JP5797587B2 - Method for producing hydrocracked product of 1,4-anhydroerythritol - Google Patents

Description

  The present invention is selected from 4-carbon alcohols (butanetriol, butanediol, and butanol) by hydrocracking 1,4-anhydroerythritol (3,4-dihydroxyoxolane) in the presence of a catalyst. The present invention relates to a method for producing a hydrocracked product of 1,4-anhydroerythritol for producing a hydrocracked product such as at least one compound.

  Currently, crude oil is the starting material for chemical products. And a chemical product uses a carbon atom as a main structural component. Looking at the flow of carbon on a global scale, the carbon that was sleeping in the ground as crude oil is brought to the ground as a chemical product and used for various purposes. At that time, carbon becomes carbon dioxide and accumulates in the atmosphere. There are many chemical products, such as gasoline and light oil, whose combustion is intended for use. Carbon dioxide accumulated in the atmosphere due to the flow of carbon causes global warming and is said to cause various harms such as abnormal climate and sea level rise.

  As one of the solutions, it has been proposed to use biomass (for example, cellulose, glucose, vegetable oil, etc.), which is a plant-derived resource, as a starting material for chemical products. This is because the plant that is the source of biomass absorbs carbon dioxide by photosynthesis during its growth process, and the amount of carbon dioxide absorbed by the combustion of chemical products is offset by the amount of carbon dioxide absorbed.

  It is known that a compound having 2 carbon atoms represented by ethylene among raw materials for chemical products is produced by dehydration of bioethanol. In addition, it is known that compounds having 3 carbon atoms such as propylene, 1,2-propanediol, 1,3-propanediol can be produced by hydrocracking and dehydrating glycerin produced as a by-product during biodiesel production. (See, for example, Non-Patent Document 1).

  On the other hand, examples of the compound having 4 carbon atoms include erythritol, succinic acid, 1,4-butanediol, 1-butanol and the like derived from saccharides such as glucose by a fermentation technique. Among them, since erythritol has hydroxyl groups on all four carbons, for example, alcohols having 4 carbon atoms in which one to three of the four hydroxyl groups are replaced with hydrogen atoms (specifically, engineering plastics and fiber 1,4-butanediol useful as a raw material; 1-butanol which is an excellent fuel; 1,2,3-butanetriol and 1,2,4-butanetriol useful as a raw material for explosives; raw materials for pharmaceuticals and cosmetics; foods 1,3-butanediol, 2,3-butanediol and the like useful as raw materials for additives and various solvents. However, a method for producing alcohols having 4 carbon atoms from erythritol has not yet been put into practical use.

Yoshinao Nakagawa, et al. "Direct hydrogenolysis of glycerol into 1,3-propanediol over rhenium-modified iridium catalyst", Journal of Catalysis, 2010, 272, p.191-194.

  The present inventors have found that alcohols having 4 carbon atoms (butanetriol, butanediol, butanol) as hydrogenolysis products of erythritol can be obtained by using erythritol as a raw material and reacting it with hydrogen. . However, in this reaction, isomers such as 1,2,4-butanetriol and 1,2,3-butanetriol are formed as trivalent alcohol (butanetriol), and divalent alcohol (butanetriol) is produced. Diols), such as 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, and the like. It was not generated selectively. Each of these isomers (each isomer in an equivalent alcohol) has a boiling point close to each other, which may cause problems such as difficulty in separation or requiring very large energy for separation.

  Therefore, the object of the present invention is to select specific isomers (particularly 1,2,3-butanetriol, 1,3-butanediol) among alcohols having 4 carbon atoms (particularly butanetriol, butanediol). It is to provide a method (manufacturing method) that can be selectively generated.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have reacted 1,4-anhydroerythritol derivable from erythritol with hydrogen in the presence of a specific catalyst. As hydrogenated hydrolysates of erythritol, it has been found that specific isomers (particularly 1,2,3-butanetriol and 1,3-butanediol) can be selectively produced among butanetriol and butanediol. It was. The present invention has been completed based on these findings.

  That is, the present invention provides 1,4- in the presence of a catalyst comprising a support and at least one metal selected from the group consisting of iridium, platinum, rhodium, cobalt, palladium, and nickel supported on the support. Provided is a method for producing a hydrocracked product of 1,4-anhydroerythritol, which comprises a step A in which a hydrocracked product of 1,4-anhydroerythritol is produced by the reaction of anhydroerythritol and hydrogen. To do.

  Furthermore, the present invention provides the method for producing a hydrocracked product of 1,4-anhydroerythritol, wherein the catalyst further contains at least one metal selected from the group consisting of rhenium, molybdenum, tungsten, and manganese.

  Furthermore, the present invention provides a method for producing a hydrocracked product of the above 1,4-anhydroerythritol in which at least one metal selected from the group consisting of rhenium, molybdenum, tungsten, and manganese is supported on a support.

  Furthermore, the present invention provides a method for producing a hydrocracked product of the above 1,4-anhydroerythritol, wherein the catalyst contains at least iridium supported on a carrier.

  Further, the present invention provides a method for producing a hydrocracked product of 1,4-anhydroerythritol, wherein the catalyst contains iridium and rhenium in a ratio of 50/1 to 1/6 [iridium / rhenium (molar ratio)]. To do.

