KR101821182B1 - Catalyst for hydrodeoxygenation and method for preparing biofuel using the same - Google Patents

Abstract

Disclosed herein is a catalyst for hydrocracking reaction for producing a deoxygenated hydrocarbon compound from a biomass containing an oxygen-containing hydrocarbon compound, a process for producing the catalyst, and a process for producing a biofuel using the same. The catalyst for hydrocracking reaction includes a carrier on which ruthenium (Ru) and rhenium (Re) bimetallic metals are supported, and is capable of producing a deoxygenated hydrocarbon compound from the biomass-derived oxygen-oxygen hydrocarbon compound in a high yield .

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst for hydrothermal reaction and a method for producing biofuel using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention discloses a catalyst for hydrocracking, a method for producing the same, and a method for producing a biofuel using the same.

Recently, there is a growing interest in technologies that utilize biomass as sustainable energy source as a carbon resource due to the depletion of fossil fuels and the implementation of the Convention on Climate Change. In the case of bioethanol, the first-generation biofuel, corn and sugar cane, which are edible crops, are used as raw materials to raise the price of grain. In recent years, in order to solve these problems, R & D on technologies utilizing edible biomass is actively under way.

The woody biomass, which is distinguished from edible biomass mainly composed of cellulose, is composed of cellulose (40-80%), hemicellulose (15-30%) and lignin (10-25%). Among them, cellulose and hemicellulose can be used as raw materials for fuel production such as bioethanol through biological processes, but since lignin is a random phenol polymer, it is discarded as a by-product after the production process of bioethanol, thereby improving economical efficiency of production process of woody bioethanol Research and development are being actively pursued to find ways to utilize this technology.

Lignin has a complex three-dimensional structure of a three-dimensional polymer structure composed of various carbon-carbon or carbon-oxygen bonds of oxygen-containing aromatic rings. It is an aromatic monomer that can break the polymer structure of lignin and be used as various fuels and chemicals. The technology of switching is being studied all over the world. Such lignin decomposition techniques include pyrolysis, supercritical fluid liquefaction, chemical catalytic cracking, and gasification. In the case of a lignin-derived liquid compound obtained by such a chemical decomposition technique, it is composed of an aromatic hydrocarbon compound containing oxygen. In order to utilize the oxygenated hydrocarbon compounds of the lignin decomposition product as a fuel for transporting gasoline, diesel, and aviation oil, oxygen is selectively removed through a hydrocracking reaction, and oxygen is removed from the oxygen-containing aromatic hydrocarbon or cyclic hydrocarbon, The process is receiving much attention. Therefore, there is a need to develop a catalyst for hydrocracking reaction in which a lignin-derived oxygen hydrocarbon compound is stably converted into a deoxygenated hydrocarbon compound at a high yield.

Korean Patent Publication No. 10-2014-0095005

In one aspect, the present invention aims to provide a catalyst for hydrocracking oxygen reaction for producing a high-yield deoxygenated hydrocarbon compound from a biomass-derived oxygen-oxygen hydrocarbon compound.

In another aspect, the present invention relates to a process for producing a high-yield oxygen-free hydrocarbon compound from a hydrogen-oxygen hydrocarbon compound derived from biomass using a catalyst for hydrocracking oxygen reaction having a high deoxidization activity and a high stability, And a method for producing the biofuel.

In one aspect, the techniques disclosed herein include a carrier; And ruthenium (Ru) and rhenium (Re) bimetallic metals supported on the carrier.

In an exemplary embodiment, the carrier may be carbon, titania, zirconia, alumina, or a silica carrier.

In an exemplary embodiment, the ruthenium metal content may be 1 to 10 parts by weight based on 100 parts by weight of the carrier.

In an exemplary embodiment, the rhenium metal content may be supported at a molar ratio of 0.1 to 0.7 relative to the ruthenium metal.

In another aspect, the technique disclosed in the present specification is a method for producing the catalyst for hydrocracking oxygen reaction, comprising the step of reducing a catalyst having ruthenium and rhenium binary metal supported on a carrier at 150 to 350 DEG C under a hydrogen flow, A method for producing a catalyst for an oxygen reaction is provided.

In another aspect, the technique disclosed in this specification provides a method for producing a biofuel comprising the step of producing a deoxygenated hydrocarbon compound from a biomass containing an oxygen-containing hydrocarbon compound using the catalyst for hydrocracking reaction.

