JP6859657B2 - Method for producing diol compound - Google Patents

Description

The present invention relates to a method for producing a diol compound by hydrogenation hydration of an unsaturated cyclic ether compound.

Diol compounds are useful chemicals that can be used as raw materials for producing polycondensation polymers, and their production methods are diverse. Known chemical production methods include hydrogenation of dicarboxylic acids, diesters and hydroxycarboxylic acids, and hydrolysis of diesters obtained by oxidative esterification, all of which consume large amounts of hydrogen and are also known. , Thermodynamic equilibrium often exists, making it an energy-intensive process. Further, in addition to the fact that the diol compound generally has a high boiling point, when it is obtained as an aqueous solution, it is necessary to distill water in order to separate and recover the diol compound, which causes further energy consumption. There is.

On the other hand, a method for producing a diol compound by hydrolyzing or hydrating a saturated cyclic ether or cyclic carbonate compound is also known. Ring-opening by hydration is characterized in that it is easy to produce a diol compound having a hydroxyl group at the terminal. However, in the case of this method, an unstable evoxide or oxetane ring compound is likely to open the ring, but a saturated cyclic ether compound having a 5-membered ring or a 6-membered ring is very stable and thermodynamically. However, the equilibrium is biased toward the closed ring side, and it is practically difficult to open the ring by hydration.

On the other hand, there is a method of hydrogenating a 5-membered unsaturated cyclic ether compound while hydrating it in one step. In this method, furan is used as the raw material unsaturated cyclic ether compound, and by utilizing the high reactivity of the intermediate vinyl ether, hemiacetalization and hydrolysis are promoted by water, and further hydrogenation is performed to obtain a diol. It is presumed that a compound will be obtained. However, in this method, hydrogenation of the double bond of the vinyl ether also proceeds at the same time. That is, hydrogenation to a saturated cyclic ether compound and hydration to a diol compound (subsequent hydrogenation) become competitive reactions. As a result, the saturated cyclic ether compound and the diol compound are produced at the same time, and it is not easy to selectively obtain the diol compound.

Therefore, in Patent Documents 1-3, a supported or non-supported solid catalyst made of Ru or Ni is used, and a carboxylic acid or the like is added to the reaction system as a water-soluble reaction aid to hydrate the intermediate. A method of promoting and increasing the amount of diol compound produced has been proposed. However, when an acid that dissolves in water is used in combination, problems such as corrosion of the reactor and dissolution of a metal that is an active component of hydrogenation occur in the hydrogenation hydration reaction of the unsaturated cyclic ether compound. In a situation where the action of acid is strong, the intermediate (unsaturated diol) produced by hemiacetalization and hydrolysis of vinyl ether becomes an aldehyde compound by remutability before further hydrogenation, and is condensed and polymerized. However, this causes a decrease in the selectivity of the diol compound.
Furthermore, when the reaction is carried out in the coexistence of a reaction aid such as a water-soluble acid, if these remain in the mixture containing the target diol compound and water, in a subsequent step such as separation of the diol compound and water, There is also a problem that the diol compound is dehydrated and cyclized by the acid. In order to avoid this problem, after the reaction, a step of neutralizing or separating and removing these reaction aids such as water-soluble acids is required, which has a demerit that the manufacturing process becomes complicated and complicated.

Attempts have also been made to improve the yield of the diol compound by improving the solid catalyst in order to avoid such a problem of adding a reaction aid (water-soluble acid). A combination of metal elements centered on an activated carbon-supported catalyst composed of Ni has been proposed. However, when the present inventor produced the catalyst exemplified in Patent Document 4 and carried out the same reaction, the exemplified catalyst had poor catalytic activity in the hydration reaction, and a saturated cyclic ether compound was produced. In addition, hydrogenation decomposition to monoalcohol occurred at the same time to produce unwanted butanol, and the diol compound could not be obtained efficiently.
Although this Patent Document 4 exemplifies zeolite (ZSM-5, ZSM-10) as a carrier, there is no mention of the importance of using a solid acid (acidic zeolite) as a carrier, and solid acid is used. There is no example of using it as a carrier. Normally, the acid catalytic action of a solid acid is weak in water, and its structural stability is also poor in hot water. Patent Document 4 describes that advantageous carrier materials are aluminum oxide, titanium oxide, silicon dioxide, zirconium dioxide and activated carbon, and the carriers in the example of the catalyst are only activated carbon, silicon dioxide and aluminum oxide. The catalysts specifically used in the examples of Patent Document 4 are Re / Ru / activated carbon, Ru / activated carbon, Co / Re / activated carbon, Ru / Cu / activated carbon, Re / Ni / activated carbon, and Rh / Re. / Activated carbon, Ni / Cu / activated carbon, Ru / Ni / activated carbon, Ru / Cu / Re / activated carbon only. In addition, in Patent Document 4, it is described that the furan / water molar ratio = 1: 1 to 10 (water / furan mol ratio = 1 to 10) is preferable, but in the examples, the water / furan mol ratio is 12 to 10. 15 and a large amount of water is used. Further, Patent Document 4 lacks reference to a catalyst for obtaining a diol compound by controlling the production ratio of the saturated cyclic ether and the diol compound and preferentially advancing the hydrogenation hydration reaction, particularly a catalyst carrier.

Non-Patent Documents 1 and 2 mention Ni, Ru, Rh, Pt, and Pd catalysts as hydrogenation catalysts and hydrocracking catalysts for compounds having furan or furan rings. There is no description about catalytic action.

USP4,475,004 USP4,476,332 USP4,146,741 Special table 11-502811

"Contact Hydrogenation Reaction: Application to Organic Synthesis" by Shigeo Nishimura and Gen Takagi (Tokyo Kagaku Dojin, 1987), pp. 284-290 “Handbook of heterogeneous Catalytic Hydrogenation for Organic Synthesis” Shigeo Nishimura (John Wiley & Sons, Inc. 2001) pp. 547-555

The problem with the conventional method of producing a diol compound in one step from a 5-membered or 6-membered unsaturated cyclic ether compound by hydrogenation hydration simultaneous reaction in the presence of a catalyst is that in most catalysts, undesired hydrogenation. In addition to the simultaneous decomposition and the by-production of monool (monoalcohol), if the effect of promoting the hydration reaction of the catalyst is small, a saturated cyclic ether compound is selectively produced instead of a diol compound. In particular, under the condition that the amount of water introduced into the reaction system for hydration is not sufficient, the production ratio of the saturated cyclic ether compound is higher than that of the diol compound. Due to thermodynamic restrictions, it is difficult to hydrate and open a saturated cyclic ether compound into a diol compound. Therefore, when the purpose is to produce a diol compound by a hydrogenation hydration reaction, the saturated cyclic ether compound is used. It is necessary to use a large amount of water to reduce the production ratio. However, when a large amount of water is used, there is a problem that a large amount of energy is required to separate the produced diol compound and water. Therefore, it is desired to develop a method for producing a diol compound from a 5-membered ring or a 6-membered ring unsaturated cyclic ether compound with a high selectivity under the condition that the amount of water introduced into the reaction system is reduced.

