JP6651196B2 - Method for producing C5 + compound - Google Patents

Description

The present invention relates to, for example, a method for producing a C ₅₊ compound from a sugar alcohol having 5 or 6 carbon atoms derived from cellulosic biomass. The present invention relates to a method for producing a C5 ₊ compound by chemical decomposition.

In the process of producing a fuel substrate from cellulosic biomass, hydrocarbons, alcohols and ketones having a large number of carbon atoms are required. For example, glucose obtained by hydrolyzing cellulose is represented by the molecular formula of C ₆ H ₁₂ O ₆ , and the linear alkane having the largest number of carbon atoms obtained therefrom is hexane represented by C ₆ H _14. . However, fragmentation in the reaction process results in organic acids, alcohols and hydrocarbons having a small number of carbon atoms, and cannot increase the yield of hexane.

  For example, Patent Literature 1 discloses a method for producing a hydrocarbon in which a hydrocarbon having a large number of carbon atoms can be obtained in a higher yield from a cellulosic biomass via a saccharide in the presence of a catalyst. The first step of hydrolyzing and saccharifying cellulosic biomass to obtain saccharides and the second step of hydrocracking saccharide alcohols obtained by hydrogenating saccharides to obtain hydrocarbons are the same Ir-Re system. It is stated that the process proceeds in the presence of a catalyst to obtain a hydrocarbon mainly maintaining the carbon number of the saccharide obtained in the first reaction step.

Patent Documents 2 and 3 also disclose methods for producing hydrocarbons, ketones, and alcohols from oxygenated hydrocarbons derived from biomass. In detail, glucose, which is a cyclic sugar molecule derived from biomass, is converted into a linear polyhydric alcohol such as sorbitol by a hydrogenation reaction or a hydrogenolysis reaction, and this is defunctionalized by a deoxygenation reaction to form an alcohol. , Ketones, aldehydes, furans, diols, triols, hydroxycarboxylic acids, carboxylic acids, and the like. Further, a condensation reaction is performed on the condensation catalyst under the conditions of a predetermined temperature and pressure to obtain a compound having a larger number of carbon atoms, for example, an alcohol having 4 or more carbon atoms, a ketone, an alkane, an alkene, and having 5 or more carbon atoms. It is said to produce cycloalkanes, cycloalkenes, aryls, fused aryls, and mixtures thereof (C4 ₊ compounds). At this time, it is stated that hydrogen used in the hydrocracking is preferably obtained in situ from the above polyhydric alcohol, such as sorbitol, by utilizing aqueous phase reforming.

Further, Patent Document 4 discloses a method for producing a C ₄₊ compound by condensing an oxygenate containing C ₁₊ O _1-3 hydrocarbon by a catalytic reaction using a condensation catalyst. More specifically, a saccharide or the like is catalyzed with H ₂ in the presence of a hydrogenation catalyst to first generate oxygenated hydrocarbons including C ₁₊ O ₁₊ hydrocarbons, and a part of the oxygenated hydrocarbons is converted into an aqueous phase. and water and allowed to catalytic reaction in the presence of a quality catalyst to generate H _2, the H ₂ when is the remainder of oxygenated hydrocarbons and catalytic reaction in the presence of a deoxygenation catalyst _(generation of H ₂ in _situ) Oxygenates containing C ₁₊ O _1-3 hydrocarbons can be produced. This is condensed to C ₄₊ compounds by a catalytic reaction using a condensation catalyst. Here, it is stated that the water phase reforming catalyst and the deoxygenation catalyst can be made atomically the same, for example, alloying or additive mixing with Ni, Ru, Cu, Fe, Rh, Re, an alloy thereof, or a combination thereof. It is assumed that the Pt is included.