  Further, the hydrocracked product of 1,4-anhydroerythritol of the above-mentioned 1,4-anhydroerythritol, wherein the carrier supporting at least one metal selected from the group consisting of iridium, platinum, rhodium, cobalt, palladium, and nickel is an inorganic oxide. A manufacturing method is provided.

  Furthermore, the present invention provides a method for producing the hydrocracked product of 1,4-anhydroerythritol, wherein the carrier supporting at least one metal selected from the group consisting of rhenium, molybdenum, tungsten, and manganese is an inorganic oxide. To do.

  Furthermore, the method for producing a hydrocracked product of 1,4-anhydroerythritol as described above, wherein the inorganic oxide is at least one compound selected from the group consisting of silica, titania, zirconia, alumina, magnesia, and zeolite. provide.

  Furthermore, the present invention provides a method for producing a hydrocracked product of 1,4-anhydroerythritol, wherein the reaction between 1,4-anhydroerythritol and hydrogen in the step A proceeds in the presence of an acid.

  Further, the process for producing a hydrocracked product of 1,4-anhydroerythritol described above further includes a step B of generating 1,4-anhydroerythritol by intramolecular dehydration reaction of erythritol before the step A. To do.

  Since the method for producing a hydrocracked product of 1,4-anhydroerythritol of the present invention has the above-described configuration, an alcohol having 4 carbon atoms (at least one compound selected from butanetriol, butanediol, and butanol) is obtained. It can be manufactured efficiently and has excellent productivity. In particular, a specific isomer (especially 1,2,3-butanetriol, 1,3-butanediol) is selectively produced among alcohols having 4 carbon atoms (especially butanetriol, butanediol). It is very useful in that it can. Moreover, since the said 1, 4- anhydroerythritol can be easily induced | guided | derived from the erythritol which is a plant-derived resource, it is useful also at the point of reduction of a carbon dioxide discharge. Furthermore, since the method for producing a hydrocracked product of 1,4-anhydroerythritol according to the present invention uses a solid catalyst as a catalyst, it is easy to separate the catalyst from the reaction system, and the catalyst is regenerated. Is advantageous in terms of cost.

FIG. 1 is a flowchart showing an example of step A in the method for producing a hydrocracked product of 1,4-anhydroerythritol of the present invention when a trickle bed reactor is used.

  The method for producing a hydrocracked product of 1,4-anhydroerythritol of the present invention is at least one selected from the group consisting of a support and iridium, platinum, rhodium, cobalt, palladium, and nickel supported on the support. In the presence of a metal-containing catalyst, a reaction of 1,4-anhydroerythritol with hydrogen to produce a hydrocracked product of 1,4-anhydroerythritol (particularly an alcohol having 4 carbon atoms) (" Step A ”)).

[1,4-Anhydroerythritol]
1,4-Anhydroerythritol (3,4-dihydroxyoxolane) used as a raw material (starting raw material) in the above step A has a structure formed by dehydration condensation of the 1-position and 4-position hydroxyl groups of erythritol. And is represented by the following formula (1).

  The 1,4-anhydroerythritol is not particularly limited, and may be, for example, 1,4-anhydroerythritol produced by chemical synthesis, or may be derived from a sugar such as glucose by fermentation technology. 4-Anhydroerythritol may be sufficient. As 1,4-anhydroerythritol induced by the fermentation technique, for example, erythritol derived from a sugar such as glucose by a fermentation technique is used as a raw material, and 1,4-anhydroerythritol is produced by an intramolecular dehydration reaction of the erythritol. 4-anhydroerythritol etc. are mentioned. The intramolecular dehydration reaction can be carried out by a known or commonly used method, and is not particularly limited. In addition, as the 1,4-anhydroerythritol, 1,4-anhydroerythritol (unreacted 1,4-anhydroerythritol) recovered from the reaction mixture obtained in the step A may be reused. it can.

[catalyst]
The catalyst used in Step A of the method for producing a hydrocracked product of 1,4-anhydroerythritol of the present invention includes a carrier, iridium (Ir), platinum (Pt), rhodium (Rh) supported on the carrier. ), Cobalt (Co), palladium (Pd), and nickel (Ni), and at least one metal selected from the group consisting of metals (metal components; hereinafter sometimes referred to as “iridium etc.”). . The iridium or the like is not particularly limited as long as it is supported on the carrier. Examples of the form of iridium include a form of a simple metal, a metal salt, a metal oxide, a metal hydroxide, a metal complex, and the like. Among these, the catalyst preferably contains at least iridium supported on a carrier from the viewpoint of the hydrocracking reaction reactivity.

The carrier can be a known or conventional carrier used as a catalyst carrier, and is not particularly limited. Examples thereof include inorganic carriers such as inorganic oxides and activated carbon, and organic carriers such as ion exchange resins. Can be mentioned. As the carrier, an inorganic oxide is preferable because it has excellent reaction activity. Examples of the inorganic oxide include silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), alumina (Al ₂ O ₃ ), magnesia (MgO), and two or more kinds of these inorganic oxides. A composite (for example, zeolite etc.) etc. are mentioned. Among the inorganic oxides, silica (SiO ₂ ) and zeolite are particularly preferable in terms of excellent reaction activity. In the catalyst, the carrier can be used alone or in combination of two or more.