Further, as described above, the method of promoting hydration by coexisting a reaction aid such as a water-soluble acid involves corrosion of the reactor, elution of the active metal component, and neutralization or removal of the reaction aid. Due to problems, a method for producing a diol compound in a high yield without using these reaction aids is desired.

Therefore, according to the present invention, when a diol compound is produced in one step by a hydrogenation hydration reaction of an unsaturated cyclic ether compound, the diol compound can be produced with high selectivity, and the product can be separated and the catalyst can be easily reused. At the same time, it is an object of the present invention to provide a method for stably converting an unsaturated cyclic ether compound to produce a diol compound with high efficiency.

As a result of diligent studies on a catalyst for producing a diol compound in one step by advancing a hydrogenation hydration reaction of an unsaturated cyclic ether compound in order to solve the above problems, the present inventor is surprisingly surprised. In the hydrogenation hydration reaction of unsaturated cyclic ether having a 5-membered ring or 6-membered ring structure, a diol compound is used by using a catalyst in which at least one metal element selected from Ni and Co is immobilized on a specific solid acid. It was found that the selectivity of the diol compound was increased and the diol compound could be obtained with high efficiency and stability. In particular, it is important to select the type of metal responsible for hydrogenation and the type of solid acid responsible for hydration, and the balance between hydration and hydrogenation is achieved by appropriately arranging the hydrogenation active points and acid points on the surface of the solid catalyst. It was found that the diol compound can be selectively obtained. Further, the catalyst having a hydrogenation active site and an acid point on the surface can be easily separated by filtration or the like after the reaction, and the diol compound is ringed in a step of separating the obtained diol compound from water or the like. It is possible to avoid becoming a compound.
The present invention has been achieved based on such findings, and the gist of the present invention is as follows.

[1] In a method for producing a diol compound by hydrogenating and hydrating an unsaturated cyclic ether compound raw material with a catalyst in the presence of hydrogen and water, at least one selected from Ni and Co as the catalyst. A method for producing a diol compound, which uses a catalyst in which a metal element is immobilized on a solid acid.

[2] The solid acid is an acidic high-silica zeolite having a three-dimensional pore structure, not having an 8-membered ring pore size, and having a pore size of 10-membered ring or more, and the Si / Al ratio of the zeolite. The method for producing a diol compound according to [1], wherein the ratio is 10 or more and 1000 or less.

[3] The solid acid is at least one selected from an oxide containing niobium, a hydrous oxide containing niobium, a phosphate, and _{a composite oxide containing SiO 2 [1].} The method for producing a diol compound according to the above.

[4] The catalyst is a Ni-supporting catalyst in which at least Ni is supported on the solid acid, and the amount of Ni supported is 0.5% by mass or more and 10% by mass or less with respect to the total mass of the catalyst. The method for producing a diol compound according to any one of [1] to [3].

[5] The catalyst is a carrier catalyst in which Ni and / or Co is supported on the solid acid and one or more of Mn, Re and W are supported as modification aids, and the amount of the modification aids supported is Ni. The method for producing a diol compound according to any one of [1] to [4], which is 100% by mass or less with respect to the mass of Co and / or Co.

[6] Any of [1] to [5], wherein the molar ratio (water / unsaturated cyclic ether compound) of water to the unsaturated cyclic ether compound subjected to the reaction is 0.5 or more and 8 or less. A method for producing a diol compound according to the above.

[7] The method for producing a diol compound according to any one of [1] to [6], wherein the hydrogen pressure in the hydrogenation hydration reaction is 1 MPa or more and 5 MPa or less.

[8] Described in any one of [1] to [7], wherein the diol compound produced by the hydrogenation hydration reaction has a molar ratio of 0.4 or more to the saturated cyclic ether compound produced as a by-product. Method for producing a diol compound.

[9] Described in any one of [1] to [8], which comprises performing a reduction treatment in which the catalyst is brought into contact with a reducing gas at a temperature of 320 ° C. or higher prior to being subjected to the hydrogenation hydration reaction. Method for producing a diol compound.

[10] The method for producing a diol compound according to any one of [1] to [9], wherein the unsaturated cyclic ether compound is a dihydrofuran ring compound or a dihydropyran ring compound.

In the present invention, the diol compound has a high selectivity by carrying out a hydrogenation hydration reaction of an unsaturated cyclic ether compound using a catalyst in which at least one metal element selected from Ni and Co is immobilized on a solid acid. Therefore, it is possible to produce the diol compound with high efficiency even under the condition that the amount of water used is reduced. Further, since sufficient selectivity can be obtained without using a reaction aid such as a water-soluble acid, the product and the catalyst can be easily separated, and the catalyst can be easily replaced or regenerated.

Hereinafter, embodiments of the method for producing a diol compound of the present invention will be described in detail.

In the method for producing a diol compound of the present invention, when a diol compound is produced by a hydrogenation hydration reaction of an unsaturated cyclic ether compound raw material, a hydrogenation hydration reaction is carried out in the presence of a specific hydrogenation hydration reaction catalyst. It is a thing.

[Raw materials / objects]
First, an unsaturated cyclic ether compound as a raw material and a diol compound as a target product will be described.

<Unsaturated cyclic ether compound>
The unsaturated cyclic ether compound as a raw material used in the method for producing a diol compound of the present invention is not particularly limited, and a known unsaturated cyclic ether compound can be used. Examples of the unsaturated cyclic ether compound include 5-membered or 6-membered unsaturated cyclic ether compounds represented by the following general formulas (1), (2), (3), (4), or (5). Can be mentioned.

In the above general formulas (1) to (5), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may be the same or different, and have, for example, a hydrogen atom and a functional group. Examples thereof include various functional groups such as an aliphatic hydrocarbon group which may be present, an aromatic hydrocarbon group which may have a functional group, and an aldehyde group, and specific examples thereof are -H, -OH, and -CH. ₂ OH, -CH ₃ , -CHO and the like can be mentioned.

Specific examples of the unsaturated cyclic ether compound represented by the general formula (1) include furfuryl alcohol, 2-methylfuran, 3-methylfuran, flualdehyde, and furan, with furan being particularly preferable. Is.
Specific examples of the unsaturated cyclic ether compound represented by the general formula (2) are 2-hydroxymethyl-2,3-dihydrofuran, 2-methyl-2,3-dihydrofuran, 3-methyl-2,3. −Dihydrofuran and 2,3-dihydrofuran are preferred examples, with 2,3-dihydrofuran being particularly preferred.
Specific examples of the unsaturated cyclic ether compound represented by the general formula (3) are 2-hydroxymethyl-2,5-dihydrofuran, 2-methyl-2,5-dihydrofuran, 3-methyl-2,5. -Dihydrofuran and 2,5-dihydrofuran are preferred examples, with 2,5-dihydrofuran being particularly preferred.
Specific examples of the unsaturated cyclic ether compound represented by the general formula (4) include 2-hydroxymethyl-3,4-2H-dihydropyran, 2-methyl-3,4-2H-dihydropyran, and 3-methyl. -3,4-2H-dihydropyran, 4-methyl-3,4-2H-dihydropyran and 3,4-2H-dihydropyran are preferred examples, with 3,4-2H-dihydropyran being particularly preferred. Is.
Specific examples of the unsaturated cyclic ether compound represented by the general formula (5) include 2-hydroxymethyl-3,6-2H-dihydropyran, 2-methyl-3,6--2H-dihydropyran and 3-methyl. -3,6-2H-dihydropyran, 4-methyl-3,6-2H-dihydropyran and 3,6--2H-dihydropyran are preferred examples, with 3,6-2H-dihydropyran being particularly preferred. Is.