In an exemplary embodiment, the oxygen-containing hydrocarbon compound may include at least one selected from the group consisting of a guaiacol, diphenyl ether, and benzyl phenyl ether.

In one exemplary embodiment, the guaiacol, diphenyl ether, and benzyl phenyl ether may be lignin monomers obtained from pyrolysis oils of woody biomass.

In an exemplary embodiment, the deoxygenated hydrocarbon compound may be at least one selected from the group consisting of cyclohexane (C ₆ H ₁₂ ) and alkylated cyclohexane.

In an exemplary embodiment, the hydropathic oxygenation reaction may be conducted at a temperature of 200 to 350 < 0 > C.

In one aspect, the technique disclosed in this specification has an effect of providing a catalyst for hydrocracking oxygen reaction for producing a deoxidized hydrocarbon compound in high yield from a biomass-derived oxygen-hydrocarbon compound.

In another aspect, the technique disclosed in the present specification uses a catalyst for hydrocracking oxygen reaction having high deoxidizing activity and high stability to produce a high yield of oxygen-free hydrocarbons from hydrocarbons derived from biomass, There is an effect of providing a method for producing a biofuel for producing a compound.

FIG. 1 shows the results of TEM and STEM-EDX analysis of a catalyst for hydrogenation of ruthenium-rhenium binary metal according to an experimental example of the present invention.
FIG. 2 shows the results of XPS analysis of a catalyst for hydrogenation of ruthenium-rhenium binary metal according to an experimental example of the present invention.

Hereinafter, the present invention will be described in detail.

In one aspect, the technology disclosed herein is a catalyst for hydrocracking oxygenation reaction for producing a high yield deoxygenated hydrocarbon compound from a biomass-derived oxygen-hydrocarbon compound, comprising: a carrier; And ruthenium (Ru) and rhenium (Re) bimetallic metals supported on the carrier.

The catalyst promotes the hydrocracking of the biomass, thereby producing a high yield biofuel.

In an exemplary embodiment, the carrier may be a carbon carrier or a metal oxide carrier.

In an exemplary embodiment, the carbon carrier is selected from the group consisting of carbon black, carbon nanotubes (CNT), graphite, graphene, activated charcoal, porous carbon, ) And a carbon nanowire (Carbon nano wire).

In an exemplary embodiment, the metal oxide support may be a single metal oxide support, for example a single metal oxide support of titania, zirconia, alumina, or silica.

In a preferred embodiment, it is preferable that the carrier contains a high durable carbon carrier or a titania carrier having high water resistance because the biomass-derived compounds contain a large amount of water.

In an exemplary embodiment, the ruthenium metal content may be 1 to 10 parts by weight based on 100 parts by weight of the carrier. Specifically, the content of the ruthenium metal is 1 to 8 parts by weight, 2 to 6 parts by weight, 3 to 5 parts by weight, or 4 to 5 parts by weight based on 100 parts by weight of the support, And exhibits excellent effects in terms of yield.

In an exemplary embodiment, the rhenium metal content may be supported at a molar ratio of 0.1 to 0.7 relative to the ruthenium metal. Specifically, the content of the rhenium metal is in the range of 0.1 to 0.5 molar ratios, 0.2 to 0.5 molar ratios, or 0.3 to 0.5 molar ratios to the ruthenium metal, showing excellent effects in terms of conversion of guaiacol and yield of completely deoxygenated compounds.

In an exemplary embodiment, the catalyst for hydrocracking reaction may be reduced at 150 to 350 占 폚 under a hydrogen flow. For catalytic activation, the reduction temperature is in the range of 150 to 350 캜, specifically 150 to 320 캜, more specifically 150 to 300 캜, more specifically 180 to 300 캜, more specifically 200 to 300 캜, more specifically 220 to 280 캜 Is preferable from the viewpoints of high conversion of guaiacol and yield of fully deoxygenated compound.

The catalyst for hydrocracking reaction according to the present invention comprises: impregnating a carrier with an aqueous solution of a ruthenium precursor; Calcining the carrier impregnated with the ruthenium metal; Impregnating the sintered carrier with an aqueous solution of a rhenium precursor to prepare a catalyst carrying ruthenium and rhenium binary metal; And calcining the catalyst and reducing it under hydrogen gas.