The specific surface area of the carrier is not particularly limited, but 50 m in that metal such as iridium can be arranged in a highly dispersed state, aggregation of the metal can be suppressed, and catalytic activity per unit weight can be improved. ² / g or more (for example, 50 to 1500 m ² / g, preferably 100 to 1000 m ² / g) is preferable. When the specific surface area of the carrier is less than the above range, the catalytic activity per unit weight tends to decrease.

  The average particle size of the carrier is not particularly limited, but is preferably 100 to 10,000 μm, more preferably 1000 to 1000 μm in terms of reactivity and no excessive pressure loss when the reaction is carried out in a continuous flow mode. 10,000 μm. The shape of the carrier may be any of powder, granule, molding (molded body) and the like, and is not particularly limited.

  The amount of iridium or the like supported on the carrier (the total amount when two or more metals are included) is not particularly limited, but is 0.01% with respect to the total amount of iridium and the carrier (100% by weight). About 50% by weight is preferable, more preferably about 0.01-20% by weight, still more preferably about 0.5-15% by weight, and particularly preferably about 1.0-10% by weight. If the supported amount of iridium or the like is less than 0.01% by weight, the conversion rate of 1,4-anhydroerythritol tends to decrease. On the other hand, if the amount of iridium or the like exceeds 50% by weight, it may be uneconomical.

  The method for supporting the above iridium or the like (particularly iridium) on the carrier is not particularly limited, and can be carried out by a known or conventional supporting method. Specifically, for example, it can be supported by a method of impregnating a carrier with a solution containing iridium or the like (for example, an aqueous solution of chloroiridic acid in the case of iridium), then drying and then firing. Note that the amount of iridium or the like supported can be controlled by adjusting the concentration of the solution containing iridium or the like, the number of times the carrier is impregnated, and dried. The temperature at which the solution containing iridium or the like is impregnated and the temperature at which the carrier impregnated with the solution is dried are not particularly limited.

  The temperature (calcination temperature) at which the carrier after impregnating and drying the solution containing iridium and the like is calcined is not particularly limited, but is preferably 400 to 700 ° C. in the atmosphere, and more preferably 450 to 700 ° C. 550 ° C. Moreover, the atmosphere at the time of baking is not limited to air | atmosphere as mentioned above, For example, it can also bake in inert gas atmosphere, such as nitrogen and argon, reducing gas atmosphere, such as hydrogen.

  The catalyst is at least one metal selected from the group consisting of a support, iridium supported on the support, rhenium (Re), molybdenum (Mo), tungsten (W), and manganese (Mn). (Metal component; sometimes referred to as “rhenium etc.”). By using rhenium or the like together as the metal component in the catalyst, the conversion of 1,4-anhydroerythritol can be increased. In particular, selection of 1,2,3-butanetriol and 1,3-butanediol is possible. The rate can be increased. Especially, it is preferable that the said catalyst contains rhenium at least from the reactive viewpoint of hydrocracking reaction as said rhenium.

  The aspect of rhenium and the like contained in the catalyst is not particularly limited. For example, an aspect contained in the form (state) of a simple metal, a metal salt, a metal oxide, a metal hydroxide, or a metal complex, a simple metal, Examples include a mode in which a metal salt, metal oxide, metal hydroxide, or metal complex is contained in a state of being supported on a carrier.

Examples of the carrier for supporting rhenium and the like are the same as those for supporting iridium and the like. Among them, the carrier supporting the rhenium or the like is preferably an inorganic oxide in terms of excellent reaction activity, and particularly preferably silica (SiO ₂ ), titania (TiO ₂ ), zirconia (ZrO ₂ ), alumina (Al ₂ O ₃ ), magnesia (MgO), and at least one compound selected from a composite of two or more of these inorganic oxides (for example, zeolite, etc.), most preferably silica (SiO ₂ ), zeolite It is. The carrier supporting rhenium or the like may be the same as or different from the carrier supporting iridium or the like. Among them, in the above catalyst, it is preferable that the carrier supporting rhenium or the like and the carrier supporting iridium or the like are the same in that a superior catalytic action can be exhibited.

  When rhenium or the like is supported on a carrier, the method is not particularly limited, and a known or conventional supporting method can be used. Specifically, for example, a method of impregnating a carrier with a solution containing rhenium or the like, drying it, and baking it can be given. When rhenium or the like is supported on the same carrier as the above iridium or the like, for example, a solution containing iridium or the like is impregnated and the carrier after drying is further impregnated with a solution containing rhenium or the like. And a method of firing after drying. The temperature at which the solution containing rhenium or the like is impregnated, the temperature at which the carrier impregnated with the solution is dried, and the temperature at which the carrier is fired are not particularly limited.

  Among them, a catalyst containing a carrier and iridium supported on the carrier, and further containing rhenium or the like (particularly rhenium) supported on the carrier is preferable. In particular, the catalyst is more excellent in that it is a catalyst containing a carrier, iridium supported on the carrier, and rhenium supported on the carrier (that is, a catalyst in which iridium and rhenium are supported on the same carrier). This is preferable in that it can exert its action and the catalyst after the reaction can be easily recovered.