Although it is possible to use two or more kinds of these unsaturated cyclic ether compounds, usually only one kind is used.

<Diol compound>
The diol compound obtained by the method for producing a diol compound of the present invention is not particularly limited, and is a diol compound obtained by the hydrohydration reaction of the unsaturated cyclic ether compound described above. For example, the following general formula (6) or Examples thereof include the diol compound represented by (7).

In the general formulas (6) and (7), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are synonymous with those in the general formulas (1) to (5).

The diol compound represented by the general formula (6) is a diol compound obtained by hydrogenation hydration of the unsaturated cyclic ether compounds represented by the general formulas (1) to (3), and specific examples thereof include. , 2-Methyl 1,4-butanediol, 3-methyl-1,4-butanediol, 1,2,5-pentanetriol, 1,4-butanediol, and 1,4-butanediol is particularly preferable. Is.
The diol compound represented by the general formula (7) is a diol compound obtained by hydrogenation hydration of the unsaturated cyclic ether compound represented by the general formulas (4) and (5), and specific examples thereof include. , 2-Methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,2,6-hexanetriol, 1,5-pentanediol, especially 1,5-pentanediol. Suitable

<Saturated cyclic ether compound raw material>
In the present invention, the unsaturated cyclic ether compound raw material is hydrogenated and hydrated in the presence of a specific catalyst. Here, the unsaturated cyclic ether compound raw material is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass, based on the whole raw material (100% by mass). % Or more, particularly preferably 99% by mass or more.

The method for producing the unsaturated cyclic ether compound raw material used in the present invention is not particularly limited, but is that the plant-derived raw material is hydrolyzed or hydrolyzed by an acid, the furfural compound is decarbonylated, the butanediene or epoxybutene is partially oxidized, and tetrahydrofurfuryl is used. In addition to the dehydration rearrangement (isomerization) reaction of alcohol, a method using a deal alder reaction of α, β-unsaturated aldehyde can be mentioned.

The purity (content) of the unsaturated cyclic ether compound in the unsaturated cyclic ether compound raw material is as described above, but hydrogenation used in the present invention is performed by removing impurities contained in the unsaturated cyclic ether compound raw material. The decrease in activity of the hydration reaction catalyst over time can be further suppressed, and the diol compound can be produced more stably and with high efficiency. In particular, among impurities contained in the unsaturated cyclic ether compound raw material, a high effect can be obtained by reducing sulfur or sulfur compounds, nitrogen compounds, and various acids.

The form of the sulfur or the sulfur compound contained in the unsaturated cyclic ether compound raw material is not particularly limited, and examples of the valence include a sulfur component ^{of S 0} , S ^2- or S ⁶⁺ (SO _x). More specifically, a thiol group, a sulfhydryl group, a sulfide group, a compound having a disulfide group, an aromatic compound having S as a skeleton, sulfuric acid, a sulfonic acid and salts thereof, sulfite and sulfite, or a complex salt can be mentioned. The amount of these sulfur components contained in the unsaturated cyclic ether compound raw material is usually 50 ppm or less, preferably 30 ppm or less, more preferably 20 ppm or less, more preferably 10 ppm or less, and particularly preferably 6. It is 0 ppm or less. By subjecting an unsaturated cyclic ether compound raw material in which the content of the sulfur component is controlled to 50 ppm or less as the concentration in terms of sulfur element to the hydrogenation hydration reaction step, the catalytic effect of the hydrogenation hydration reaction catalyst used in the present invention can be obtained. It is even more effective. The method for analyzing the amount of sulfur component contained in the unsaturated cyclic ether compound raw material is not particularly limited, but can be quantified as the sulfur element concentration by, for example, a combustion-absorption-ion chromatography method.

The form of the nitrogen compound contained in the unsaturated cyclic ether compound raw material is not particularly limited, and examples of the valence include nitrogen components of ^{N 3-,} N ⁵⁺ , and N ^3+. More specifically, it is ammonia, amines and salts thereof, aromatic compounds having N as a skeleton, nitric acid and nitrate, nitrite and nitrite, or complex salts. The amount of the nitrogen component contained in the unsaturated cyclic ether compound raw material is usually 50 ppm or less, preferably 30 ppm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less, and particularly preferably 4.0 ppm or less in terms of nitrogen element equivalent concentration. Is. By subjecting the unsaturated cyclic ether compound raw material in which the content of the nitrogen component is controlled to 50 ppm or less as the concentration in terms of nitrogen element to the hydrogenation hydration reaction step, the catalytic effect of the hydrogenation hydration reaction catalyst used in the present invention can be obtained. It is even more effective. The method for analyzing the amount of nitrogen component contained in the unsaturated cyclic ether compound raw material is not particularly limited, but can be quantified as the nitrogen element concentration by, for example, the combustion decomposition-chemiluminescence method.

The form of the acid component contained in the unsaturated cyclic ether compound raw material is not particularly limited, but is limited to inorganic acids such as sulfuric acid, sulfonic acid and nitric acid, and organic acids having a sulfon group and a carboxyl group, for example, furansulfonic acid and furancarboxylic. Examples include acid, formic acid and acetic acid. The amount of the acid component contained in the unsaturated cyclic ether compound raw material is usually 2 mgKOH / g or less, preferably 1 mgKOH / g or less, more preferably 0.50 mgKOH / g or less, still more preferably 0.25 mgKOH / g or less as an acid value. , Particularly preferably 0.10 mgKOH / g or less. By subjecting an unsaturated cyclic ether compound raw material in which the amount of these acid components is controlled to 2 mgKOH / g or less as an acid value to a hydrogenation hydration reaction step, the activity of the hydrogenation hydration reaction catalyst used in the present invention over time The drop can be further reduced. The method for measuring the acid value is not particularly limited, but a neutralization titration method can be used. Specifically, the acid value can be measured by diluting the unsaturated cyclic ether compound raw material with ethanol and then titrating with a 0.01 N potassium hydroxide aqueous solution.

The unsaturated cyclic ether compound used in the present invention is usually colorless and transparent. Therefore, the color tone of the unsaturated cyclic ether compound raw material is a value calculated based on the YI (Yellowness Index: yellowness) value of the APHI (American Public Health Association) standard color solution, and is usually 500 or less, preferably 300. Below, it is more preferably 100 or less, and particularly preferably 50 or less. The color tone of the unsaturated cyclic ether compound raw material can be analyzed and calculated by transmission measurement using a color difference meter or the like.

The method for removing impurities from the unsaturated cyclic ether compound raw material is not particularly limited, and examples thereof include methods such as distillation purification and adsorption removal of impurities.