In an exemplary embodiment, the catalyst for hydrocracking is formed by impregnating a carrier with an aqueous solution of a ruthenium precursor, firing the carrier impregnated with the ruthenium metal at 100 to 500 ° C for 3 to 8 hours, Followed by calcination at 100 to 500 ° C for 3 to 8 hours, and reduction at 150 to 350 ° C for 2 to 5 hours under hydrogen gas. For catalytic activation, the reduction temperature is in the range of 150 to 350 캜, specifically 150 to 320 캜, more specifically 150 to 300 캜, more specifically 180 to 300 캜, more specifically 200 to 300 캜, more specifically 220 to 280 캜 Is preferable from the viewpoints of high conversion of guaiacol and yield of fully deoxygenated compound.

In another aspect, the technique disclosed in this specification provides a method for producing a biofuel comprising the step of producing a deoxygenated hydrocarbon compound from a biomass containing an oxygen-containing hydrocarbon compound using the catalyst for hydrocracking reaction. The method for producing the biofuel has the effect of producing a deoxygenated hydrocarbon compound from a deoxygenated hydrocarbon compound through a hydrocracking reaction using alcohols such as ethanol, butanol, and propanol as a hydrogen donor at a high yield. Therefore, the use of alcohol as a hydrogen donor instead of high-pressure hydrogen gas having low process economy provides an advantage in terms of efficiency as well as economy.

In an exemplary embodiment, the oxygen-containing hydrocarbon compound may include at least one selected from the group consisting of a guaiacol, diphenyl ether, and benzyl phenyl ether.

In one exemplary embodiment, the guaiacol, diphenyl ether, and benzyl phenyl ether may be lignin monomers obtained from pyrolysis oils of woody biomass.

In an exemplary embodiment, the deoxygenated hydrocarbon compound is one or more selected from the group consisting of cyclohexane (C ₆ H ₁₂ ) and alkylated cyclohexane (eg, methylcyclohexane (CH ₃ C ₆ H ₁₁ )) .

In an exemplary embodiment, the hydropathic oxygenation reaction may be conducted at a temperature of 200 to 350 < 0 > C. The reaction temperature is preferably from 220 to 350 ° C, specifically from 240 to 350 ° C, more specifically from 240 to 300 ° C, from the viewpoints of high guaiacol conversion and a complete deoxygenated compound yield.

In an exemplary embodiment, the hydropathic oxygenation reaction may be conducted at a pressure of 20 to 80 bar.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example 1.

Activated charcoal Carbon carrier was dried in an oven at 120 ° C for 4 hours and impregnated with an aqueous solution of ruthenium chloride (RuCl ₃ ). The amount of ruthenium metal supported was 4 parts by weight with respect to the carbon carrier. The ruthenium metal-impregnated carbon catalyst (Ru / C) was again dried in an oven at 120 ° C. for 4 hours and then impregnated with an aqueous solution of ammonium perrhenate (NH ₄ ReO ₄ ). The rhenium metal loading was adjusted so that the molar ratio (Re / Ru) to ruthenium metal was 0.25. The carbon catalyst (RuRe / C) impregnated with a ruthenium metal and a rhenium metal was dried in an oven at 120 ° C. for 4 hours and then reduced again in a hydrogen stream at 250 ° C. for 3 hours to prepare a catalyst.

Example 2.

A catalyst was prepared in the same manner as in Example 1, except that the molar ratio (Re / Ru) of rhenium metal loaded to ruthenium metal was adjusted to be 0.5.

Example 3.

A catalyst was prepared in the same manner as in Example 1 except that the molar ratio (Re / Ru) of the rhenium metal loaded to the ruthenium metal was adjusted to be 0.75.

Example 4.

A catalyst was prepared in the same manner as in Example 2, except that the catalyst was reduced in a hydrogen stream at 150 ° C for 3 hours during the reduction of the catalyst.

Example 5.

The catalyst was prepared in the same manner as in Example 2 except that the catalyst was reduced in a hydrogen stream at 400 ° C. for 3 hours during the reduction of the catalyst.

Example 6.

A catalyst was prepared in the same manner as in Example 2 except that a titania carrier (TiO ₂ ) was used in place of the carbon carrier, and the titania carrier was calcined at 500 ° C. for 4 hours in an air atmosphere before ruthenium metal impregnation. After rhenium metal impregnation, the catalyst was calcined at 300 ° C for 4 hours in an air atmosphere, and then reduced at 250 ° C for 3 hours in a hydrogen stream to prepare a catalyst (RuRe / TiO ₂ ).

Comparative Example  1 to 5.

