KR101799932B1 - Process for selective hydrogenation of hydroxymethylfurfural using Ru nanoparticles supported catalysts - Google Patents
Process for selective hydrogenation of hydroxymethylfurfural using Ru nanoparticles supported catalysts Download PDFInfo
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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- 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
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- 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
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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Abstract
The present invention relates to a selective hydrogenation process of hydroxymethylfurfural (HMF) using a ruthenium nano-particle-supported catalyst, and more particularly to a process for selectively hydrogenating hydroxymethylfurfural (HMF), which comprises ruthenium nanoparticles supported on a porous polymer functionalized with a nitrogen- The present invention relates to a method for producing furandimethanol (FDM) at a high yield by selectively hydrogenating hydroxymethyl furfural using a ruthenium nano-particle-supported catalyst as a catalyst.
Description
The present invention relates to a selective hydrogenation method of hydroxymethylfurfural (HMF) using a ruthenium nano-particle-supported catalyst, and more particularly to a method for selectively hydrogenating ruthenium nanoparticles in which ruthenium nanoparticles are supported on a functionalized porous polymer The present invention relates to a method for producing furandimethanol (FDM) in high yield by selectively hydrogenating hydroxymethyl furfural using a supported catalyst as a reaction catalyst.
Renewable energy, based on lignocellulosic or cellulosic biomass, is seen as a means for the sustainable production of chemicals and fuels as an alternative to non-renewable petroleum resources. Recently, due to the limited availability of petroleum resources and environmental problems caused by excessive use of petroleum resources, catalyst conversion methods for producing renewable energy from cellulose-based biomass or biomass derivatives have attracted great interest . Over the years, a variety of chemicals have been produced by the chemical or biological transformation of cellulosic biomass and biomass derivatives. For example, 5-hydroxymethylfurfural (HMF) was produced from carbohydrate or cellulose in the presence of an acid catalyst, and the 5-hydroxymethyl furfural is a biomass-based It is classified as one of 10 compounds. U.S. Pat. No. 4,740,905, U.S.P. 8563756 and U.S.P. 8729281 disclose that ethyl levulinate (EL) is produced by selective conversion of HMF by two functional groups present in the HMF structure Ethoxymethylfurfural (EMF), 2,5-dihydroxymethylfuran (BHMF), 2,5-dimethylfuran (DMF), C9-C15alkane, The use value of levulinic acid (LA), 2,5-diformylfuran (DFF), and 2,5-furandicaboxylic acid (FDCA) Lt; RTI ID = 0.0 > biofuel < / RTI >
(2,5-bis (hydroxymethyl) furan, BHMF), 2,5-furandimethanol (FDM), 2 , 2,5-bis (hydroxymethyl) tetrahydrofuran, BHMTHF) and 2,5-dimethylfuran can be prepared. The furan dimethanol prepared from the hydrogenation reaction of the carbonyl group (-C═O) of the HMF can be used in various aspects such as the production of resin, polymer, and chemical fiber having various properties, and thus its potential is excellent. In addition, the furan dimethanol can be used as an intermediate compound in the synthesis of pharmaceutical compositions, crown ethers, and can be used in the production of 2,5-bis (hydroxymethyl) tetrahydrofuran. Due to the various applications and commercial importance of furan dime methanol as described above, there have been actively studied hydrogenation methods of HMF capable of selectively producing furan dmethanol from HMF using metal complexes and metal supported catalysts in various environments. The kind of product produced through the hydrogenation reaction of HMF is greatly influenced by the selectivity of the metal used as a catalyst in this reaction and the reaction environment conditions. For example, USP 3083236 discloses that furan dimethanol (FDM) having a purity of 90% can be prepared using copper chromium iron (Cu 2 Cr 2 O 5 ) as a catalyst in the hydrogenation reaction of HMF . However, the method of hydrogenating HMF using a copper chromium iron catalyst disclosed in the above prior art has a problem of low efficiency of 30 hours or more of reaction at a high temperature of 150 ° C or more. In addition, chromium, which is a heavy metal component contained in the copper chromium iron used as the catalyst, has a problem that harmful to the natural environment may occur when the hydrogenation method is carried out. A hydrogenation method using Raney-type metals (Cu, Co and Ni) as a catalyst has been disclosed as a hydrogenation method of HMF for improving the problems of the prior art ( Bull. Soc . Chim. Fr. , 128 (1991) 704] . However, in the case of the hydrogenation method of HMF using the Raney type metal catalyst, most of the produced products are 2,5-bis (hydroxymethyl) tetrahydrofuran (BHMTHF), and the production of furan dimethanol (FDM) The yield is as low as 27%. In addition, the Raney-type metal catalyst used as the catalyst has a problem of low self-ignitability and very low safety.