The adsorbent used for separating and removing impurities by adsorption is not particularly limited, but is a porous substance such as activated carbon or ion exchange resin, ion exchange zeolite or silica, or a metal or noble metal, or the metal or noble metal is silica. Those supported on a carrier such as alumina, zeolite or activated carbon are preferably used. A plurality of adsorbents may be used at the same time. As a method of adsorbing and removing, a method of adding an adsorbent to an unsaturated cyclic ether compound raw material and separating the adsorbent by filtration or the like after a certain treatment time may be used, or an unsaturated cyclic ether compound-filled column or the like may be unsaturated. A method of distributing the cyclic ether compound raw material may also be used.

Further, a method of loading a raw material and an adsorbent into a distillation pot at the time of distillation purification and purifying by distillation while adsorbing and removing impurities is also mentioned as a preferable method. As the adsorbent at that time, in addition to the substances listed above, alkaline hydroxides such as NaOH and alkaline carbonates such as _{Na 2} CO _{3 which are effective in removing the acid component are also preferably used.}

Further, it is also preferable to remove impurities by using an adsorbent and then further perform distillation purification to remove impurities that could not be removed by adsorption and impurities derived from the adsorbent. Further, adsorption removal may be performed after distillation purification.

The conditions for storing the unsaturated cyclic ether compound raw material in which the amount of impurities has been reduced by purification or the like are not particularly limited, but it is preferable to store it in an atmosphere of 30 ° C. or lower in which oxygen and light are blocked. The concentration of oxygen in the storage atmosphere is usually 20% or less, preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less.
In some cases, it is also preferable to add a stabilizer for storage. As the stabilizer, antioxidants such as dibutylhydroxytoluene (BHT) and t-butylcatechol (TBC), and polymerization inhibitors are preferably used.

[Hydrogenation hydration reaction catalyst]
Next, the hydrogenation hydration reaction catalyst used in the present invention (hereinafter, may be referred to as “catalyst of the present invention”) will be described.

In the present invention, as the hydrogenation hydration reaction catalyst, a catalyst in which at least one metal element selected from Ni and Co (hereinafter, may be referred to as “Ni and Co”) is immobilized on a solid acid is used. Use.

In the present invention, when a diol compound is produced by hydrogenation hydration of an unsaturated cyclic ether compound raw material, by using such a specific hydrogenation hydration reaction catalyst, it is stable even under low water conditions. Moreover, it becomes possible to produce a diol compound with high efficiency.

That is, since the substance containing Ni and Co has a hydrogenation ability of a carbonyl group, an intermediate having an aldehyde group generated by hydration and tautomerization of an unsaturated cyclic ether compound can also be rapidly hydrogenated. .. Therefore, the progress of undesired side reactions such as condensation involving an intermediate having an aldehyde group is avoided.
Further, for the same reason, it is possible to avoid the progress of an undesired reaction such as polymerization of these compounds, so that it is possible to prevent the situation where the polymer is accumulated on the surface of the catalyst. As a result, effective catalytic active sites for the hydrogenation hydration reaction of unsaturated cyclic ether compounds continue to act for a long time.
By using Ni and Co as the catalytically active metal element, the unsaturated cyclic ether compound can be converted into a diol compound with high selectivity, and the diol compound can be efficiently produced.
For example, when a catalyst containing Ni and Co is used, the selectivity of the total amount of the diol compound produced by the hydrogenation hydration reaction of the unsaturated cyclic ether compound and the saturated cyclic ether compound produced by dehydration cyclization thereof is usually high. It is 90% or more, and the yield of the diol compound is maximized.

Ni and Co are preferably immobilized by adding or supporting a solid acid composed of a specific oxide to a carrier constituting at least a part thereof. Preferably, Ni and Co are used as a supported metal catalyst by being supported on a carrier containing a solid acid.

<Carrier>
The solid acid used as a carrier for Ni and Co is not particularly limited, but phosphates, sulfates and hydroxides, hydroxide-containing oxides, oxides and composite oxides are preferable. Phosphate, the _{sulphate, Al x P y O n,} Zr 3 (PO 4) 4, ZrP 2 O 7, Zr (SO 4) 2 · 4H 2 O, niobium phosphate and the like. Examples of hydroxides, hydrous oxides and oxides include ZrO (OH) ₂ , ZrO ₂ , SiO ₂ , Nb ₂ O ₅ · nH ₂ O (n is usually 3.5 to 4.5). _{Other, ZrSiO 4, ZrO 2 -SiO 2} , ZrO 2 -TiO 2, ZrO 2 -Al 2 O 3, SiO 2 -Al 2 O 3, complex oxides such as _{MgO-SiO 2, MgO-Al} 2 O 3 is Can be mentioned. Among them, preferably, _Al x P _y O _n, phosphate niobium phosphate, etc., double oxide such as _{ZrSiO 4, ZrO 2 -SiO 2,} ZrO 2 -TiO 2, ZrO 2 -Al 2 O 3, Examples thereof include amorphous composite oxides such as SiO _{2- Al 2} O ₃ , MgO-SiO ₂ , MgO-Al ₂ O _{3 , and Nb 2} O ₅ · nH ₂ O. More preferably, the oxide or hydrous oxide containing niobium, _Al x P _y O _n phosphate amorphous, such as, preferably a composite oxide of amorphous containing SiO _2, particularly preferably amorphous _SiO 2 -Al ₂ O ₃ , Nb ₂ O ₅ · nH ₂ O can be mentioned.
Further, in the amorphous SiO _2- Al ₂ O ₃ , the Si / Al ratio is usually 1 or more and 50 or less, preferably 2 or more and 25 or less, more preferably 3 or more and 12 or less, and particularly preferably 4 or more and 8 or less. Is preferable.

The carriers of Ni and Co include the above-mentioned phosphates, sulfates and hydroxides, hydrous oxides, oxides and composite oxides, as well as porous oxides such as acidic clay minerals and acidic zeolites, and mesopores. Oxides having the above can also be used. Of these, a porous oxide such as acidic zeolite is preferable.

The type of acidic zeolite is preferably one having a three-dimensional pore structure, and more preferably one having a pore diameter of 10-membered ring or more without having a pore diameter of 8-membered ring. This is because when the acidic zeolite has an 8-membered ring pore size, the activity and diol selectivity of the catalyst supporting the metal on the acidic zeolite are lowered. If it has a three-dimensional pore structure, does not have a pore diameter of an 8-membered ring, and has a pore diameter of 10-membered ring or more, particularly 12-membered ring or more, diffusion in the pores in a catalyst supporting a metal thereof. Is in a state suitable for hydrogenation and hydration, and the activity of the catalyst and the diol selectivity are increased. Specifically, the acidic zeolite has a three-dimensional pore structure of 8 from the MOR type having a two-dimensional pore structure and an 8-membered ring pore size and the A type having a three-dimensional pore structure having an 8-membered ring pore size. MFI type such as ZSM5, BEA type, MWW type, FAU type such as USY, which does not have a pore diameter of a member ring and has a pore diameter of 10 member rings or more are preferable, and MFI type such as ZSM5 and FAU such as USY are particularly preferable. It is a type.