A ruthenium catalyst (Ru / C, manufactured by Sigma Aldrich) supported on a carbon carrier was used as the catalyst of Comparative Example 1.

Further, a ruthenium catalyst (Ru / Al ₂ O ₃ , manufactured by Sigma Aldrich) supported on an alumina support was used as a catalyst of Comparative Example 2.

The catalyst (Ru / H-Beta) was prepared by impregnating an aqueous solution of ruthenium chloride (RuCl ₃ ) with zeolite H-Beta (CP814C manufactured by Zeolyst)

In addition, a palladium catalyst (Pd / C, manufactured by Sigma Aldrich) supported on a carbon carrier with another noble metal catalyst was used as the catalyst of Comparative Example 4.

Also, a catalyst (Ni / C) was prepared by impregnating a carbon carrier with an aqueous solution of nickel chloride (NiCl ₂ ) as a non-noble metal catalyst, and used as a catalyst of Comparative Example 5.

The amount of metal supported on each catalyst of Comparative Examples 1 to 5 was 5 parts by weight based on the carrier. In the case of the catalysts of Comparative Examples 1 to 4, the catalysts were reduced in a hydrogen stream at 300 ° C for 3 hours and used for the reaction. In the case of the catalyst of Comparative Example 5, the catalysts were reduced in a hydrogen stream at 450 ° C for 3 hours Were used for the reaction.

Comparative Example 6

A catalyst (Ru / C) in which 4 parts by weight of ruthenium was supported on a carbon support was prepared in the same manner as in Example 1 above. Thereafter, the dried Ru / C catalyst was impregnated with an aqueous solution of ammonium molybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ ). The amount of molybdenum metal supported was controlled so that the molar ratio (Mo / Ru) to the ruthenium metal was 0.1. The ruthenium-molybdenum-loaded carbon catalyst (RuMo / C) was dried in an oven at 120 ° C for 4 hours, then reduced again in a hydrogen stream at 250 ° C for 3 hours and then used for hydrocracking.

Comparative Example 7

A catalyst was prepared in the same manner as in Comparative Example 6 except that the dried Ru / C catalyst was impregnated with an aqueous solution of ammonium tungstate ((NH ₄ ) ₁₀ W ₁₂ O ₄₂ ). The ruthenium-tungsten-loaded carbon catalyst (RuW / C) was prepared by adjusting the molar ratio (W / Ru) of tungsten metal to ruthenium metal to 0.1.

Comparative Example  8.

The catalyst was prepared in the same manner as in Comparative Example 7 except that the amount of tungsten metal supported was adjusted to 0.5 (W / Ru) relative to that of ruthenium metal to prepare a ruthenium-tungsten supported carbon catalyst (RuW / C).

Experimental Example 1. Hydrophobic Oxygen Reaction with Various Catalysts

A 160 mL batch reactor was used to carry out the hydrocracking reaction of guaiacol. Each of the catalysts prepared in Example 2 and Comparative Examples 1 to 7 (0.1 g) was charged into a reactor, and 0.1 M of guanacrole mixed with 2-propanol (24 mL) was added to the reactor. Then, the nitrogen gas was filled up to 20 bar and the impeller attached to the reactor was operated at 500 rpm and stirred to raise the reaction temperature to 200 ° C. After reaching the reaction temperature, the reaction was maintained for 5 hours and the reaction products were analyzed by GC. The hydrogen required for deoxygenation was fed from the hydrogen produced by the dehydrogenation of 2-propanol during the reaction. The experimental results are shown in Table 1 below.

practice
Example 2 compare
Example 1 compare
Example 2 compare
Example 3 compare
Example 4 compare
Example 5 compare
Example 6 compare
Example 7 compare
Example 8 RuRe / C Ru / C Ru / Al ₂ O ₃ Ru / H-Beta Pd / C Ni / C RuMo / C RuW / C RuW / C Gui Icool Conversion Rate (%) 99.1 99.3 99.3 9.9 89.3 17.5 94.4 85.0 56.9 Total Deoxygenated Compound Yield (%) 37.9 0.8 2.2 0.0 8.8 0.3 24.5 27.9 4.5 Compound yield (%) containing one oxygen 51.1 73.7 70.3 0.0 27.4 10.9 64.3 53.0 43.5 Yield of compound containing two oxygen (%) 2.2 13.1 16.1 77.5 44.6 4.1 4.6 3.0 45.07 Cyclohexane yield (%) 37.9 0.8 2.2 0.0 8.8 0.3 24.5 27.9 4.5