JP-A-2015-67800 JP 2014-159597 A JP 2014-167004 A JP 2010-535703 A

In the case of obtaining hydrocarbons, monoalcohols, and monoketones from sugar alcohols, in order to obtain hydrogen used for hydrocracking in situ by aqueous phase reforming, an aqueous phase reforming reaction and a hydrocracking reaction are required. It is necessary to proceed in the same environment. For example, in the case of sorbitol, which is a sugar alcohol having 6 carbon atoms, in the aqueous phase reforming, the higher the temperature is 200 ° C. or higher, the more efficiently the reaction proceeds and hydrogen can be obtained efficiently. The more it is, the more the carbon chain tends to be cut, and the number of carbon atoms of the obtained hydrocarbon becomes small. In other words, big number most carbon obtained from sorbitol, i.e. hydrocarbons having a carbon number of 6, the yield of C ₆ compounds are monoalcohols, and monoketone becomes lower. For example, The same applies to the case of obtaining a hydrocarbon having 5 carbon atoms xylitol is a sugar alcohol having 5 carbon atoms, monoalcohols, and C ₅ compounds are monoketones. In the following, the C ₆ compound and the C ₅ compound are collectively referred to as a C ₅₊ compound.

The present invention has been made in view of the above situation, and an object thereof is to reform a part of a sugar alcohol having 5 or 6 carbon atoms in an aqueous phase and hydrocrack the remainder. To provide a method for producing a C5 ₊ compound at a high yield while maintaining the carbon number of the sugar alcohol.

The method for producing a C ₅₊ compound according to the present invention is a method for producing a C ₅₊ compound while maintaining the carbon number by reforming a part of a sugar alcohol having 5 or 6 carbon atoms in an aqueous phase and hydrocracking the remainder. Wherein the raw material solution containing the sugar alcohol is mixed with a catalyst selected from Pt, Pd, Rh and a catalyst selected from Ir-ReO _x , Rh-MoO _{x on} SiO ₂ or TiO _2. It is characterized by heating and holding in the presence of the supported catalyst particles.

According to this invention, even if the amount of hydrogen produced by aqueous phase reforming is reduced, the obtained hydrogen can be efficiently used for hydrocracking, and the yield can be increased while maintaining the carbon number of the sugar alcohol. C ₅₊ compounds can be prepared.

In the above invention, the raw material solution may be heated to a temperature at which hydrogen gas is not desorbed. According to the invention, hydrogen obtained by aqueous phase reforming can be efficiently used for hydrocracking by reducing the diffusion rate of hydrogen gas, and as a result, desorption of hydrogen gas can be suppressed, and sugar alcohol can be suppressed. C5 ₊ compounds can be produced with high yield while maintaining the carbon number of

In the above invention, an organic solvent may be provided so as to cover the raw material solution. According to this invention, the C ₅₊ compound can be produced in a high yield while maintaining the carbon number of the sugar alcohol, and the C ₅₊ compound is dissolved in an organic solvent to facilitate the recovery.

In the above invention, the sugar alcohol may be sorbitol, and the sugar alcohol may be heated to a temperature at which the CO ₂ yield relative to the amount of the sorbitol in the raw material solution is 50% or less. According to this invention, the reaction can be promoted while maintaining the carbon number even by hydrogenolysis, and the C ₅₊ compound can be produced in high yield while maintaining the carbon number of the sugar alcohol, and The yield can be improved.

In the above invention, the raw material solution may be heated at 190 ° C. or lower. According to this invention, the reaction can be promoted while maintaining the carbon number even by hydrogenolysis, and the C ₅₊ compound can be produced in high yield while maintaining the carbon number of the sugar alcohol, and The yield can be improved.

In the above invention, the raw material solution may be heated at 170 ° C. or higher. According to this invention, the aqueous phase reforming can be efficiently promoted, and the C ₅₊ compound can be produced in a high yield while maintaining the carbon number of the sugar alcohol, and the yield can be improved. .

FIG. 3 is a view showing a reaction step in the present invention. FIG. 3 is a view showing an elementary reaction in a reaction step in the present invention. FIG. 3 is a view showing a reaction step in the present invention. FIG. 2 is a view showing an elementary reaction in a reaction step in the present invention. It is a figure which shows the reaction process in this invention typically.

Hereinafter, one example of the method for producing a C ₅₊ compound according to the present invention will be described in detail.