As the acidic zeolite, a proton-type zeolite or a zeolite ion-exchanged with a divalent or higher cation is preferable, but a proton-type zeolite is more preferable. In this case, it is also preferable to exchange ions in advance with ions of a reducible metal such as Ni, and then reduce the metal ions to form a proton type. In addition, ammonium-type zeolite is usually converted into a proton-type by a treatment such as calcination.

Generally, when the Si / Al ratio of an acidic zeolite is low, the acidity becomes weak, and when it is high, the number of acid points decreases. However, the acidic zeolite used as a carrier of Ni and Co in the catalyst of the present invention has a high Si / Al ratio. High silica type is preferable. This is because if the Si / Al ratio is too low, the zeolite structure is likely to collapse and desorption from the zeolite due to the ionization of immobilized Ni and Co is likely to occur under the conditions of the hydrogenation hydration reaction of the unsaturated cyclic ether. ..

The nature and number of acid points that depend on the Si / Al ratio of the acidic zeolite of high silica affect the balance between hydrogenation and hydration in the hydrogenation hydration reaction. When the acid property is insufficient, hydrogenation proceeds with priority over hydration, so that a saturated cyclic ether compound is likely to be produced, and it becomes difficult to obtain a target diol compound. The Si / Al ratio of the acidic zeolite of high silica is usually 5 or more and 10000 or less, preferably 10 or more and 2000 or less, more preferably 15 or more and 1500 or less, and particularly preferably 20 or more and 1000 or less. By utilizing the effect of the Si / Al ratio on the balance between hydrogenation and hydration and controlling the amount of Ni and Co carried and the Si / Al ratio of the acidic zeolite of high silica, the target compound in the hydrogenation hydration reaction. It is possible to control the production ratio of the diol compound, which is a hydrogenated product, and the saturated cyclic ether compound, which is a by-product.

In the catalyst of the present invention, the amount of alkali such as Na remaining in the acidic zeolite of high silica used as a carrier also affects the hydrogenation hydration reaction. The amount of alkali (M) remaining, the oxide _(M 2 O) weight ratio (wt%) Conversion usually 0.2 wt% or less, preferably 0.1 wt% or less, more preferably 0.05 It is mass% or less. The number of acid points of the acidic zeolite of high silica used as a carrier is usually 0.001 mmol / g or more and 2.0 mmol / g or less, preferably 0.002 / g or more and 1.0 mmol / g or less, and more preferably 0. It is 004 mmol / g or more and 0.5 mmol / g or less, and particularly preferably 0.005 mmol / g or more and 0.1 mmol / g or less. The number of these acid sites can be quantified by elimination NH ₃ amount and the like in TPD (program thermal desorption) analysis of the adsorption NH _3.

The specific surface area of the carrier is not particularly limited, but is usually 1 m ² / g or more and 1000 m ² / g or less, preferably 5 m ² / g or more and 600 m ² / g or less, and more preferably 10 m ² / g or more and 500 m ² / g or less. is there. The pore volume of the carrier is not particularly limited, but is usually 0.1 ml / g or more and 1 ml / g or less, preferably 0.2 ml / g or more and 0.5 ml / g or less. If the specific surface area and pore volume of the carrier are small, the unsaturated cyclic ether compound is not sufficiently converted and the unreacted unsaturated cyclic ether compound needs to be recovered, which is not efficient. If it is too large, it tends to produce an undesired polymer. Here, the specific surface area of the carrier is determined by a gas adsorption method such as nitrogen. The pore volume of the carrier is determined by a gas adsorption method such as nitrogen or a mercury intrusion method.

Only one of these solid acids may be used, or two or more of these solid acids may be mixed and used.

<Supported metal element>
In the present invention, as at least one metal element selected from Ni and Co, only Ni may be used, only Co may be used, or Ni and Co may be used, but Ni is preferably used. Be done. The reason is that Ni is not only inactive in the decomposition reaction of the diol compound, which is the target product, but also hydrogenalytic decomposition of unsaturated cyclic ether compounds of raw materials and intermediates into monool compounds such as butanol. This is because the side reaction of is unlikely to occur.

<Supported amount (content in catalyst)>
The content of Ni and Co in the catalyst (the amount supported on the carrier) depends on the type of metal and the type of solid acid used as the carrier, so it cannot be said unconditionally, but it is based on the total mass of the catalyst (100% by mass). Usually 0.05% by mass or more and 30% by mass or less, preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass or more and 10% by mass or less, and particularly preferably 0.5% by mass or more. It is 5% by mass or less. If the Ni and Co contents are low, the unsaturated cyclic ether compound will not be sufficiently converted, and recovery of the unreacted unsaturated cyclic ether compound will be required, which is not only inefficient, but also from the used catalyst. The recovery efficiency when recovering a metal element is reduced. On the other hand, if the contents of Ni and Co are too large, the rate of hydrogenation is higher than that of hydration in the reaction of the unsaturated cyclic ether compound, and an undesired reaction such as hydrocracking is likely to occur. As a result, the production ratio of by-products such as the saturated cyclic ether compound increases, and the diol compound cannot be efficiently produced, which is not preferable.

In particular, when a Ni-supported catalyst is used as the catalyst of the present invention, the amount of Ni supported is preferably 0.5% by mass or more and 20% by mass or less based on the total mass of the catalyst (100% by mass). It is more preferably 0% by mass or more and 10% by mass or less.

<Modifying aid>
The catalyst of the present invention in which Ni and Co are immobilized on a solid acid can contain a modification aid in order to improve the performance and stability of the catalyst. Examples of the modifying aid include metals of Group 6-11 of the Periodic Table and their ions. Mn, Re, W and their ions are preferred, Mn, Re and their ions are more preferred, and Re and its ions are particularly preferred. A plurality of these metals and ions may be used in combination. By including these modifying aids in the catalyst, the selectivity of the diol compound may be further improved, and the decrease in the activity of the catalyst over time may be suppressed, so that the diol compound can be produced more efficiently. is there.

The forms of these modifying aids in the catalyst of the present invention are not particularly limited, but are metal metals, chlorides, carboxylates, carbonates, phosphates, nitrates, sulfates, ammonium salts, hydroxides, and oxidations. Products, composite oxides, and mixtures thereof include, preferably metal metals, chlorides, carboxylates, carbonates, ammonium salts, hydroxides, oxides, composite oxides, and mixtures thereof. .. These modification aids may be compounded in advance by adding to the above-mentioned solid acid carrier, or may be added after supporting Ni and Co on the solid acid carrier. Further, it may be used by compounding or alloying with Ni and Co. Preferably, when Ni and Co are immobilized on the above-mentioned solid acid carrier, these modifying aids are added at the same time to form a complex.

When the catalyst of the present invention contains these modification aids, the content thereof depends on the metal elements of Ni and Co and the type of carrier, and therefore cannot be unequivocally determined, but is based on the total mass of the catalyst (100 mass). %), Usually 0.01% by mass or more and 20% by mass or less, preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and particularly preferably 0.2% by mass. % Or more and 2% by mass or less.
Further, the content ratio of these modification aids to Ni and Co cannot be unequivocally determined because it depends on the type of metal element and carrier, but it is preferably smaller than the content of Ni and Co, and the mass of Ni and Co is preferable. Is usually 0% by mass or more and 100% by mass or less, preferably 1% by mass or more and 80% by mass or less, more preferably 2% by mass or more and 70% by mass or less, and particularly preferably 5% by mass or more and 50% by mass. It is mass% or less.