According to Table 1, it can be seen that the RuRe binary metal catalyst (Example 2) supported on the carbon carrier exhibits the highest activity in the conversion of the guaiacol and the yield of the completely deoxygenated compound. Compared with this, ruthenium single metals (Comparative Examples 1 and 2) supported on a carbon or alumina support exhibited a high conversion of guaiacol, but a completely deoxygenated compound was hardly produced. In addition, palladium (Comparative Example 4) and nickel (Comparative Example 5) supported carbon catalysts, which are other transition metal catalysts, also exhibited remarkably low deoxygenation activity. In the case of the carbon catalyst carrying molybdenum (Comparative Example 6) or tungsten (Comparative Example 7) instead of rhenium in ruthenium, it exhibited higher deoxygenation activity than the ruthenium single metal-loaded carbon catalyst (Comparative Example 1) The alcohol conversion and the total deoxygenated compound yield were still lower than in Example 2, and the catalysts loaded with increasing amounts of tungsten metal (Comparative Example 8) showed significantly lower activity. As a result, it was found that the carbon carrier on which the RuRe binary metal was supported exhibited a very high conversion of the guaiacol and the complete deoxygenated compound yield.

Experimental Example 2. Various Re / Ru molar ratios, catalytic reduction temperature and hydrocracking oxygenation reaction

Each of the catalysts prepared in Examples 1 to 5 (0.1 g) was introduced into a reactor, and the hydrocracking reaction of guaiacol was carried out at a reaction temperature of 200 ° C. for 5 hours in the same manner as in Experimental Example 1. However, in the case of the catalysts of Examples 1 and 2, it was also tested at a hydrocracking reaction temperature of 240 ° C. The experimental results are shown in Table 2 below.

catalyst Example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Example 2 RuRe / C RuRe / C RuRe / C RuRe / C RuRe / C RuRe / C RuRe / C Re / Ru ratio 0.25 0.5 0.75 0.5 0.5 0.25 0.5 Catalyst reduction temperature (캜) 250 250 250 150 400 250 250 Reaction temperature (캜) 200 200 200 200 200 240 240 Gui Icool Conversion Rate (%) 94.6 99.1 70.9 97.2 67.6 98.9 99.0 Total Deoxygenated Compound Yield (%) 30.7 37.9 21.6 29.9 13.1 46.1 56.4 Compound yield (%) containing one oxygen 59.1 51.1 43.6 61.2 46.9 41.4 30.5 Yield of compound containing two oxygen (%) 3.6 2.2 2.5 3.5 3.1 2.0 1.1 Cyclohexane yield (%) 30.7 37.9 21.6 29.9 13.1 46.1 56.4

According to Table 2, it can be seen that among the RuRe / C catalysts prepared with various Re / Ru molar ratios, the catalyst having the Re / Ru ratio of 0.5 (Example 2) exhibited the highest spherical ion conversion and the total yield of the completely deoxygenated compound . In the case of the catalyst having a high content of rhenium having Re / Ru ratio of 0.75 (Example 3), the conversion of guaiacol and the yield of completely deoxygenated compound were drastically lowered.

Also, it was confirmed that the catalyst reduction temperature during the catalyst production also had a great effect on the deoxygenation activity. Specifically, when the catalyst was reduced at temperatures of 150 ° C. and 250 ° C. (Examples 4 and 2), excellent deoxidizing activity was exhibited. On the other hand, when the catalyst was reduced at a high temperature such as 400 ° C. (Example 5) Lt; / RTI >

Also, it was confirmed that when the catalytic reaction was carried out by increasing the hydrogenation reaction temperature to 240 ° C, the deoxygenation efficiency increased sharply. Specifically, in the case of RuRe / C (Re / Ru = 0.5, Example 2) catalyst, 99% conversion of guaiacol and yield of complete deoxygenated compound of 56.4% were shown.

Experimental Example 3 TEM and H of ruthenium-rhenium catalyst ₂ -TPR analysis

The TEM and STEM-EDX analysis results of the ruthenium-rhenium catalyst (RuRe / C, Example 2) supported on carbon are shown in FIG. TEM analysis showed that the nanometer-sized particles of 1 to 2 nm in size were well dispersed in the carbon carrier. From the STEM-EDX analysis, it was found that ruthenium and rhenium were uniformly distributed on the catalyst surface. there was.