In order to improve the above problems, US Pat. No. 7,994,347, US Pat. No. 8,367,851 and US Pat. No. 5,054,194 disclose that nickel, cobalt, copper, palladium, ruthenium or platinum Discloses a hydrogenation method of HMF using a supported metal supported catalyst. It has been disclosed that furan dimethanol having a purity of 90 to 98% can be prepared by using a metal supported catalyst having platinum carried on a carbon carrier among the above-mentioned literatures. However, since platinum is expensive, . In addition, the remaining documents using metal supported catalysts containing nickel, cobalt, copper, ruthenium or palladium other than platinum include a problem that the yield of furan dimethanol (FDM) is very low.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a ruthenium nanocomposite supported catalyst having a ruthenium nanoparticle supported on a porous polymer carrier functionalized with a nitrogen- (HMF) hydrogenation method which is capable of producing furan di-methanol efficiently and economically, and which is excellent in safety.
A) preparing a mixture by adding to the reactor a ruthenium nano-particle-supported catalyst carrying ruthenium nanoparticles supported on a porous polymer carrier functionalized with a nitrogen-containing functional group and hydroxymethyl furfural; b) hydrogenating the hydroxymethyl furfural by pressurizing, heating and stirring the mixture of step a); And c) separating the furan dimethanol from the mixture obtained via step b); To a process for the hydrogenation of hydroxymethyl furfural.
In the present invention, the reactor may be a liquid ash type reactor or a continuous stationary phase reactor.
In the present invention, the ruthenium nano-particle-supported catalyst may be prepared by (1) preparing a suspension by adding a porous polymer carrier functionalized with a nitrogen-containing functional group to a ruthenium solution prepared by dissolving a ruthenium salt in a solvent, step; And (2) reducing the suspension through step (1).
In the present invention, the ruthenium salt may be at least one selected from the group consisting of ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium oxide, ruthenium hydroxide, ruthenium cyanide, ruthenium trifluoroacetate, ruthenium acetate, ruthenium acetylacetonate, And the ruthenium salt may be included in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polymer carrier.
In the present invention, the reduction of step (2) may be carried out by adding at least one reducing agent selected from sodium borohydride, potassium borohydride and hydrazine hydrate to the suspension.
In the present invention, the ruthenium nano-particle-supporting catalyst of step a) may be contained in an amount of 0.05 to 100 parts by weight based on 100 parts by weight of hydroxymethyl furfural.
In the present invention, the pressurization of the step b) may be performed by injecting hydrogen gas into the reactor including the mixture, and the internal pressure of the reactor may be 15 to 900 psig.
In the present invention, the heating of step b) may be performed at a temperature of 30 to 200 ° C, and the hydrogenation may be performed for 30 to 600 minutes.
The method for hydrogenating hydroxymethylfurfural in the present invention may further comprise separating the solid catalyst ruthenium nano-particle supporting catalyst from the mixture obtained through step b) before the step c) Can be reused for the hydrogenation of hydroxymethyl furfural.
In the present invention, the separation of the step c) can be performed by distillation, and the furan dimethanol obtained through the separation step exhibits a selectivity of 90 to 98%.
The ruthenium nano-particle-supported catalyst according to the present invention, which has high safety and reusability in the form of nontoxic and relatively inexpensive ruthenium nanoparticles supported on a porous polymer carrier functionalized with a nitrogen-containing functional group, (HMF) hydrogenation method using a hydroxymethyl furfural (HMF) hydrogenation method using a copper chromium iron, a Raney nickel and a carbon supported catalyst as a reaction catalyst, Furan de-methanol can be prepared.
Hereinafter, a method for hydrogenating hydroxymethylfurfural (HMF) according to the present invention will be described in more detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It will be apparent to those skilled in the art that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, And a description of the known function and configuration will be omitted.
