and the solvent is effectively any one of an ionic liquid or an aprotic polar solvent. This helps in the conversion reaction.

The ionic liquid can be any one of ethylmethylimidazolium chloride ([EMIM] Cl), ethylmethylimidazolium bromine ([EMIM] Br) or ethylmethylimidazolium iodine ([EMIM] I). Preferably, the aprotic polar solvent is dimethylacetamide, dimethyl sulfoxide, dimethylformamide, dimethylmethylphosphorotriamide, N-methylpyrrolidone, or tetrahydrofuran. (THF) or γ-butyrolact is effective.

Next, as shown in Figure 1, the method for producing a furfural derivative directly from the wood-based biomass raw material of the present invention, mixing step (S10), heating step (S20), addition step (S30) and reaction step It includes (S40).

Here, the mixing step (S10) 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.

In the mixing step (S10), 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 It is any one of the functional group consisting of, wherein n is characterized in that 1 to 3.

In addition, 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).

In addition, the metal catalyst is characterized in that consisting of ruthenium (RuCl2) and chromium chloride (CrCl2), relative to 100 parts by weight of ruthenium chloride (RuCl2), the chromium chloride (CrCl2) comprises 300 to 500 parts by weight It is preferable.

In addition, in the mixing step (S10), the solvent is preferably any one of an ionic liquid or an aprotic polar solvent, the ionic liquid is ethyl methyl imidazolium chloride ([EMIM] Cl) , Ethylmethylimidazolium bromine ([EMIM] Br) or ethylmethylimidazolium iodine ([EMIM] I), and the aprotic polar solvent is dimethylacetamide dimethyl sulfoxide ( dimethyl sulfoxide), dimethylformamide, hexamethylphosphorotriamide, N-methylpyrrolidone, tetrahydrofuran (THF) or γ-butyrolact.

The detailed description of the contents is as described above.

Next, the heating step (S20) is a step of heating the mixture. This is a process of mixing the solvent and the metal catalyst effectively to facilitate the reaction.

In the heating step (S20), the heating temperature is preferably 60 to 100 ℃, more preferably 80 to 90 ℃ 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.

In the heating step (S20), it is preferable to stir at the same time as the heating, 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.

Next, the addition step (S30) 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.

In the addition step (S30), 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. In addition, as shown in Formula I below, cellulose forms glycosidic bonds at C1 and C4 positions of D-glucose and is connected by ß (1 → 4) linkage. consist of. However, unlike cellulose, which is a linear polymer, hemocellulose has a two-dimensional chemical structure with some branches.

(I)

In terms of chemical composition, wood-based biomass is most effective to contain 20 to 70% of carbohydrate polymers, that is, at least one of cellulose or hemicellulose.

In addition, in the addition step (S30), the reactant, with respect to 100 mol% of the wood-based biomass raw material, the metal catalyst preferably comprises 1 to 20 mol%, more preferably 5 to 10 mol Including% is effective. The description is as described above.

In addition, 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.

In addition, the temperature in the addition step (S30) is reduced in the heating step (S20), it is preferable to maintain at 15 to 30 ℃, more preferably it is effective to maintain at 20 to 25 ℃. If the temperature is less than 15 ℃, 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 ℃, 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.

Finally, the reaction step (S40) is a step of reacting by heating the reactants. This is a process for producing a furfural derivative finally through a conversion reaction.

In the reaction step (S40), the reaction temperature is preferably 100 to 200 ℃, more preferably 120 to 150 ℃ 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.

In the reaction step (S40), 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 between the product and the by-product occurs, rather the quality of the product is reduced.

In addition, in the reaction step (S40), 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.

In addition, the stirring speed of the stirrer is 500 to 1000 RPM, which can bring about the reactivity and the yield.

That is, 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. At this time, 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.

In the following Scheme 1, as a preferred embodiment of the present invention, 5-hydroxymethyl-2-furfural and 2-furfural by a single reaction from a wood-based biomass source containing carbohydrate polymer cellulose and hemicellulose as main components. The process of obtaining simultaneously is shown briefly.

[Reaction Scheme 1]

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 land, 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.).

Hereinafter, an experimental result for demonstrating the superiority of a metal catalyst composition for directly preparing a furfural derivative from the wood-based biomass raw material of the present invention and a method for directly producing the furfural derivative from the wood-based biomass raw material using the same to be.

First, the results obtained by performing component analysis on the content of cellulose and hemicellulose in various wood-based biomass sources are shown in Table 1 below.

Wood based biomass
Source English name Ingredient cellulose Hemicellulose Lignin ashes Straw rice straw 35.0 25.0 12.0 - Barley straw barley straw 37.0 22.2 - - straw wheat straw 38.2 21.2 23.4 - Tritice triticale 35.8 24.3 21.9 7.4 Rapeseed rape stem 31.2 17.2 20.5 6.5 Silver grass grass 39.7 26.4 24.3 2.4 Reed reed 40.0 22.0 26.1 5.2 Particleboard MDF board 33.2 12.1 32.2 1.1 abolition waste paper 63.9 10.4 1.5 11.5 Coffee bean residue coffee bean residue 5.9 37.4 41.6 0.4

Example

In a tubular type reactor, 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 占 폚 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.