The method for producing a C5 ₊ compound according to the present invention maintains the carbon number from sorbitol which is a sugar alcohol having 6 carbon atoms derived from cellulosic biomass or xylitol which is a sugar alcohol having 5 carbon atoms. ₆ is a compound or method to be produced C ₅ compounds having 5 carbon atoms in higher yields. Here, the C ₆ compound is a hydrocarbon having 6 carbon atoms, monoalcohol and monoketone, and includes hexane, hexanol, hexanone and their structural isomers, and the C ₅ compound is a hydrocarbon having 5 carbon atoms, monoalcohol and monoketone. And includes pentane, pentanol, pentanone and their structural isomers.

FIG. 1 is a diagram showing an example of the reaction in the present invention. Hydrogen is obtained from a portion of sorbitol by aqueous phase reforming, and the hydrogen is used to hydrolyze the remainder of sorbitol (or cellulose or glucose before being decomposed into sorbitol) to obtain, in particular, hydrogen. It is intended to obtain a C ₆ compound having the largest carbon number. The sorbitol can be obtained, for example, by hydrolyzing cellulose in cellulosic biomass and hydrogenating saccharified glucose.

In detail, referring also to FIG. 2, in the aqueous phase reforming, a Pt-based catalyst can be used, and carbon dioxide (CO ₂ ) and hydrogen can be obtained from sorbitol and water. In such an aqueous phase reforming reaction, the higher the temperature, the more the reaction can proceed and the amount of generated hydrogen can be increased, and the ideal reaction temperature is 200 ° C. or higher. Meanwhile in the hydrogenolysis reaction, for example, to obtain using Ir-Re-based catalysts, may be sorbitol and hydrogen hexane to give C ₆ compound with water hexanol and hexanone. In such a hydrogenolysis reaction, the lower the temperature, the higher the selectivity to cut the C—O bond without cutting the C—C bond. That is, the reaction can proceed without breaking the carbon chain, and the ideal reaction temperature is about 140 ° C.

FIG. 3 is a diagram showing another example of the reaction in the present invention. Hydrogen is obtained from a portion of xylitol by aqueous phase reforming, and the hydrogen is used to hydrolyze the remainder of xylitol (or hemicellulose and xylose before decomposing to xylitol). it is intended to obtain the greatest C ₅ carbon number compounds. Xylitol can be obtained, for example, by hydrolyzing saccharified xylose by hydrolyzing hemicellulose in cellulosic biomass.

Specifically, referring also to FIG. 4, in the aqueous phase reforming, a Pt-based catalyst can be used, and carbon dioxide (CO ₂ ) and hydrogen can be obtained from xylitol and water. In such an aqueous phase reforming reaction, the higher the temperature, the more the reaction can proceed and the amount of generated hydrogen can be increased, and the preferable reaction temperature is 200 ° C. or higher. Meanwhile in the hydrogenolysis reaction, for example, to obtain using Ir-Re catalysts can be obtained pentane xylitol and hydrogen, a C ₅ compound and water pentanol and pentanone. In such a hydrogenolysis reaction, the lower the temperature, the higher the selectivity to cut the C—O bond without cutting the C—C bond. That is, the reaction can proceed without cutting the carbon chain, and the preferable reaction temperature is about 140 ° C.

Referring to FIG. 5, in the present invention, such an aqueous phase reforming reaction and a hydrocracking reaction are allowed to proceed in a single aqueous phase 2 of a single vessel 4, that is, under the same environment. For that purpose, it is considered to use a catalyst having high catalytic activity in combination for each of the aqueous phase reforming reaction and the hydrocracking reaction. Such catalysts, catalyst particle 1 by _{Pt / Ir-ReO x / SiO} 2 catalysts were co carrying Pt and Ir-ReO _x to SiO ₂ is preferable. With such a Pt / Ir-ReO _x / SiO ₂ catalyst, the generation of hydrogen and the hydrocracking reaction in the aqueous phase reforming reaction can proceed at the same time as compared with the case where the Pt catalyst and the Ir-ReO _x catalyst are provided, respectively. C ₅₊ compounds can be produced in high yields. The carrier of the catalyst may be TiO ₂ . It is also possible as Pd or Rh in place of Pt, may be Rh-MoO _x in place of Ir-ReO _x. Here, _x in ReO _x and MoO _x indicates an oxidation number, and is an arbitrary real number.