  When the catalyst contains rhenium or the like, the conversion of 1,4-anhydroerythritol can be improved as the content of rhenium or the like increases. Further, as the content of rhenium and the like increases, the selectivity for triol decreases and the selectivity for diol and monool tends to increase. The ratio (molar ratio, metal conversion) of iridium or the like (total amount when containing two or more) and rhenium or the like (total amount when containing two or more) [the former / the latter] Although not particularly limited, for example, 50/1 to 1/6 is preferable, 4/1 to 1/4 is more preferable, and 3/1 to 1/3 is more preferable. The amount of rhenium or the like used can be appropriately adjusted within the above range depending on the reaction temperature, reaction time, and target product.

  In particular, when the catalyst contains at least iridium supported on a carrier and rhenium, the ratio of iridium and rhenium (molar ratio, metal conversion) [iridium / rhenium] is not particularly limited, but in the hydrocracking reaction From the viewpoint of conversion, 50/1 to 1/6 is preferable, more preferably 4/1 to 1/4, and still more preferably 3/1 to 1/3.

  The average particle diameter of the catalyst is not particularly limited, but is preferably from 100 to 10,000 μm, more preferably from 1,000 to 10,000, in terms of reactivity and not accompanied by excessive pressure loss when the reaction is carried out in a continuous flow mode. 10,000 μm. The shape of the catalyst is not particularly limited, and examples thereof include powder, granule, and molding (molded body).

[hydrogen]
Hydrogen (hydrogen gas) used in the above step A can be used in a substantially hydrogen-only state, or can be used in a state diluted with an inert gas such as nitrogen, argon or helium. . Moreover, the hydrogen (unreacted hydrogen) recovered from the reaction mixture obtained as a result of the step A can be reused.

[Step A]
In the process for producing a hydrocracked product of 1,4-anhydroerythritol of the present invention, step A is carried out by reacting 1,4-anhydroerythritol with hydrogen in the presence of the above catalyst. This is a step of producing alcohols having 4 carbon atoms (butanetriol, butanediol, butanol) or the like as hydrocracked products. The reaction between 1,4-anhydroerythritol and hydrogen is a gas-solid two-phase reaction in which gaseous (vaporized) 1,4-anhydroerythritol and hydrogen are reacted in the presence of a solid catalyst. It may be a gas-liquid solid three-phase reaction in which liquid 1,4-anhydroerythritol and hydrogen are reacted in the presence of a solid catalyst. In particular, from the viewpoint of suppressing the formation of a compound having 3 or less carbon atoms due to the cleavage of the carbon-carbon bond, the above reaction is preferably allowed to proceed in a gas-liquid solid three-phase system.

  More specifically, the reaction of 1,4-anhydroerythritol and hydrogen in step A is performed by, for example, sealing a raw material solution containing 1,4-anhydroerythritol as essential components and hydrogen in a reactor. , And can proceed by heating in the presence of the catalyst.

  In addition to 1,4-anhydroerythritol, the raw material liquid may contain, for example, a solvent such as water or an organic solvent, or may contain substantially no solvent. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol, n-butanol and 2-butanol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc) and the like. Examples include polar organic solvents. The raw material liquid preferably contains at least water as a solvent in terms of excellent reactivity and easy handling and disposal. Moreover, as said raw material liquid, the reaction mixture obtained by the intramolecular dehydration reaction of erythritol in the process B, the liquid which removed the acid catalyst etc. as needed from this reaction mixture, etc. can be used.

  The concentration of 1,4-anhydroerythritol in the raw material liquid (content of 1,4-anhydroerythritol with respect to 100% by weight of the raw material liquid) is not particularly limited, but is preferably 5 to 98% by weight, more preferably 8 It is -90 weight%, More preferably, it is 10-90 weight%, Most preferably, it is 15-80 weight%. When the concentration of 1,4-anhydroerythritol is less than 5% by weight, the reaction rate (conversion rate) of 1,4-anhydroerythritol may decrease. On the other hand, when the concentration of 1,4-anhydroerythritol exceeds 98% by weight, the viscosity may increase and the operation may become complicated.

  The reaction of 1,4-anhydroerythritol and hydrogen may be allowed to proceed in the presence of an acid. That is, the raw material liquid may contain an acid in addition to the above 1,4-anhydroerythritol and the solvent. The acid is not particularly limited, and examples thereof include known or commonly used acids such as sulfuric acid, phosphoric acid, trifluoromethanesulfonic acid and the like. By proceeding the reaction in the presence of an acid, the hydrogenolysis reaction of 1,4-anhydroerythritol can be promoted.

  Although the usage-amount (content) of the said acid is not specifically limited, It is 0.1-10 mol times with respect to iridium etc. which are contained in a catalyst (in metal conversion, when these 2 types are included, these total amounts). Is more preferable, and 0.5 to 3 mole times is more preferable. When an acid is allowed to coexist, it is preferable to provide a step of neutralizing the acid after completion of the reaction.