Throughout the specification, the term " HMF " has been used to abbreviate the term " hydroxymethyl furfural " of the present invention, " FDM " refers to the word " furan dmethanol " Respectively. The term " nitrogen-containing functional group " refers to an amide group, an amine group, a ketimine group, an aldimine group, an imide group, an azide group, an azo group, a cyanic acid group, an isocyanic acid group, an isocyanic acid group, The term " ruthenium nano-particle supporting catalyst " is used to refer to a functional group containing a nitrogen atom such as nitro group, nitro group, pyridine group and the like, Ruthenium nanoparticle supported ruthenium nanoparticle supported catalyst ".
The present invention relates to a process for hydrogenating hydroxymethylfurfural, which comprises the steps of: (i) reacting ruthenium nano-particles having a characteristic of being less toxic, having a small amount of impurities generated due to no spontaneous ignition characteristic, The present invention relates to a method for producing furandimethanol (FDM) in an economical and efficient manner by selectively hydrogenating hydroxymethyl furfural using a particle-supported catalyst as a reaction catalyst, and more particularly, to a method for producing furandimethanol Preparing a mixture by adding a ruthenium nano-particle-supported catalyst and ruthenium nanoparticle-supported catalyst carrying a porous polymer carrier functionalized with a nitrogen-containing functional group and hydroxymethyl furfural; b) hydrogenating the hydroxymethyl furfural by pressurizing, heating and stirring the mixture of step a); And c) separating the furan dimethanol from the mixture obtained via step b); To a process for the hydrogenation of hydroxymethyl furfural.
The reactor of step a) used to carry out the hydrogenation reaction in the present invention may be a liquid phase batch reactor or a continuous fix bed reactor.
The ruthenium nano-particle-supported catalyst used as a reaction catalyst in the hydroxymethylfurfural hydrogenation process of the present invention is characterized in that (1) a ruthenium solution prepared by dissolving a ruthenium salt in a solvent is added to a porous polymer functionalized with a nitrogen- Adding a carrier to prepare a suspension, and refluxing the suspension; And (2) reducing the suspension through step (1); But it is not particularly limited thereto.
In the production of the ruthenium nano-particle-supported catalyst used as the reaction catalyst in the hydroxymethyl furfural hydrogenation process of the present invention, the solvent used in step (1) may be any material that can dissolve the ruthenium salt N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide and the like, preferably water, methanol, ethanol, isopropanol, 1,4-dioxane, tetrahydrofuran, acetone, acetonitrile, toluene, benzene, cyclohexane, Dimethylacetamide, chloroform, carbon tetrachloride, dichloromethane, dichloroethane and the like may be used, but the present invention is not limited thereto. The ruthenium salt used in the step (1) may be at least one selected from the group consisting of ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium oxide, ruthenium hydroxide, ruthenium cyanide, ruthenium trifluoroacetate, ruthenium acetate, Tetraamine dichloro ruthenium, and the like. In addition, in the step (1), the porous polymer carrier used as a carrier for supporting the ruthenium salt has a nanopore structure and has a large surface area and can form a bond with the ruthenium salt supported in the nano- An amide group, a ketimine group, an aldimine group, an imide group, an azide group, an azo group, a cyanic acid group, an isocyanic acid group, an isocyanic acid group, an iso May be a porous polymer whose surface is functionalized with a functional group containing a nitrogen atom such as a thiocyanic acid group, a nitric acid group, a nitrile group, a nitro group, a nitro group, a nitroso group and a pyridine group, May be a functionalized porous polymer. The type of the functional group for functionalizing the surface of the polymer carrier is not particularly limited. However, when a polymer carrier having a surface functionalized with a functional group containing a nitrogen atom is used in the production of the ruthenium nano-particle-supported catalyst, The ruthenium ion is chemically strongly bonded to the functional group by the electron-rich nitrogen atom, so that the ruthenium nanoparticles are uniformly dispersed and bonded to the overall portion of the polymer carrier without agglomeration, and the ruthenium nanoparticles and the polymer Even if a large number of ruthenium nanoparticles are reused in the hydrogenation reaction of the present invention due to the chemical bonding of the carrier, ruthenium nanoparticle supported catalyst which can exhibit constant catalytic activity can be produced because the ruthenium nanoparticles are not desorbed from the support. In addition, when a polymer carrier having a surface functionalized with an amine group as a functional group is used as the functional group on the ruthenium nano-particle-supported catalyst, the wettability of the ruthenium nano-particle-supported catalyst can be remarkably improved by the hydrophilicity of the amine group and the catalytic activity can be maximized . In the step (1), the polymer used as the carrier for supporting the ruthenium salt may be any polymer having good solubility in a solvent, and preferably, a polystyrene and a polystyrene-divinylbenzene copolymer And the like may be used, but are not particularly limited thereto. By using a polymer having excellent solubility in a solvent as a support, the produced ruthenium nano-particle-supported catalyst can maintain its original solid state without being dissolved in a solvent even after being used in the hydrogenation reaction of the present invention, After the hydrogenation reaction, it can be separated from the reaction solvent by a simple method such as centrifugation, filtration or decantation and can be reused in large numbers.