The catalyst particles 1 are put into an aqueous phase (raw material solution) 2 containing sorbitol or xylitol, and the aqueous phase reforming reaction and the hydrocracking reaction proceed under the same environment. Here, it is important that hydrogen generated by the aqueous phase reforming reaction be efficiently used for the hydrocracking reaction without being desorbed, that is, consumed in the hydrocracking reaction. Therefore, it cause adjacent the active sites of the active sites and hydrocracking reactions in the aqueous phase reforming reaction by co-loading Pt and Ir-ReO _x to SiO ₂ in the catalyst. In such a co-supported catalyst, the hydrogen generated by the aqueous phase reforming reaction can be efficiently consumed in the hydrocracking reaction, so that the reaction temperature can be relatively low, and the carbon chain is cut by the hydrocracking reaction. And a C5 ₊ compound can be obtained with a high yield.

The surface of the aqueous phase 2 stored in the container 4 is covered with an oil phase 3 made of an organic solvent. Then, only the generated C ₅₊ compound is moved to the oil phase 3, and the C ₅₊ compound can be relatively easily recovered from the oil phase 3.

  In the above, the reaction vessel 4 needs to have an inner surface that can withstand the temperature and pressure of the reaction conditions described below and does not impair the catalytic activity. For example, a glass-made reaction vessel or a metal-made reaction vessel can be used, but in the case of a metal-made reaction vessel, it is preferable that the content of Fe or Ni is small without impairing the catalytic activity.

The solvent forming the oil phase 3 does not inhibit the above-described aqueous phase reforming reaction and hydrocracking reaction. For example, when ether is used as the solvent, the ether itself is decomposed, so that the function as the oil phase 3 for dissolving the alcohol may be impaired. Further, alcohol having an OH group or the like is adsorbed by the catalyst and covers the active site, so that the catalytic ability may be impaired. Further, unsaturated hydrocarbons, for example, olefinic hydrocarbons, may themselves be hydrogenated in the presence of a metal catalyst, in which case they consume hydrogen used in the hydrocracking of sorbitol or xylitol, resulting in C The yield of the ₅₊ compound is reduced. Although aromatic hydrocarbons can be hydrogenated, they can also be used as a solvent because the reaction rate of hydrogenation is slow.

  Further, the solvent forming the oil phase 3 needs to be in a liquid phase (liquid) at the temperature and pressure as the reaction conditions described above. Typically, preferable reaction conditions are 170 ° C. to 190 ° C., and the pressure at room temperature in the reaction vessel is 0.5 MPa to 2 MPa (described later). For example, the boiling point of the solvent is 170 ° C. or more at 0.5 MPa. , Preferably 190 ° C or more at 0.5 MPa, more preferably 200 ° C or more. Further, when the oil phase 3 is taken out, if it becomes a solid phase, it becomes difficult to recover the alcohol. Therefore, it is preferable to maintain the liquid phase even at normal temperature and normal pressure. As such a saturated hydrocarbon, for example, n-dodecane or n-decane can be used. Further, two or more kinds of solvents for forming the oil phase 3 may be used as a mixture.

  Incidentally, as described above, the ideal reaction temperature differs between the aqueous phase reforming reaction and the hydrocracking reaction. Therefore, if the hydrogen obtained in the water phase reforming reaction can be efficiently consumed in the hydrocracking reaction, the amount of generated hydrogen can be reduced, and the reaction proceeds at a temperature lower than the ideal temperature in the water phase reforming reaction. be able to.

  Referring again to FIG. 2 and FIG. 4, the carbon dioxide generated by the aqueous phase reforming reaction is not used in a subsequent reaction step such as a hydrocracking reaction. Therefore, the yield of the obtained carbon dioxide with respect to the amount of sorbitol or xylitol is proportional to the amount of hydrogen generated by the aqueous phase reforming reaction. Here, as described above, in order to set the reaction temperature by reducing the amount of generated hydrogen to a predetermined amount or less, for example, when a raw material solution containing sorbitol is used, the yield of carbon dioxide is set to 50% or less. The reaction temperature is preferably set to such a temperature, and such a reaction temperature is preferably 190 ° C. or lower.