If the content of the modifying aid in the catalyst of the present invention is too small, the effect of improving the selectivity of the diol compound and the effect of suppressing the decrease in activity of the catalyst over time can be sufficiently obtained by using the modifying aid. Can not. On the other hand, if the content of the modification aid is too large, the activity of the catalyst is lowered and the side reaction of the unsaturated cyclic ether compound is accompanied, and the selectivity of the diol compound is lowered, which is not efficient.

<Fixing method>
As a method for immobilizing Ni and Co in a solid acid, a method in which a liquid in which a compound of Ni and Co is dissolved is added to the above-mentioned solid acid is preferably used. Further, a method of adding or supporting a substance containing Ni and Co to the above-mentioned substance on which a solid acid is supported can also be adopted, and a target catalyst may be obtained by means such as physical mixing.

Examples of the Ni and Co compounds used for immobilizing Ni and Co include complex compounds such as Ni and Co nitrates, chlorides, ammine complexes and nitroammin compounds, and preferably ammine complexes, nitroammin compounds and nitrates. Examples thereof include water-soluble raw materials that do not contain sulfur and halogen elements, and particularly preferably nitrates. After adding the Ni and Co compounds to the solid acid carrier, subsequent removal of water and liquid components, drying and firing in a gas containing oxygen may be carried out.
When producing a catalyst containing Ni and Co and a modification aid, the same procedure as described above may be carried out using a solution in which the compound of the modification aid is dissolved together with the compound of Ni and Co.

Hereinafter, a method for supporting Ni, Co, and a modification aid used as needed will be described.
The method of supporting Ni and Co on a solid acid carrier is not particularly limited, and examples thereof include an ion exchange method, an impregnation supporting method, a pore filling method, an incident-wetness method, and a spray supporting method. Here, the amount of supported can be controlled by adjusting the concentration and pH of the aqueous solution of the Ni and Co compounds used for supporting and the compound used as a modification aid.

The solid acid carrier supporting Ni and Co may be calcined in advance in a gas atmosphere containing oxygen. In this case, the firing temperature is usually 200 ° C. or higher and 800 ° C. or lower, preferably 300 ° C. or higher and 600 ° C. or lower, more preferably 350 ° C. or higher and 550 ° C. or lower, and particularly preferably 400 ° C. or higher and 500 ° C. or lower.

After supporting Ni, Co and, if necessary, a modification aid used by an ion exchange method or an impregnation carrying method on a solid acid carrier, water and liquid components are removed by filtration, centrifugal deflation, and drying. After that, firing in air or the like is also preferably performed. The firing temperature at this time is usually 200 ° C. or higher and 800 ° C. or lower, preferably 300 ° C. or higher and 600 ° C. or lower, more preferably 350 ° C. or higher and 550 ° C. or lower, and particularly preferably 400 ° C. or higher and 500 ° C. or lower. It is also preferable to load the solid acid carrier after the support into a tube and bake while flowing a gas containing oxygen.

Furthermore, Ni and Co are reduced by reacting the catalyst with a reducing agent in the liquid phase, or by loading the catalyst into a tube and allowing a gas containing hydrogen or alcohol to flow and treating the catalyst under a reducing gas stream. Can be activated. Examples of the reducing agent used for reduction in the liquid phase include formalin, hydrazine, hydroxylamine, hydroxyacetone, ethanol, formic acid, oxalic acid, and hydrogen, and preferably formalin and hydrazine. Examples of the reducing gas include hydrogen, ammonia, carbon monoxide, nitric oxide, and hydrogen is preferable. The temperature when treated with a reducing gas is usually 200 ° C. or higher and 900 ° C. or lower, preferably 300 ° C. or higher and 600 ° C. or lower, and particularly preferably 320 ° C. or higher and 550 ° C. or lower. Such a reduction treatment may be carried out immediately before the unsaturated cyclic ether compound raw material is subjected to a hydrogenation hydration reaction. Further, it may be carried out in the same reactor as the reactor in which the hydrogenation hydration reaction of the unsaturated cyclic ether compound raw material is carried out.

[Hydrogenation hydration reaction]
The reaction method of the hydrogenation hydration reaction in the present invention is not particularly limited, and either a batch reaction or a continuous flow reaction can be carried out, but it is industrially preferable to use a continuous flow reaction method. .. The reaction form of the hydrogenation hydration reaction can be carried out in either a liquid phase reaction or a gas phase reaction, but the unsaturated cyclic ether compound raw material and the catalyst of the present invention are brought into contact with each other by a highly efficient liquid phase reaction. It is preferable to carry out the reaction.

In the case of the continuous flow reaction method, usually, a mixed raw material containing an unsaturated cyclic ether compound raw material is continuously supplied to a tubular reactor loaded with a catalyst or a reactor in which the catalyst is suspended, and used as a catalyst in the reactor. The reaction proceeds by contact to obtain a diol compound.

In the hydrogenation hydration reaction of the unsaturated cyclic ether compound using the catalyst of the present invention, hydrogen for hydrogenation is supplied. The amount of hydrogen to be supplied is not particularly limited, but the molar ratio (hydrogen / unsaturated cyclic ether compound) to the unsaturated cyclic ether compound in the unsaturated cyclic ether compound raw material is usually 0.1 or more and 50 or less, preferably 0. It is 2 or more and 25 or less, more preferably 0.5 or more and 10 or less, and particularly preferably 1 or more and 5 or less. If the amount of hydrogen is small, the unsaturated cyclic ether compound is not sufficiently converted, and it is necessary to recover the unreacted unsaturated cyclic ether compound, which is not efficient. If the amount of hydrogen is too large, the amount of hydrocracking products of the unsaturated cyclic ether compound increases, and the yield of the diol compound decreases, which is not preferable. The purity of the hydrogen gas used is usually 99% or more, preferably 99.9% or more, more preferably 99.99% or more, and particularly preferably 99.999% or more.

In addition, it is necessary to supply water in order to proceed with the hydrogenation hydration reaction. The amount of water to be supplied is not particularly limited, but the molar ratio (water / unsaturated cyclic ether compound) to the unsaturated cyclic ether compound in the unsaturated cyclic ether compound raw material is usually 0.5 or more and 100 or less, preferably 1 or more. It is 50 or less, more preferably 2 or more and 20 or less, particularly preferably 3 or more and 10 or less, and most preferably 4 or more and 8 or less. If the amount of water is small, the hydration reaction will not proceed easily, and the cyclic ether compound will be the main product and the yield of the diol compound will decrease. If the amount of water is too large, a large amount of energy is required to separate the produced diol compound from water, which is not preferable.
Further, by controlling the amount of water to be supplied and the raw material of the unsaturated cyclic ether compound (water / unsaturated cyclic ether compound molar ratio), the diol compound which is the target product in the hydrogenation hydration reaction and the saturated cyclic ring which is a by-product. It is possible to control the production ratio of ether compounds.