In the present invention, the ruthenium salt used in the step (1) in preparing the catalyst for supporting the ruthenium nano-particles may be contained in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polymer carrier . The content of the ruthenium salt supported on the polymer carrier is not particularly limited. When the ruthenium nano-particle-supported catalyst prepared in the above range is used in the HMF hydrogenation process of the present invention, FDM) can be obtained.
In the present invention, the solvent, the ruthenium salt, and the polymer carrier used for preparing the ruthenium nano-particle-supported catalyst may be mixed through the step (1) to prepare a suspension, and the suspension may be subjected to a reflux step. The reflux of the step (1) may be carried out at a temperature of 70 to 85 ° C for 2 to 24 hours, preferably 10 to 18 hours, but is not particularly limited thereto. The suspension after the refluxing step of step (1) may be reduced through step (2), wherein the suspension may be further cooled to a room temperature of 15 to 35 ° C before the reducing step. In the present invention, the reduction of the step (2) is carried out by adding sodium borohydride (NaBH 4 ), potassium borohydride (KBH 4 ) and hydrazine hydrate to the suspension after the cooling step, , And then the mixture is stirred for 1 to 20 hours, preferably 3 to 12 hours. However, the present invention is not limited thereto. The suspension containing the solid material in which the ruthenium nanoparticles are supported on the pores of the porous polymer carrier is prepared through the reducing step of step (2), and the suspension is subjected to solid-liquid separation, more specifically, centrifugation centrifugation, filtration or decantation, or the like, into an insoluble component and a liquid-phase mixture. The ruthenium nano-particle-supported catalyst used as the reaction catalyst in the HMF hydrogenation process of the present invention can be prepared through washing the separated insoluble components in a mixed solvent of water and ethanol, followed by drying.
The ruthenium nanoparticle supported catalyst prepared by the above method can be mixed with hydroxymethyl furfural in the presence of a reaction solvent in the reactor as a reaction catalyst in step a) of the HMF hydrogenation process of the present invention, As the particle-bearing catalyst has dissolvability with respect to the solvent, the mixture prepared through the mixing may be a suspension-like mixture in which the ruthenium nanoparticle-supporting catalyst is dispersed in a solid state on the reaction solvent.
The solvent used in step a) of the HMF hydrogenation process of the present invention may be any solvent having a boiling point lower than the boiling point of hydroxymethyl furfural, preferably room temperature ionic liquid, water Methanol, ethanol, propanol, isopropanol, butanol, 1,4-dioxane, tetrahydrofuran, acetone, and the like. N, N-dimethylformamide, chloroform, carbon tetrachloride (N, N-dimethylformamide), acetonitrile, toluene, benzene, cyclohexane, hexane, carbon tetrachloride, dichloromethane, and dichloroethane, but is not particularly limited thereto.
Further, in step a) of the HMF hydrogenation process of the present invention, the ruthenium nano-particle-supported catalyst is used in an amount of 0.05 to 100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably 0.5 To 50 parts by weight. In the present invention, the use amount of the ruthenium nano-particle-supported catalyst is not particularly limited. However, when the above range is satisfied, the reaction selectivity for producing furandimethanol from hydroxymethyl furfural is remarkably improved and the production of efficient furandimethanol It is even better.