  In the above reaction, other components may be allowed to coexist as long as the effects of the present invention are not impaired. That is, the raw material liquid may contain other components (for example, alcohols and the like) as long as the effects of the present invention are not impaired. In addition, the above-mentioned raw material liquid includes, for example, sulfur-containing compounds such as long-chain fatty acids, metal salts, thiols and thioethers derived from 1,4-anhydroerythritol raw materials (erythritol, raw materials of the erythritol, etc.) , Nitrogen-containing compounds such as amines) may be contained, but since such impurities may deteriorate the catalyst, known or conventional methods (for example, distillation, adsorption, ion exchange, crystallization, extraction) Etc.) is preferably removed from the raw material liquid.

  The raw material liquid is not particularly limited, and can be obtained by uniformly mixing 1,4-anhydroerythritol and, if necessary, a solvent, an acid, and other components. A known or conventional stirrer can be used for mixing.

  The molar ratio of hydrogen to 1,4-anhydroerythritol [hydrogen (mol) / 1,4-anhydroerythritol (mol)] to be subjected to the reaction (hydrocracking reaction) is not particularly limited, but is preferably 1 to 100. More preferably, it is 1.5-50, More preferably, it is 2-30. When the molar ratio is less than 1, the reaction rate (conversion rate) of 1,4-anhydroerythritol may decrease. On the other hand, when the molar ratio exceeds 100, the utility cost for recovering unreacted hydrogen tends to increase.

  The reaction temperature of 1,4-anhydroerythritol and hydrogen in the above reaction (hydrogenolysis reaction) is not particularly limited, but is preferably 50 to 200 ° C, more preferably 60 to 150 ° C, and still more preferably 70 to 130 ° C. It is. When the reaction temperature is less than 50 ° C., the reaction rate (conversion rate) of 1,4-anhydroerythritol may decrease. On the other hand, when the reaction temperature exceeds 200 ° C., 1,4-anhydroerythritol is likely to be decomposed (for example, cleavage of carbon-carbon bond), and the target compound (for example, alcohol having 4 carbon atoms, particularly 1 , 2,3-butanetriol, 1,3-butanediol) may be reduced. The reaction temperature may be controlled to be constant (substantially constant) in the above reaction, or may be controlled to change stepwise or sequentially.

  The reaction time of 1,4-anhydroerythritol and hydrogen in the above reaction (hydrogenolysis reaction) is not particularly limited, but is preferably 0.1 to 100 hours, more preferably 0.2 to 5 hours, still more preferably. 0.5 to 4 hours. If the reaction time is less than 0.1 hour, the reaction rate (conversion rate) of 1,4-anhydroerythritol may not be sufficiently increased. On the other hand, when the reaction time exceeds 100 hours, the production of butane in which 1,4-anhydroerythritol is completely hydrocracked increases rapidly. For example, alcohols having 4 carbon atoms (especially 1,2,3 -Butanetriol, 1,3-butanediol) may be reduced.

  The reaction pressure of 1,4-anhydroerythritol and hydrogen in the above reaction (hydrogenolysis reaction) (hydrogen pressure in the reaction of 1,4-anhydroerythritol and hydrogen) is not particularly limited, but is preferably 1 to 50 MPa, More preferably, it is 3-30 MPa, More preferably, it is 5-15 MPa. If the reaction pressure is less than 1 MPa, the reaction rate (conversion rate) of 1,4-anhydroerythritol may decrease. On the other hand, when the reaction pressure exceeds 50 MPa, the reactor needs to have a high pressure resistance, and thus the production cost tends to increase.

  The above reaction (hydrocracking reaction) can be carried out in any format such as a batch format, a semi-batch format, and a continuous flow format. Further, when it is desired to increase the amount of 1,4-anhydroerythritol hydrocracked product obtained from a predetermined amount of 1,4-anhydroerythritol, unreacted 1,4-anhydrocracked product after the hydrocracking is performed. A process of separating and collecting anhydroerythritol and recycling it may be adopted. If this recycling process is adopted, the amount of 1,4-anhydroerythritol hydrocracked product generated when a predetermined amount of 1,4-anhydroerythritol is used can be increased.

  In the step A, a known or conventional reactor can be used as the reactor, and for example, a batch reactor, a fluidized bed reactor, a fixed bed reactor, or the like can be used. As the fixed bed reactor, for example, a trickle bed reactor can be used. A trickle bed reactor has a catalyst packed bed filled with a solid catalyst inside, and liquid (in the process A, the raw material liquid) and gas (hydrogen in the process A) are supplied to the catalyst packed bed. Both are reactors (fixed-bed continuous reaction devices) of a type that flows from above the reactor in a downward flow (gas-liquid downward parallel flow).

  FIG. 1 is a flowchart showing an example of step A in the method for producing a hydrocracked product of 1,4-anhydroerythritol when a trickle bed reactor is used. In FIG. 1, 1 is a reactor (a trickle bed reactor), 2 is a feed line for raw material liquid, and 3 is a supply line for hydrogen. 4 is a reaction mixture take-out line, 5 is a high-pressure gas-liquid separator, and 6 is a hydrogen recycle line. Hereinafter, a method for producing a hydrocracked product of 1,4-anhydroerythritol using a trickle bed reactor will be briefly described with reference to FIG.