  Here, it is preferable to reduce the diffusion rate of hydrogen so that hydrogen generated by the aqueous phase reforming reaction can be consumed before desorbing from the vicinity of the active point of the hydrocracking reaction in the catalyst particles 1 described above. . That is, it is preferable to set the reaction temperature to a temperature at which hydrogen having a low diffusion rate is efficiently consumed in the hydrocracking reaction, and as a result, hydrogen is not desorbed from the aqueous phase 2. Such a reaction temperature can be, for example, 200 ° C. or lower, and preferably 190 ° C. or lower.

  As described above, cutting the carbon chain in the hydrocracking reaction can be suppressed by lowering the reaction temperature. On the other hand, when the reaction temperature is too low, the amount of hydrogen generated by the aqueous phase reforming reaction decreases. Therefore, for example, when a raw material solution containing sorbitol is used, the reaction temperature can be set to 160 ° C. or higher, and preferably 170 ° C. or higher, in order to secure the amount of generated hydrogen.

  Further, in order to efficiently consume the generated hydrogen in the hydrocracking reaction, a pressurized environment is used. However, if the pressure is too high, the amount of hydrogen generated in the aqueous phase reforming reaction decreases. Thus, the pressure can be in the range of 0.5 to 5 MPa, preferably in the range of 0.5 to 2 MPa.

As described above, despite the fact that the reaction temperature is lower than the ideal temperature only for the aqueous phase reforming, the obtained hydrogen is efficiently used in the hydrocracking reaction by using the above-described co-supported catalyst. It can be consumed and produce C5 ₊ compounds in high yield. Typically, for example, when a raw material solution containing sorbitol is used, the yield of the C ₆ compound can be 19.0% or more under the above-mentioned predetermined environmental conditions.

Hereinafter, one specific embodiment of the present invention will be further described. Here, using the raw material solution containing sorbitol, compound maintaining the number of carbon atoms of the C ₅₊ compounds, namely for the purpose of obtaining a C ₆ compound, to produce a C ₆ compounds in the conditions shown in Table 1 to be described later tested Was done.

[Preparation of catalyst]
First, an aqueous solution of iridium chloride (H ₂ IrCl ₆ ) is dropped on silicon dioxide (SiO ₂ ) (“CARiACT G-6” manufactured by Fuji Silysia Chemical Ltd.), and the whole is wetted and dried at about 90 ° C. These wet and dry steps were repeated so that Ir became 4% by mass with respect to the whole catalyst, and further, drying was performed at 110 ° C. for about half a day. Next, the same wetting and drying steps were repeated with an aqueous solution of ammonium perrhenate (NH ₄ ReO ₄ ) to carry the molar ratio of Re to Ir, that is, [Re] / [Ir], to 2. Thereafter, the mixture was fired at 500 ° C. for 3 hours in an air atmosphere to obtain Ir—ReO _x / SiO ₂ . Further, an aqueous solution of chloroplatinic acid (H ₂ PtCl ₆ ) is dropped into Ir-ReO _x / SiO ₂ to wet the whole, and dried at about 90 ° C. By repeating such a wet and dry process, Pt is supported at 0.5 to 5% by mass with respect to the entire catalyst, and calcined at 500 ° C. for 3 hours to convert Pt and Ir—ReO _x into SiO _2. A co-supported catalyst, that is, a Pt / Ir-ReO _x / SiO ₂ catalyst was obtained. The same applies to other catalysts, and details are omitted.

[Reduction treatment]
A SUS316 autoclave (capacity: 190 mL) having a glass inner tube was used as a reaction vessel. An electric furnace is arranged around the reaction vessel so that the inside can be heated. In addition, the reaction vessel is placed on a magnetic stirrer so that the inside can be stirred, and a magnetic stirrer chip (stirrer) coated with Teflon (registered trademark) is housed inside the inner tube of the reaction vessel. did. 150 mg of each of the catalysts shown in Table 1 and 9.5 g of water prepared as described above are placed in a reaction vessel, and hydrogen replacement is repeated three times or more. When the temperature inside the reaction vessel reached 200 ° C., hydrogen was introduced so as to bring the total pressure to 8 MPa. Thereafter, the reaction vessel was heated and kept at 200 ° C. for 1 hour to reduce the catalyst. A reaction vessel containing the catalyst after the reduction treatment was prepared for each of Examples and Comparative Examples described below.