The mixture prepared through step a) of the present invention may undergo the process of pressurization, heating and stirring of step b) of the present invention.
In the present invention, the pressurization of the step b) may be performed by injecting hydrogen gas into the reactor containing the mixture, and the pressure of the reactor in the state where the hydrogen gas is injected is 15 to 900 psig, 600 psig. ≪ / RTI >
In the present invention, the heating of step b) may be carried out at a temperature of 30 to 200 ° C, preferably 40 to 150 ° C, stirring may be carried out at 100 to 3000 rpm, and the pressure of step b) , Heating and stirring may be performed independently of each other or simultaneously, but are not particularly limited thereto.
In the present invention, the hydrogenation reaction of hydroxymethyl furfural present in the mixture prepared in step a) can be carried out by the pressure, heating and stirring of step b), and the pressure, heating and stirring of step b) May be carried out for 30 to 600 minutes, preferably 60 to 420 minutes. In the present invention, the time for performing the hydrogenation reaction is not particularly limited. However, when the above range is satisfied, the conversion rate of hydroxymethyl furfural is remarkably improved, and the production rate of furandimethanol is also improved It is better to be able.
The method for hydrogenating hydroxymethylfurfural of the present invention comprises the steps of separating the ruthenium nano-particle supported catalyst in solid state from the mixture produced through the hydrogenation reaction before and after step b) and after step c) ; And the ruthenium nano-particle-supported catalyst separated through the separation step may be reused in the hydrogenation reaction of hydroxymethyl furfural. The mixture produced through the hydrogenation reaction in the step b) of the present invention may be a suspension mixture containing a hydrogenation product of hydroxymethyl furfural and a ruthenium nano-particle-supporting catalyst dispersed in a solid state. Ruthenium Separation of the nanoparticle-supported catalyst can be performed simply by centrifugation, filtration, or decantation.
The liquid mixture obtained by separating the ruthenium nano-particle-supported catalyst through the separation step may be subjected to the separation step of the step c) of the present invention, and the furan dimethanol may be separated from the liquid mixture through the separation step of the step c) .
In the present invention, the separation of the step c) may be performed by a method of separating a liquid mixture, specifically, a simple distillation, a fractional distillation, etc., but not limited thereto, From the mixture, the remaining liquid mixture such as a solvent or a by-product having a lower boiling point than that of the product of the present invention, which is the product of the present invention, is removed by evaporation to obtain furan di-methanol as a main product by the HMF hydrogenation reaction of the present invention. When the liquid mixture is separated using the distillation method in step c) of the present invention, the liquid mixture may be separated by heating to a temperature lower than the boiling point of furan di-methanol, specifically, 273 Lt; RTI ID = 0.0 > C, < / RTI > In the present invention, the furan dimethanol obtained through the separation step of step c) may exhibit a high selectivity of 90 to 98%.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, it is to be understood that the present invention is not limited to the disclosed embodiments, but various modifications and alterations may be possible without departing from the scope of the present invention.
First, the experimental method performed in the present invention is presented.
In this case, the words " reaction catalyst " used in Experiments 1) to 3 below are 'ruthenium nanoparticles carrying ruthenium nanoparticles supported on a porous polystyrene-divinylbenzene support functionalized with amine functional groups of Examples 1 to 11 (AFPS, PS, Ru-PS, Ru-C, and Ru-AFPS) prepared through Comparative Examples 1 to 7 or catalysts (hereinafter referred to as ruthenium nanoparticle- Al 2 O 3 , Ru-TiO 2 or Ru-SiO 2 ) '.
Experiment 1) Measurement of pore size and pore volume of reaction catalyst
The pore size and pore volume of the reaction catalyst were measured by BET analysis method (Brunauer-Emett-Teller analysis).
Experiment 2) Conversion of hydroxymethyl furfural (HMF) and hydrogenation selectivity of furan dmethanol (FDM) from HMF
The conversion of the hydroxymethyl furfural (Conv; Conv.) And furan dmethanol (Fmoc) were carried out by gas chromatography analysis (GC analysis) using a liquid mixture in which the hydrogenation reaction was completed and the reaction catalyst was removed The selectivity (S FDM ) was measured.