  First, the raw material liquid and hydrogen are continuously supplied from above the trickle bed reactor 1, and then 1,4-anhydroerythritol and hydrogen in the raw material liquid are converted into the catalyst in the catalyst packed bed inside the reactor. To produce a hydrogenolysis product (reaction product) of 1,4-anhydroerythritol. Then, the reaction mixture containing the hydrocracked product of 1,4-anhydroerythritol is continuously taken out from the reaction mixture take-out line 4 below the trickle bed reactor 1, and then, if necessary, high-pressure gas-liquid separation. After separating hydrogen from the reaction mixture by the vessel 5, the hydrocracked product of 1,4-anhydroerythritol is purified and isolated in a purification step. The hydrogen separated by the high-pressure gas-liquid separator 5 can be supplied again to the trickle bed reactor 1 through the hydrogen recycling line 6 and reused for the reaction.

  Adopting a trickle bed reactor as a reactor is advantageous in terms of cost because the reaction can proceed in a gas-liquid solid three-phase system without vaporizing 1,4-anhydroerythritol as a raw material. Further, in the trickle bed reactor, the raw material liquid containing 1,4-anhydroerythritol flows downward while forming a thin film on the catalyst surface, so that from the interface between the raw material liquid and hydrogen (gas-liquid interface) to the catalyst surface. , The hydrogen dissolved in the raw material liquid can be easily diffused to the catalyst surface, and the hydrocracked product of 1,4-anhydroerythritol can be efficiently generated. In addition, a process for separating the catalyst from the reaction product of 1,4-anhydroerythritol and hydrogen is not required, and the catalyst regeneration process is easy. Therefore, the manufacturing process is simple and excellent in terms of cost.

  The material, shape, size, etc. (for example, tower diameter, tower length, etc.) of the trickle bed reactor are not particularly limited, and are selected from known or conventional trickle bed reactors depending on the scale of the reaction, etc. It can be selected appropriately. Further, the trickle bed reactor may be constituted by a single reaction tube or a multi-stage reactor constituted by a plurality of reaction tubes. When the trickle bed reactor is a multistage reactor, the number of reaction tubes can be selected as appropriate and is not particularly limited. Further, when the trickle bed reactor is a multistage reactor, the reactor may be one in which a plurality of reaction tubes are installed in series, or a plurality of reaction tubes are arranged in parallel. It may be a thing.

  Furthermore, the catalyst packed bed inside the trickle bed reactor may be divided (separated) into two or more positions, for example, in order to suppress overheating due to reaction heat.

Liquid hourly space velocity of the raw material liquid (LHSV) is not particularly limited, but is preferably 0.05～100Hr ^-1, more preferably 0.1～50Hr ^-1, even more preferably at 0.5～20Hr ^-1 . When the liquid standard space velocity of the raw material liquid is less than 0.05 h ⁻¹ , the productivity of 1,4-anhydroerythritol hydrocracked product may be reduced. On the other hand, when the liquid standard space velocity of the raw material liquid exceeds 100 hr ⁻¹ , the reaction rate (conversion rate) of 1,4-anhydroerythritol may decrease. The liquid reference space velocity is a ratio of the feed rate (volume flow rate) of the raw material liquid to the reactor to the catalyst filling volume [feed rate of raw material liquid (L · hr ⁻¹ ) / catalyst filling volume (L)]. expressed.

  The method for producing a hydrocracked product of 1,4-anhydroerythritol according to the present invention may include other steps as needed in addition to the above step A. Other steps include, for example, a step of preparing and purifying the raw material liquid before supplying the raw material liquid and hydrogen to the reactor, and a reaction mixture discharged (outflowed) from the reactor (for example, 1,4-anhydro). And a step of separating and purifying a mixture of erythritol, hydrogen, and a hydrocracked product of 1,4-anhydroerythritol). Note that these steps may be performed in a separate line from the step A, or may be performed as a series of steps with the step A (in-line).

[Step B]
The method for producing a hydrocracked product of 1,4-anhydroerythritol according to the present invention comprises a step of producing 1,4-anhydroerythritol, particularly by an intramolecular dehydration reaction of erythritol, before the above step A. A step of generating 4-anhydroerythritol (referred to as “step B”) may further be included. The intramolecular dehydration reaction of erythritol can be carried out by a well-known method, and is not particularly limited. For example, the erythritol can proceed by heating erythritol in the presence of an acid catalyst. In addition, the process B may be implemented on a separate line from the process A, or may be performed as a series of processes with the process A.

  The erythritol used as a raw material (starting raw material) in the said process B is not specifically limited, The erythritol manufactured by chemical synthesis may be sufficient, and it is an erythritol induced | guided | derived by saccharides, such as glucose, with fermentation technology, Also good. Among these, from the viewpoint of reducing the burden on the environment, it is preferable to use erythritol derived from a saccharide such as glucose by a fermentation technique. Moreover, the erythritol (unreacted erythritol) collect | recovered from the reaction mixture obtained by the said process B can also be reused.