[Product yield / conversion rate]
The yield is the molar yield of the product of interest converted from sorbitol, ie, the C ₆ compound, carbon dioxide and others (see Table 1), and is given by the following equation.
Yield (%) = (total carbon mole number of product of interest) / (total carbon mole number of sorbitol) × 100
For example, the “total carbon mole number of the product of interest” can be calculated by multiplying the number of moles of the product of interest analyzed by gas chromatography and high performance liquid chromatography by the carbon number of the product. Similarly, the “total carbon mole number of sorbitol” can also be calculated by multiplying the mole number of sorbitol charged in the reaction vessel 4 by the carbon number.

The conversion is the ratio of sorbitol converted to a substance other than sorbitol, and is given by the following equation.
Conversion (%) = 100− (Amount of sorbitol after reaction) / (Amount of sorbitol before reaction) × 100

[Formation of C ₆ compound]
As shown in Table 1, in each of the tests of Examples 1 to 19 and Comparative Example, an attempt was made to produce a C ₆ compound under the respective catalysts and reaction conditions. First, 0.5 g of sorbitol was added to the reaction vessel in which the catalyst was subjected to the reduction treatment as described above. Next, 20 mL of n-decane (20 mL of n-dodecane for Examples 6 to 8) was added as an oil phase 3 in the reaction vessel, and argon gas was introduced at room temperature to obtain the pressure at room temperature shown in Table 1. At the reaction temperature and the reaction time shown in FIG. Table 1 also shows the results of analysis of the product after the reaction. In addition, the gas chromatograph and the high performance liquid chromatograph were used for the analysis. Here, in Table 1, the numerical value in parentheses in the description of the catalyst indicates the carrying ratio of Pt, Rd or Rh. For example, in the case of Pt (3) / Ir-ReO _x / SiO ₂ , 3 mass% of Pt is supported on the entire catalyst. The display of the comparative example catalyst _{Pt (3) / SiO 2 +} Ir-ReO x / SiO 2 has a catalyst particle obtained by carrying Ir-ReO _x in catalyst particles and SiO ₂ obtained by carrying Pt on SiO ₂ Are mixed, and are different from other co-supported catalysts. In this case, the loading ratio of Pt of 3% by mass is the loading ratio for Pt / SiO ₂ . In the catalyst of the comparative example, the amounts of Pt, Ir, and Re supplied to the entire reaction system were the same as those in the case of Pt (3) / Ir-ReO _x / SiO ₂ (Example 2 and the like). I made it.

[Test results]
In Table 1, "hexanone" indicates 2-hexanone and 3-hexanone, "hexanol" indicates 1-hexanol, 2-hexanol and 3-hexanol, and "hexane" indicates n-hexane, 2-methylpentane, 3 -Methylpentane, "others" means 2-pentanone, 3-pentanone, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyltetrahydrofuran, 2,5 dimethyltetrahydrofuran, 2-methyltetrahydropyran, Acetic acid, propanoic acid, butanoic acid, valeric acid, hexanoic acid, n-pentane, n-butane, propane, ethane, methane and unidentified substances are shown.

As shown in Table 1, in Examples 1 to 5, the reaction temperature was set to 180 ° C., the reaction time was set to 24 hours, and the Pt loading was set to 0.5 to 5% by mass. higher yield of C ₆ compounds in the 3 wt% and the example 2 and example 1 was the same 5 wt%. At least under the reaction conditions of Examples 1 to 5, the amount of Pt supported is preferably 3 to 5% by mass.

In Examples 6 to 8, the pressure at room temperature was 2 to 4 MPa when the amount of Pt supported was 5% by mass. The yield in turn 17.0 percent of _{C 6} compounds of Examples 6-8, 12.3%, 15.3% of the high yield 19.0% in the case of 0.5MPa in Example 1 described above It was slightly lower than the rate. In Examples 6 to 8, n-dodecane was used for the oil phase 3 as described above.