Experiment 3) Measurement of Reuse Efficiency of Reaction Catalyst
After the hydrogenation-completed mixture is filtered to reuse the insolubilized reaction catalyst in the hydrogenation reaction 1 to 3 times, the hydrogenation-completed mixture is subjected to conversion of hydroxymethylfurfural through the method of Experiment 2. Conv.) And furandimethanol selectivity (S FDM ) were measured.
[Example 1]
<Preparation of 1% ruthenium nano-particle-supported catalyst (1% Ru-AFPS)
(AFFP) having a particle diameter of 200 to 300 mesh was prepared by grinding a porous polystyrene-divinylene copolymer (AFP) granule functionalized with an amine functional group used as a support of the ruthenium nano-particle-supported catalyst of the present invention Respectively.
In a round flask equipped with a reflux condenser, 30 ml of ethanol, 2.0 g of the polymer carrier and 52 mg of ruthenium chloride (RuCl 3 3H 2 O) were added as a reaction solvent and mixed to prepare a suspension-like mixture. After the mixture was stirred for 12 hours and under reflux, cooled to 25 ℃, was added an excess of NaBH 4 as a reducing agent to the cooled mixture. The mixture to which the reducing agent was added was stirred at 25 DEG C for 6 hours and filtered to obtain a solid insoluble material. The obtained insoluble material was washed with ethanol and dried to prepare 2.05 g of a ruthenium nano-particle-supported catalyst (hereinafter referred to as 1% Ru-AFPS) carrying 1% of ruthenium nanoparticles.
≪ Production of Furan Dimethanol by Hydrogenation of HMF >
In a stainless steel reactor equipped with a magnetic stirrer, 0.4 g (3.17 mmol) of hydroxymethyl furfural, 40 g of ethanol and 80 mg of 1% Ru-AFPS were added and mixed to prepare a mixture in the form of a suspension. Hydrogen gas at room temperature was injected into the reactor where the mixture was present, and the reactor was heated to 70 캜 and stirred at 1000 rpm for 60 minutes while pressurizing the reactor to maintain the pressure at 435 psig. After the hydrogenation reaction, the reactor was cooled to 25 ° C and the pressure was reduced to atmospheric pressure. The mixture in the reactor was filtered to separate the insoluble 1% Ru-AFPS (reaction catalyst) A filtrate containing furan dime methanol was obtained.
[Example 2]
Except that 156 mg of ruthenium chloride (RuCl 3 3H 2 O) was added in the above Example 1. The remaining 3% Ru-AFPS supported 3% ruthenium nano- 2.2 g.
Thereafter, the filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 1, except that 80 mg of 3% Ru-AFPS was used instead of 1% Ru-AFPS.
[Example 3]
Except that 260 mg of ruthenium chloride (RuCl 3 3H 2 O) was added in the same manner as in Example 1, except that 5% ruthenium nano-particle supported catalyst (hereinafter, 5% Ru-AFPS) 2.3 g.
Thereafter, the filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 1, except that 80 mg of 5% Ru-AFPS was used instead of 1% Ru-AFPS.
[Example 4]
The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 2, except that 100 mg of 3% Ru-AFPS was used.
[Example 5]
The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 2, except that 120 mg of 3% Ru-AFPS was used.
[Example 6]
The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 3, except that the reactor was heated to 50 ° C during the hydrogenation reaction.
[Example 7]
The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 3, except that the reactor was heated to 60 ° C during the hydrogenation reaction.
[Example 8]
The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 3, except that the reactor was heated to 90 ° C during the hydrogenation reaction.
[Example 9]
The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner except that the hydrogenation reaction was carried out for 150 minutes in the above-mentioned Example 3.
[Example 10]
The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 5 except that the hydrogenation reaction was carried out for 120 minutes.
[Example 11]
The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner except that the hydrogenation reaction was carried out for 240 minutes in Example 5 above.
[Comparative Example 1]
Except that the porous polystyrene-divinylene polymer carrier (AFPS) functionalized with an amine functional group in which ruthenium nanoparticles were not supported was used instead of 1% Ru-AFPS as a hydrogenation catalyst in Example 1 In the same manner, a filtrate containing the reaction product of the present invention, furan dimethanol, was obtained.