  As the acid catalyst used in the step B, known or conventional acids can be used, and are not particularly limited. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, metaphosphoric acid, condensed phosphoric acid, Inorganic acids such as hydrobromic acid, perchloric acid, hypochlorous acid and chlorous acid; organic acids such as p-toluenesulfonic acid, trichloroacetic acid, trifluoroacetic acid and trifluoromethanesulfonic acid; cation exchange resin and zeolite And solid acids such as silica alumina and heteropolyacids (for example, phosphomolybdic acid). Among these, a solid acid is preferable because it can be easily separated from a product and regenerated. In addition, a commercial item can also be used as said acid catalyst, for example, a brand name "Amberlyst" (made by Dow Chemical), a brand name "Nafion" (made by DuPont Co., Ltd.), etc. as a commercial item of a solid acid. Is exemplified. In addition, an acid (acid catalyst) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The above reaction (intramolecular dehydration reaction) can be allowed to proceed in the absence of a solvent, or can be allowed to proceed in the presence of a solvent. Examples of the solvent include water; alcohols such as methanol, ethanol, isopropanol, and n-butanol; and highly polar organic solvents such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and dimethylacetamide (DMAc). . Among these, it is preferable to contain at least water as a solvent in terms of excellent reactivity and easy handling and disposal. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The reaction temperature (heating temperature) of the above reaction (intramolecular dehydration reaction) is not particularly limited, but is preferably 40 to 240 ° C, more preferably 80 to 200 ° C, and still more preferably 120 to 180 ° C. By controlling the reaction temperature within the above range, the intramolecular dehydration reaction of erythritol can proceed more efficiently. The reaction temperature may be controlled to be constant (substantially constant) in the reaction, or may be controlled to change stepwise or sequentially.

  Although the time (reaction time) for the above reaction (intramolecular dehydration reaction) is not particularly limited, it is preferably 1 to 100 hours, more preferably 2 to 50 hours, still more preferably 3 to 30 hours. If the reaction time is less than 1 hour, the reaction rate (conversion rate) of erythritol may not be sufficiently increased. On the other hand, if the reaction time exceeds 100 hours, it may be disadvantageous in terms of cost.

  The above reaction (intramolecular dehydration reaction) can be carried out in any atmosphere such as an air atmosphere or an inert gas atmosphere such as nitrogen or argon. In particular, from the viewpoint of improving the selectivity of 1,4-anhydroerythritol, it is preferably carried out in an inert gas atmosphere. The above reaction (intramolecular dehydration reaction) can be carried out under normal pressure, under pressure, or under reduced pressure. In particular, from the viewpoint of improving the conversion rate of erythritol, it is preferably carried out under pressure. For example, when water is used as a solvent, the reaction temperature can be raised to 100 ° C. or higher by carrying out the reaction under pressure, so that the conversion rate of erythritol can be increased efficiently.

  The above reaction (intramolecular dehydration reaction) can be carried out in any format such as a batch format, a semi-batch format, and a continuous flow format.

  By the above step B, 1,4-anhydroerythritol is produced. The 1,4-anhydroerythritol thus obtained is then used as a starting material in the above step A, but is known or commonly used from the reaction mixture obtained in the step B (for example, distillation, adsorption, etc.). , Ion exchange, crystallization, extraction, etc.) can be used after being isolated, or can be used without being isolated from the above reaction mixture (after removing the acid catalyst, if necessary). it can.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Example 1
[Preparation of catalyst]
Silicon dioxide (SiO ₂ ) (trade name “G-6”, manufactured by Fuji Silysia Chemical Ltd., specific surface area: 535 m ² / g) was used as a catalyst support. To the carrier, an aqueous solution of chloroiridate (H ₂ IrCl ₆ ) prepared so that the iridium (Ir) concentration is 4.47% by weight is added dropwise to wet the entire carrier, and then the carrier is cooled to 110 ° C. And dried for 3 hours. Then, the dropping and drying of the chloroiridium acid aqueous solution were repeated and the iridium was supported so as to be 4% by weight with respect to SiO ₂ .
Next, an aqueous solution of ammonium perrhenate (NH ₄ ReO ₄ ) prepared so as to have a rhenium (Re) concentration of 3% by weight on the above carrier (a carrier on which iridium is supported) is dropped and dried. Rhenium was supported so that the molar ratio of iridium and rhenium was 1/1 by repeating the dropping and drying of the iridium acid aqueous solution. Thereafter, the dried support was calcined under an air atmosphere (in the air) at 500 ° C. for 3 hours to prepare a catalyst.

[Conversion of erythritol to 1,4-anhydroerythritol: Step B]
In an autoclave, 1 g of erythritol, 4 g of water, and 0.15 g of a trade name “Amberlyst 70” as a catalyst were added and reacted under the conditions of an argon pressure of 5 MPa and 160 ° C. for 24 hours. 1,4-anhydroerythritol (3, 4-dihydroxyoxolane) was obtained. The conversion of erythritol was 98.6%, and the selectivity for 1,4-anhydroerythritol was 97.2%.