The oxidation state of the rhenium metal was measured on the surface of the catalyst by XPS analysis of the RuRe / C catalyst (Example 2), and the XPS spectrum of Re4f is shown in FIG. The XPS analysis showed that the oxidation state of rhenium before and after the reaction was almost unchanged and was present in the form of rhenium oxide of ReO ₂ and ReO ₃ . Therefore, it was found that maintaining the oxidized form of rhenium by applying an appropriate reducing temperature is important for catalyst activation since rhenium oxide acts as a catalytic active site.

Experimental Example 4 Hydrodensitivity of ruthenium-rhenium catalyst under hydrogen pressure

Each of the catalysts prepared in Examples 2 and 6 (0.1 g) was charged into a reactor, and 0.1 M of a reactant mixed with n-heptane (24 mL) was added to the reactor. As reactants, guaiacol, diphenyl ether and benzyl phenyl ether derived from lignin degradation products were used. Then, the hydrogen gas was filled up to 20 bar, and the impeller attached to the reactor was operated at 500 rpm and stirred to increase the reaction temperature to 240 ° C. After reaching the reaction temperature, the reaction was maintained for 2.5 hours and the reaction products were analyzed by GC. The experimental results are shown in Table 3 below.

Example 2 Example 6 RuRe / C RuRe / TiO ₂ Reactant Guaiacol Benzyl phenyl ether Diphenyl ether Guaiacol Conversion Rate (%) 100 100 100 100 Total Deoxygenated Compound Yield (C mol%) 87.4 96.2 96.9 76.1 Compound yield (C mol%) containing one oxygen 1.2 2 0 0 Compound yield (C mol%) containing two oxygen atoms 0 0 0 0 Cyclohexane yield (C mol%) 87.4 44.0 96.6 76.1 The yield of methylcyclohexane (C mol%) 0 50.6 0 0

Table 3 shows that bimetallic catalysts of ruthenium-rhenium under hydrogen pressure show very good activity on the hydrocracking reaction of various lignin degradation products. Specifically, in the case of the catalyst of Example 2 (RuRe / C), it was confirmed that 100% conversion and high total deoxygenated compound yields of 87 to 97% were obtained for all of the reactants of guaiacole, benzyl phenyl ether and diphenyl ether Respectively. In the case of the catalyst (RuRe / TiO ₂ ) of Example 6 carried on the titania carrier, 100% conversion and a high yield of complete deoxygenated compound of 76% were obtained for guaiacol. Accordingly, it has been found that the ruthenium-rhenium binary metal catalysts disclosed herein produce fully deoxygenated hydrocarbons in high yields from various lignin degradation product-derived oxygenated hydrocarbon compounds.

Having described specific portions of the present invention in detail, it will be apparent to those skilled in the art that this specific description is only a preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

carrier; And
A ruthenium (Ru) and a rhenium (Re) bimetal supported on the carrier,
The carrier is a carbon, titania or silica carrier,
Wherein the rhenium metal content is carried in a molar ratio of 0.1 to 0.7 based on the ruthenium metal.
The method according to claim 1,
Wherein the carrier is a carbon carrier.
The method according to claim 1,
Wherein the content of the ruthenium metal is 1 to 10 parts by weight based on 100 parts by weight of the carrier.
The method according to claim 1,
Wherein the rhenium metal content is carried in a molar ratio of 0.2 to 0.5 based on the ruthenium metal.
A process for producing a catalyst for hydrothermal reaction according to any one of claims 1 to 4,
And reducing the catalyst having ruthenium and rhenium binary metal supported on the carrier at 150 to 350 占 폚 under a hydrogen flow.
A method for producing a biofuel comprising the step of preparing a deoxygenated hydrocarbon compound from a biomass containing an oxygen-containing hydrocarbon compound using the catalyst for hydrocracking according to any one of claims 1 to 4.
The method according to claim 6,
Wherein the oxygen-containing hydrocarbon compound comprises at least one selected from the group consisting of guaiacol, diphenyl ether, and benzyl phenyl ether.
8. The method of claim 7,
Wherein said guaiacol, diphenyl ether and benzyl phenyl ether are lignin monomers obtained from pyrolyzed oils of woody biomass.
The method according to claim 6,
Wherein the deoxygenated hydrocarbon compound is at least one selected from the group consisting of cyclohexane (C ₆ H ₁₂ ) and alkylated cyclohexane.
The method according to claim 6,
Wherein the hydrocracking reaction is carried out at a temperature of 200 to 350 占 폚.

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