[Comparative Example 2]
Except that 1% Ru-AFPS was used as a hydrogenation catalyst in Example 1, except that a porous polystyrene-divinylene polymer carrier (PS) not carrying ruthenium nanoparticles and not functionalized with an amine functional group was used The filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as the rest.
[Comparative Example 3]
A catalyst in which 5% of ruthenium nanoparticles were supported on a porous polystyrene-divinylene polymer carrier (PS) which was not functionalized with an amine functional group (hereinafter, referred to as " 5% Ru-PS).
Thereafter, the filtrate containing the reaction product of the present invention, furan-dimethanol, was obtained in the same manner as in Example 3, except that 5% Ru-PS was used instead of 5% Ru-AFPS.
[Comparative Example 4]
In Example 3, 2.3 g of a catalyst carrying 5% of ruthenium nanoparticles (hereinafter referred to as 5% Ru-C) was prepared using the carbon carrier (C) instead of AFPS as the hydrogenation catalyst support.
Thereafter, the filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 3, except that 5% Ru-C was used instead of 5% Ru-AFPS.
[Comparative Example 5]
(Hereinafter referred to as 5% Ru-Al 2 O 3 ) in which 5% of ruthenium nanoparticles were supported using an aluminum oxide carrier (Al 2 O 3 ) instead of AFPS as the hydrogenation reaction catalyst support in Example 3, 2.3 g.
Thereafter, the filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 3 except that 5% Ru-Al 2 O 3 was used instead of 5% Ru-AFPS .
[Comparative Example 6]
2.3 g of a catalyst carrying 5% of ruthenium nanoparticles (hereinafter referred to as 5% Ru-TiO 2 ) was prepared using the titanium oxide support (TiO 2 ) instead of AFPS as the hydrogenation catalyst support in Example 3 Respectively.
Thereafter, the filtrate containing the reaction product of the present invention, furan di-methanol, was obtained in the same manner as in Example 3 except that 5% Ru-TiO 2 was used instead of 5% Ru-AFPS.
[Comparative Example 7]
In Example 3, 2.3 g of a catalyst carrying 5% of ruthenium nanoparticles (hereinafter referred to as 5% Ru-SiO 2 ) was prepared using a silicon oxide carrier (SiO 2 ) instead of AFPS as a hydrogenation catalyst support Respectively.
Thereafter, the filtrate containing the reaction product of the present invention, furan dimethanol, was obtained in the same manner as in Example 3, except that 5% Ru-SiO 2 was used instead of 5% Ru-AFPS.
For ease of understanding, the experimental conditions of Examples 1 to 11 and Comparative Examples 1 to 7 of the present invention are shown in Table 1 below.
The results of measuring the pore size and pore volume of the reaction catalysts of Examples 1 to 3 and Comparative Examples 1 to 3 by the method of Experiment 1 are shown in the following Table 2 and the results of Examples 1 to 11 And the hydrogenation selectivity of furandimethanol from HMF were measured using the reaction catalysts of Comparative Examples 3 to 7. The results are shown in Table 3 below and in Table 3, Table 4 shows the results of measuring the re-use efficiency of the reaction catalyst using the reaction catalyst.
The results of Table 2 indicate that the AFPS functionalized with an amine group used as a carrier of the ruthenium nanoparticle-supported catalyst of the present invention has a finer nano-scale size compared to a non-functionalized general polymer carrier And has a large number of pores and a wide surface area. Thus, it can be seen that the ruthenium nanoparticles can be efficiently supported and thus, the catalysts can have excellent catalytic properties. In Table 2, ruthenium nanoparticles were measured for the polymer carrier (AFPS) through Examples 1 to 3 through the measurement of the pore size and pore volume of Examples 1 to 3 and Comparative Example 1, ) In the pores of the catalyst layer.