In the case of a tubular reactor, the residence time of the catalyst layer is usually 0.001 seconds or more and 10 seconds or less, preferably 0.01 seconds or more and 5 seconds or less, more preferably 0.05 seconds or more and 2 seconds or less, and particularly preferably 0. . 1 second or more and 1 second or less. In the case of a batch reactor, the reaction time is usually 20 minutes or more and 10 hours or less, preferably 40 minutes or more and 8 hours or less, more preferably 1 hour or more and 6 hours or less, and particularly preferably 2 hours or more and 4 hours or less. If the amount of catalytic metal (Ni, Co) or the amount of catalyst is too small with respect to the supply amount of the unsaturated cyclic ether compound raw material, or if the residence time or reaction time is too short, the unsaturated cyclic ether compound will not be sufficiently converted. It is not efficient because it requires recovery of unreacted unsaturated cyclic ether compound. Further, when the amount of catalytic metal (Ni, Co) or the amount of catalyst relative to the supply amount of the unsaturated cyclic ether compound raw material is too large, or when the residence time or reaction time is too long, the produced diol compound undergoes a sequential reaction. It may cause a decrease in the yield of the diol compound as a result. However, when a continuous reaction is carried out for a long period of time, an excess amount of catalyst may be loaded in advance in anticipation of a decrease in catalyst activity.

The reaction temperature of the hydrogenation hydration reaction of the present invention is usually 100 ° C. or higher and 240 ° C. or lower, preferably 120 ° C. or higher and 220 ° C. or lower, more preferably 130 ° C. or higher and 200 ° C. or lower, and particularly preferably 140 ° C. or higher and 180 ° C. or lower. is there. If the reaction temperature is low, the unsaturated cyclic ether compound is not sufficiently converted, and it is necessary to recover the unreacted unsaturated cyclic ether compound, which is not efficient. Further, if the reaction temperature is too low, the hydration reaction does not proceed, and as a result, a saturated cyclic ether compound is selectively produced, and the production ratio of the target diol compound is reduced, which is not efficient. On the other hand, if the reaction temperature is too high, undesired hydrocracking proceeds and monool compounds are by-produced, resulting in a decrease in the yield of the diol compound, which is not preferable.

The hydrogen pressure (partial pressure) of the reaction system is usually 0.5 MPa or more and 6 MPa or less, preferably 1 MPa or more and 5 MPa or less, and more preferably 2 MPa or more and 4 MPa or less in absolute pressure notation. If the hydrogen partial pressure is too high, hydrogenation tends to proceed, the balance between hydrogenation and hydration in the hydrogenation hydration reaction tends to be inclined to hydrogenation, and the saturated cyclic ether compound tends to be the main product. Further, if the hydrogen pressure is too high, hydrocracking tends to proceed, and the yield of the diol compound decreases. On the other hand, if the hydrogen pressure is too low, the hydrogenation of intermediates produced by the hydration reaction (which may become aldehydes due to remutability) may not proceed, in which case condensation or polymerization of them may occur. Side reactions become prominent and the selectivity of the diol compound decreases.

In the case of a liquid phase reaction, a solvent can be used. The solvent used is not particularly particular, but in consideration of separation from the product, an organic compound such as a diol compound as a product, a saturated cyclic ether compound which is a major by-product, or cyclohexane which is stable under hydrogenation conditions is used. Is preferable. Specifically, when the unsaturated cyclic ether compound as a raw material is furan or dihydrofuran, the product 1,4-butanediol or THF (tetrahydrofuran) can be used as the solvent. When the unsaturated cyclic ether compound as a raw material is dihydropyran, the product 1,5-pentanediol or THP (tetrahydropyran) can be used as the solvent. It is also preferable to circulate a part of the product and use it as a solvent.

During the hydrogenation hydration reaction, by-products can be purged and removed, and catalysts can be added or replaced, if necessary. It is also preferably used to continuously supply the unsaturated cyclic ether compound raw material. When excess hydrogen is used, the hydrogen escaped from the reactor can be circulated and used.

When the unsaturated cyclic ether compound raw material is continuously supplied to the hydrogenation hydration reaction step, the step of producing the unsaturated cyclic ether compound can be linked before the hydrogenation hydration reaction step. Examples of methods for producing unsaturated cyclic ether compounds include, as described above, decarbonylation of furfural compounds, production of furan or dihydrofuran by partial oxidation of butadiene and epoxybutene, and dihydro by dehydration isomerization of tetrahydrofurfuryl alcohol. The production of pyran is mentioned.

It is preferable that the unsaturated cyclic ether compound raw material obtained in the first-stage production step is purified by distillation or adsorption / removal of impurities, and then continuously supplied to the hydrogenation hydration reaction step. .. In the case of distillation purification, it is effective not only to eliminate impurities having a high boiling point but also to remove impurities having a low boiling point and supply them to the hydrogenation hydration reaction step.

Depending on how the pre-stage step or purification step is connected to the hydrogenation hydration reaction step, and the conditions for recycling the product or solvent used in the hydrogenation hydration reaction step, the purpose of the unsaturated cyclic ether compound as a raw material is The diol compound and the saturated cyclic ether compound produced as a by-product may be contained or accompanied. However, as long as there is no problem such as a decrease in the reaction rate, a raw material containing such a compound may be used.

In the method for producing a diol compound according to the present invention, a reaction aid can be used for the purpose of reinforcing the acid property in order to promote hydration (production of the diol compound). As the reaction aid, in addition to acids such as sulfuric acid and p-toluenesulfonic acid, acidic sulfates such as aluminum sulfate and zinc sulfate are used in a state of being dissolved in water. However, if the diol compound produced with these reaction aids remaining is heated in separation from water, the diol compound produced will be dehydrated and cyclized by the acid to become a cyclic saturated ether compound. Inconvenience occurs. Therefore, in this case, it is necessary to neutralize and remove these reaction aids after the reaction is completed. On the other hand, according to the catalyst of the present invention, the hydrogenation hydration reaction can be carried out with a sufficient conversion rate, selectivity and yield. Therefore, these reaction aids should not be used in the method for producing a diol compound of the present invention. Therefore, such a post-treatment step can be omitted, which is preferable.

According to the method of the present invention, not only can the hydrohydration reaction proceed efficiently, but also hydrocracking can be suppressed. For example, taking furan as an unsaturated cyclic ether compound, the selectivity of butanol produced as a by-product by hydrocracking is 5% or less. In addition, since Ni and Co can sufficiently promote hydrogenation of carbonyls, hydrogenation of aldehydes generated by hydration and tautomerism of intermediates proceed smoothly, and by-products due to condensation and polymerization of aldehydes. There is also a feature that there are few. Moreover, since the reaction is in the coexistence of water and hydrogen, the formation of hemiacetal is small.

The obtained diol compound is separated from a solvent, water, a saturated cyclic ether compound, and other by-products to obtain a product. The method for separating the diol compound is not particularly particular, but usually distillation purification is preferably used. In some cases, a further purification step is provided to obtain a high-purity diol compound. The purity of the diol compound to be produced is usually 95% or more, preferably 98% or more, and more preferably 99%.