In Examples 9 to 12, the pressure at room temperature was 0.5 to 4 MPa and the reaction temperature was 190 ° C. when the amount of supported Pt was 3% by mass. In each case, the yield of the C ₆ compound is as high as 22% or more.

In Example 13, 5% by mass of Pd was supported instead of Pt in the catalyst, and in Example 14, 5% by mass of Rh was supported instead of Pt. Although the yield is lower than in the case of Example 1 using Pt or the like, it can be seen that the C ₆ compound was obtained in each case.

Example 15 but the reaction time was 48 hours and the reaction temperature of 170 ° C., and the C ₆ compounds can be obtained in 21.3% of the high yield. On the other hand, in Example 16 in which the reaction time was 24 hours, the yield of the C ₆ compound was 13.9%, which was compared with Example 2 in which the reaction temperature was 180 ° C. and Example 9 in which the reaction temperature was 190 ° C. Then it is slightly lower.

The reaction temperature was set to 190 ° C. and increase the yield of the reaction time 18 hours and Shortened Example 17 In 23.4% of high C ₆ compound was obtained. In contrast, in the catalyst was obtained similarly high yield and 19.6% also in Example 18 using TiO ₂ as a carrier instead of the Si0 _2. That is, TiO ₂ can be used as the catalyst carrier. Further, the resulting 21.2% and high yields also in Example 19 using Rh-MoO _x in place of Ir-ReO _x for Examples 17. That is, the catalyst material to be co-supported with Pt or the like may be Rh-MoO _x .

As described above, as a catalyst for allowing the aqueous phase reforming reaction and the hydrocracking reaction to proceed in the same environment, Pt / Ir-ReO _x / Pt and Ir—ReO _x co-supported on SiO ₂ are used. It turns out that the SiO ₂ catalyst is suitable. Further, the catalyst carrier may be TiO _2, and give a Pd or Rh in place of Pt, it was also shown that instead of Ir-ReO _x may be Rh-MoO _x.

On the other hand, in the comparative example, the aqueous phase reforming catalyst and the hydrocracking catalyst are mixed as respective catalyst particles. Yield is very low in the C ₆ compounds as compared to any of the test results using the catalyst by co-supported as described above, was only 0.7%. Since the conversion of sorbitol was low and the yield of CO ₂ was low, it is considered that the aqueous phase reforming reaction did not proceed so much. From these results, in order for the water phase reforming reaction and the hydrocracking reaction having different reaction temperatures, which are originally ideal, to proceed in the same environment, it is not sufficient to simply mix the water phase reforming catalyst and the hydrocracking catalyst. It can be seen that the yield of the C ₆ compound is very low.

  The embodiments according to the present invention and the modifications based thereon have been described above. However, the present invention is not necessarily limited thereto, and those skilled in the art may depart from the spirit of the present invention or the scope of the appended claims. Without departing, various alternative embodiments and modifications could be found.

Claims (4)

A method for producing a C ₅₊ compound while maintaining a carbon number by reforming a part of a sugar alcohol having 5 or 6 carbon atoms in an aqueous phase and hydrocracking the remainder under the same environment ,
A catalyst in which a raw material solution containing the sugar alcohol is co-supported on SiO ₂ or TiO ₂ with a catalyst selected from Pt, Pd, and Rh, and a catalyst selected from Ir-ReO _x and Rh-MoO _x. and heating maintained in the presence of a particle, method for producing C ₅₊ compounds characterized Rukoto with water phase reforming hydrogen gas generated in the hydrocracking without detaching from the raw material solution. The method for producing a C5 ₊ compound according to claim 1, wherein the raw material solution is heated to a temperature of 160C to 200C . The method for producing a C5 ₊ compound according to claim 1 or 2, wherein an organic solvent is provided so as to cover the raw material solution. Said sugar alcohol is sorbitol, claim 1, characterized in that heating the CO ₂ yield the raw material solution below 190 ° C. 170 ° C. or more to 50% or less relative to the amount of the sorbitol of the raw material solution The method for producing a C ₅₊ compound according to any one of _claims 1 to 3.

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