The samples were separated through a C18 reverse phase column on high performance liquid chromatography (HPLC) (Agilent 1200 series), and the peak area was measured using a UV detector (283 nm). At this time, HPLC shows the same pattern as in FIG. 2, and each peak was identified as HMF and 2-furfural. As a result of HPLC analysis, the yields of HMF and 2-furfural produced from the woody biomass raw materials under the conversion reaction conditions were as shown in FIGS. 3 and 4.

That is, through this experiment, according to the embodiment of the present invention, it was confirmed that the wood-based biomass raw material is effectively converted to the furfural derivative in a single reactor, and the yield was very excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is clear that the present invention can be suitably modified and applied in the same manner. Accordingly, the above description does not limit the scope of the invention as defined by the limitations of the following claims.

Claims (22)

In the metal catalyst composition for producing furfural derivatives directly from wood-based biomass raw materials,
Including MXn or MXn? H ₂ O,
M is a metal element, X is any one of a functional group consisting of a halogen element, triflate, nona plate, mesylate, tosylate, or diazonium, wherein n is 1 to 3 wood-based biomass, characterized in that Metal catalyst composition for directly preparing furfural derivatives from raw materials
The method of claim 1,
With respect to 100 mol% of the wood-based biomass raw material, the MXn or MXn? H ₂ O is a metal for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that it comprises 1 to 20 mol% Catalyst composition
3. The method according to claim 1 or 2,
The metal element is manganese (Mn), nickel (Ni), iron (Fe), chromium (Cr), copper (Cu), cobalt (Co), ruthenium (Ru), tin (Sn), zinc (Zn), aluminum Furfural from wood-based biomass raw materials, characterized in that any one of (Al), cerium (Ce), lanthanum (La), neodymium (Nd), scandium (Sc), ytterbium (Yb) or indium (In). Metal Catalyst Compositions for Producing Derivatives Directly
Metal catalyst composition for the direct preparation of furfural derivatives from wood based biomass raw materials, comprising ruthenium chloride (RuCl ₃ ) and chromium chloride (CrCl ₂ )
The method of claim 4, wherein
Based on 100 parts by weight of the ruthenium chloride (RuCl ₃ ), the chromium chloride (CrCl ₂ ) is 300 to 500 parts by weight of the metal catalyst composition for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that
The method according to claim 1 or 4,
Further comprising a solvent, wherein the solvent is any one of an ionic liquid or an aprotic polar solvent metal catalyst composition for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that
The method according to claim 6,
The ionic liquid can be any one of ethylmethylimidazolium chloride ([EMIM] Cl), ethylmethylimidazolium bromine ([EMIM] Br) or ethylmethylimidazolium iodine ([EMIM] I). Metal catalyst composition for directly preparing furfural derivatives from woody biomass raw materials, characterized in that
The method according to claim 6,
The aprotic polar solvent is dimethylacetamide dimethyl sulfoxide, dimethylformamide, hexamethylphosphorotriamide, N-methylpyrrolidone, tetrahydrofuran (THF) or γ. A metal catalyst composition for directly preparing furfural derivatives from woody biomass raw materials, characterized in that it is any one of butyrolact.
In the method for producing a furfural derivative directly from wood-based biomass raw material,
A mixing step of preparing a mixture by mixing a metal catalyst and a solvent;
A heating step of heating the mixture;
An addition step of preparing a reactant by adding the woody biomass raw material to the mixture;
A reaction step of heating and reacting the reactants; a method for directly producing furfural derivatives from a wood-based biomass raw material, characterized in that it comprises a.
The method of claim 9,
In the mixing step, 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, wherein n is a method for producing a furfural derivative directly from wood-based biomass raw material, characterized in that 1 to 3
The method of claim 10,
In the mixing step, 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), characterized in that the wood-based biomass Method for directly preparing furfural derivatives from raw materials
The method of claim 9,
In the mixing step, the metal catalyst is a method for directly producing a furfural derivative from wood-based biomass raw material, characterized in that consisting of ruthenium chloride (RuCl ₃ ) and chromium chloride (CrCl ₂ ).
13. The method of claim 12,
Based on 100 parts by weight of the ruthenium chloride (RuCl ₃ ), the chromium chloride (CrCl ₂ ) is a method for producing a furfural derivative directly from wood-based biomass raw material, characterized in that it comprises 300 to 500 parts by weight

The method of claim 9,
In the mixing step, the solvent is a method for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that any one of an ionic liquid or an aprotic polar solvent.
The method of claim 14,
The ionic liquid can be any one of 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 γ-butyrolact, which is a method of directly preparing furfural derivatives from a wood-based biomass raw material
The method of claim 14,
In the heating step, the heating temperature is a method for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that 60 to 100 ℃ The method of claim 9,
In the addition step, the wood-based biomass raw material is a method for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that it comprises at least one of cellulose or hemicellulose.
The method of claim 9,
In the addition step, the reactant is a furfural derivative directly from the wood-based biomass raw material, characterized in that the metal catalyst comprises 1 to 20 mol% with respect to 100 mol% of the wood-based biomass raw material. How to make
The method of claim 9,
The wood-based biomass raw material, the method for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that it comprises 50 to 500g with respect to 1L of the solvent.
The method of claim 9,
The temperature of the addition step, a method for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that 15 to 30 ℃
The method of claim 9,
In the reaction step, the method for producing a furfural derivative directly from the wood-based biomass raw material, characterized in that the reaction temperature is 100 to 200 ℃
The method of claim 9,
In the reaction step, the reaction time is a method for producing a furfural derivative directly from wood-based biomass raw material, characterized in that 1 to 4 hours

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