Also, from the results of Table 3 above, it can be seen that the embodiment of the present invention shows that the conversion ratio of hydroxymethyl furfural is at least 20% or more as compared with the comparative example in which the maximum conversion ratio of hydroxymethyl furfural is 19% As a result of performing the short-time hydrogenation reaction for 150 minutes to 240 minutes in the case of Example 9 and Example 11, the conversion ratio of hydroxymethylfurfural was 99 to 100%. As a result, the ruthenium nano- It can be confirmed that the hydrogenation reaction of hydroxymethyl furfural is effectively generated according to use. Particularly, in the case of the hydrogenation reaction under the same conditions and the ruthenium nano-particle-supported catalyst of the present invention as the reaction catalyst, the conversion of hydroxymethylfurfural Which is up to 813%. In addition, the embodiment of the present invention shows a remarkably high hydroxymethyl furfural conversion rate as compared with the comparative example, and the selectivity of furan dmethanol through the hydrogenation reaction of HMF is also 96% or more as high as that of hydroxymethyl furfural It can be confirmed that a large amount of furan di-methanol can be efficiently obtained in a short time when the ruthenium nano-particle-supported catalyst of the present invention is used as a reaction catalyst instead of the catalyst used conventionally in the hydrogenation reaction.
The ruthenium nanoparticle supported catalyst of the present invention exhibits remarkably excellent catalytic reactivity even after being reused several times in the hydrogenation reaction of HMF through the results of Table 4, It can be reused repeatedly as a reaction catalyst in the hydrogenation reaction of loxymethyl furfural, and thus it is possible to produce economical and efficient furandimethanol.
Claims (10)
b) hydrogenating the hydroxymethyl furfural by pressurizing, heating and stirring the mixture of step a); And
c) separating the furan dimethanol from the mixture obtained via step b);
Wherein the nitrogen-containing functional group is at least one functional group selected from the group consisting of an amide group, an amine group, a ketimine group, an aldimine group, an imide group, an azide group, an azo group, a cyanogenic group, an isocyanuric acid group, an isothiocyanic acid group, A nitro group, a nitroso group, and a pyridine group,
Wherein the selectivity of furan dmethanol is 96 to 98% at a conversion of 81 to 100%.
Wherein the reactor is a liquid ash type reactor or a continuous stationary phase reactor.
The ruthenium nano-particle-supported catalyst
(1) preparing a suspension by adding a porous polymer carrier functionalized with a nitrogen-containing functional group to a ruthenium solution prepared by dissolving a ruthenium salt in a solvent, and refluxing the suspension; And
(2) reducing the suspension through step (1);
Lt; RTI ID = 0.0 > ofhydroxymethylfurfural < / RTI >
Wherein the ruthenium salt is selected from the group consisting of ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium oxide, ruthenium hydroxide, ruthenium cyanide, ruthenium trifluoroacetate, ruthenium acetate, ruthenium acetylacetonate and tetramine dichloro ruthenium And the ruthenium salt is contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polymer carrier.
Wherein the reduction of step (2) is carried out by adding at least one reducing agent selected from sodium borohydride, potassium borohydride and hydrazine hydrate to the suspension.
Wherein the ruthenium nano-particle-supporting catalyst of step a) is contained in an amount of 0.05 to 100 parts by weight based on 100 parts by weight of hydroxymethyl furfural.
Wherein the pressurization of step b) is performed by injecting hydrogen gas into the reactor containing the mixture, and the internal pressure of the reactor is 15 to 900 psig.
Wherein the heating of step b) is carried out at a temperature of 30 to 200 ° C, and the hydrogenation is carried out for 30 to 600 minutes.
The method for hydrogenating hydroxymethylfurfural further comprises separating the solid catalyst ruthenium nano-particle supporting catalyst from the mixture obtained through step b) before and after step c) Wherein the supported ruthenium nanoparticle supported catalyst can be reused for the hydrogenation of hydroxymethyl furfural.
The separation of step c) can be carried out by distillation, and the furan dimethanol obtained through the separation step exhibits a selectivity of 90 to 98%.
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| US20070287845A1 (en) * | 2006-06-09 | 2007-12-13 | Battelle Memorial Institute | Hydroxymethylfurfural Reduction Methods and Methods of Producing Furandimethanol |
| JP4770173B2 (en) * | 2002-07-26 | 2011-09-14 | 和光純薬工業株式会社 | Polymer-supported ruthenium compounds having tertiary amino groups |
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| US20070287845A1 (en) * | 2006-06-09 | 2007-12-13 | Battelle Memorial Institute | Hydroxymethylfurfural Reduction Methods and Methods of Producing Furandimethanol |
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