[1,4-Anhydroerythritol hydrocracking reaction: Step A]
A reactor composed of a 190 mL autoclave made of SUS316 equipped with a glass inner can and a magnetic stirrer chip coated with Teflon (registered trademark), and a heating / stirring device comprising a magnetic stirrer and an electric furnace are used. It was.
The reactor was charged with 300 mg of the catalyst prepared above and 4 g of water, and after hydrogen replacement work of evacuating to normal pressure after filling with 1 MPa of hydrogen was repeated three times, the inside of the can was heated to 200 ° C. Occasionally, hydrogen was added so that the total pressure was 8 MPa, and the catalyst was reduced by heating at 200 ° C. for 1 hour.
After the reduction, the autoclave was cooled and opened, 1 g of 1,4-anhydroerythritol obtained above and 300 mg of 1% sulfuric acid were added, and the replacement operation with 1 MPa of hydrogen was repeated three times. Then, when heated and the inside of the can reached 100 ° C., hydrogen was charged so that the total pressure became 8 MPa, and the reaction was performed by heating at 100 ° C. for 4 hours (reaction pressure: 8 MPa, stirring rotation speed: 250 rpm).
After completion of the reaction, the autoclave was cooled to room temperature and then opened, and the exhaust gas and the reaction solution were analyzed by gas chromatography. As a result, the conversion of 1,4-anhydroerythritol was 31.2%; the selectivity of 1,2,3-butanetriol was 39.2%; the selectivity of 1,3-butanediol was 31.1%. The selectivity for 2,3-butanediol was 0.7%; the selectivity for 1-butanol was 7.4% and the selectivity for 2-butanol was 17.9%. The production of 1,4-butanediol, 1,2-butanediol, and 1,2,4-butanetriol was not observed. Thus, in Example 1, 1,3-butanediol was selectively produced as butanediol and 1,2,3-butanetriol was selectively produced as butanetriol.

Comparative Example 1
The erythritol hydrocracking reaction was carried out in the same procedure as the above "1,4-anhydroerythritol hydrocracking reaction" except that erythritol was used instead of 1,4-anhydroerythritol.
As a result of analyzing the product after completion of the reaction, the conversion of erythritol was 26.4%; the selectivity of 1,2,4-butanetriol was 36.8%, and the selection of 1,2,3-butanetriol The selectivity is 20.8%; the selectivity for 1,4-butanediol is 20.1%, the selectivity for 1,3-butanediol is 7.5%, and the selectivity for 1,2-butanediol is 3.2. %, 2,3-butanediol selectivity was 0.4%; 1-butanol selectivity was 6.7% and 2-butanol selectivity was 4.2%. Thus, in Comparative Example 1, a considerable amount of 1,4-butanediol, 1,3-butanediol, and 1,2-butanediol were produced as diols, respectively, and 1,2,4-butanetriol and triol were A considerable amount of 1,2,3-butanetriol was produced.

The conversion rate (%) of 1,4-anhydroerythritol (or erythritol) described above is the amount of 1,4-anhydroerythritol (or erythritol) in the reaction mixture (composition containing raw materials and products). The amount of decrease from the charged amount of 1,4-anhydroerythritol (or erythritol) is calculated and calculated as the ratio of the decreased amount to the charged amount [100 × (reduced amount) / (charged amount)]. It was.
In addition, each product (1,2,3-butanetriol, 1,2,4-butanetriol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butane The selectivity (%) of diol, 1-butanol, and 2-butanol) is the ratio of the amount of each product (production amount) to the reduction amount of 1,4-anhydroerythritol [100 × (of each product Production amount) / (Reduction amount of 1,4-anhydroerythritol)] (molar basis).
The amount of each component (raw material and product) was measured under the following conditions using gas chromatography (gas chromatograph apparatus: trade name “GC-2010”, manufactured by Shimadzu Corporation).
Measurement conditions Column: FFAP (manufactured by QUADREX)
Detector: FID

1: Trickle bed reactor 2: Raw material supply line 3: Hydrogen supply line 4: Reaction mixture take-out line 5: High-pressure gas-liquid separator 6: Hydrogen recycle line

Claims (8)

A step of producing a hydrocracked product of 1,4-anhydroerythritol by reaction of 1,4-anhydroerythritol and hydrogen in the presence of a support, a catalyst containing iridium supported on the support , and rhenium. A process for producing a hydrocracked product of 1,4-anhydroerythritol, comprising A. Method for producing 1,4-anhydroerythromycin erythritol hydrogenolysis product of claim 1, wherein the rhenium is supported on a carrier. The hydrocracked product of 1,4-anhydroerythritol according to claim 1 or 2 , wherein the catalyst contains iridium and rhenium in a ratio of 50/1 to 1/6 [iridium / rhenium (molar ratio)]. Production method. The process according to claim 1 1,4-anhydroerythromycin erythritol hydrogenolysis product according to any one of 3 carrier carrying the iridium beam is an inorganic oxide. The process according to claim 2 ~ 1,4-anhydroerythromycin erythritol hydrogenolysis product according to any one of 4 carriers carrying the rhenium is an inorganic oxide. The hydrocracked product of 1,4-anhydroerythritol according to claim 4 or 5 , wherein the inorganic oxide is at least one compound selected from the group consisting of silica, titania, zirconia, alumina, magnesia, and zeolite. Manufacturing method. The hydrocracked product of 1,4-anhydroerythritol according to any one of claims 1 to 6 , wherein the reaction between 1,4-anhydroerythritol and hydrogen in the step A proceeds in the presence of an acid. Manufacturing method. The step of 1,4-anhydroerythritol according to any one of claims 1 to 7 , further comprising a step B of generating 1,4-anhydroerythritol by intramolecular dehydration reaction of erythritol before the step A. A method for producing a hydrocracked product.

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