By using the catalyst of the present invention, a diol compound having a low impurity content can be obtained extremely efficiently. The purity of the obtained diol compound is usually 95% or more. In the catalyst of the present invention, since the polymerization reaction and the like on the surface of the catalyst are avoided, the proportion of by-products due to the polymerization reaction and the like contained in the obtained diol compound is extremely low.

The diol compound obtained by the present invention is colorless and transparent, and is 50 or less when calculated by a number based on the YI (Yellowness Index: yellowness) value of an APHI (American Public Health Association) standard color solution.

Since the diol compound obtained by the present invention has an extremely low impurity content, it is useful as a raw material for various polymers and a solvent. Further, for the same reason, it is useful as an intermediate for the synthesis of derivative products, and a synthetic reaction using a diol compound as a raw material can be efficiently carried out.

Further, according to the method of the present invention, it is possible to co-produce a saturated cyclic ether compound together with a diol compound. In particular, by controlling the amount ratio of the unsaturated cyclic ether compound as the raw material to the water to be introduced, or by adjusting the reaction temperature and hydrogen pressure, both are controlled while controlling the production ratio of the diol compound and the saturated cyclic ether compound. Can be manufactured.

When a diol compound is produced as a target product by the method of the present invention, the molar ratio (diol compound / saturated cyclic ether compound molar ratio) of the diol compound produced by the hydrogenation hydration reaction to the by-produced saturated cyclic ether compound is 0. It is preferably 0.4 or more, more preferably 0.6 or more, and particularly preferably 0.8 or more.

By using the catalyst of the present invention, in producing a diol compound from an unsaturated cyclic ether compound, the amount of by-products produced can be reduced, and the components adhering to the catalyst during the hydrogenation hydration reaction can be reduced. Since the catalyst can be used continuously for a long period of time, the frequency of catalyst replacement and regeneration can be reduced.

When the catalyst is deactivated, the catalyst regeneration method and regeneration treatment are not particularly limited. For example, a method in which the catalyst is removed from the reactor, dried, and then treated with a gas containing nitrogen or hydrogen at a high temperature to remove components adhering to the surface of the catalyst, or a gas containing oxygen. It is possible to restore the catalyst performance by a method of performing treatment at a high temperature with the above method and burning off the components adhering to the surface of the catalyst.
In addition, the catalyst performance can be restored by removing impurities and cork adhering to the catalyst surface by washing with an organic solvent such as alcohol and drying.

After removing the adhering components, the same reduction treatment as in the preparation of the catalyst is also carried out before being subjected to the hydrogenation hydration reaction of the unsaturated cyclic ether compound again. That is, the metal responsible for the catalytic activity can be reduced by reacting with a reducing agent in the liquid phase or by loading the tube into a tube to circulate a gas containing hydrogen or alcohol and treating the metal in a reducing gas stream. It is preferably performed.

These series of regeneration treatments may be carried out with the catalyst loaded in the reactor that carries out the hydrogenation hydration reaction. In this case, it is preferable to provide a plurality of reactors for performing a hydrogenation hydration reaction in advance. By doing so, while the catalyst loaded in one reactor is regenerated, the hydrogenation and hydration reaction of the unsaturated cyclic ether compound is continuously carried out by the catalyst loaded in another reactor. It becomes possible to produce a diol compound.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded.

The purity of the unsaturated cyclic ether compound, which is the raw material of the unsaturated cyclic ether compound, is estimated from the peak area ratio of gas chromatography, and the sulfur element equivalent concentration and nitrogen element equivalent concentration of impurities are measured by combustion-absorption-ion chromatograph, respectively. Method (combustion device: sample combustion device QF-02 manufactured by Mitsubishi Chemical Co., Ltd., analyzer: ion chromatograph DX-500 manufactured by Nippon Dionex Co., Ltd.), combustion decomposition-chemical emission method (manufactured by Mitsubishi Chemical Co., Ltd.) Trace nitrogen analyzer TN-10).
Further, in the following, "%" in the notation of the catalyst indicates "mass%".

[Hydrogenation and hydration reaction of furan]
[Example 1: Hydrogenation hydration reaction with ZSM5 (Si / Al = 75) supported 2% Ni-0.5% Re catalyst]
As a carrier, a commercially available proton-type MFI zeolite (ZSM5, Si / Al = 75, specific surface area = 410 m ² / g, Na ₂ O content 0.05% by mass) powder is used at 500 ° C. under an air stream of about 100 ml / min. It was fired for 4 hours. 5.0 g of this calcined zeolite was impregnated with Ni and Re by the incident-wetness method using a mixed aqueous solution in which _{Ni nitrate and Re 2} O _{7 were dissolved.} After removing the water in a hot water bath, it was dried at 120 ° C. for 12 hours under an air flow of about 100 ml / min, and then calcined at 500 ° C. for 4 hours. Further, it was reduced at 450 ° C. for 2 hours under a hydrogen stream of 75 ml / min, and a ZSM5 (Si / Al = 75) -supported 2% Ni-0.5% Re catalyst (2% by mass Ni, 0.5% by mass Re, The balance ZSM5 (Si / Al = 75)) was obtained.

Furan, a commercially available reagent, was used as a raw material for an unsaturated cyclic ether compound in a hydrogenation hydration reaction without any particular purification. The purity of this furan was 99% by mass or more, and the impurity content was 2 ppm or less in terms of sulfur element and 5 ppm or less in terms of nitrogen element.

An autoclave equipped with a 200 mL induction stirring mechanism was immersed in a vat filled with ice water to cool it, 48 g of water was added, and then 2 g of a ZSM5-supported 2% Ni-0.5% Re catalyst obtained by the above method was added. Input. Further, 34 g of the above-mentioned franc was charged. At this time, the molar ratio of water to furan was 5.33. The autoclave was closed and the internal gas was replaced with hydrogen (general industrial hydrogen gas purity 99.99 vol% or more) while cooling with ice water. After checking if there is any leakage in the autoclave, the temperature of the autoclave is raised while stirring (300 rpm) by the induction stirring method, and just before the internal temperature reaches 150 ° C., the stirring speed is increased to 1000 rpm and the hydrogen pressure is increased to the reactor. The pressure was adjusted to 4 MPa, and the hydrogenation hydration reaction was started at an internal temperature of 150 ° C.

After a lapse of a predetermined time, the reactor was air-cooled, and when the internal temperature became 50 ° C. or lower, the reactor was further cooled by placing it in a vat filled with ice water. When the internal temperature reaches 6 ° C, open the purge valve and return to normal pressure.
The autoclave lid was then opened and the contents were quickly sampled. The contents were diluted with ethanol, diethylene glycol dimethyl ether was added as an internal standard, and the contents were analyzed quantitatively by FID-GC. The unsaturated cyclic ether conversion rate and the diol selectivity were determined from the following formulas.

Franc conversion rate (%) =
[1- {Remaining amount of unsaturated cyclic ether after reaction (mol)
/ Unsaturated cyclic ether supply amount (mol)}] × 100

Diol selectivity (%) =
{Diol yield (%) / unsaturated cyclic ether conversion rate (%)} x 100
= [{Diol production amount (mol) / unsaturated cyclic ether charge amount (mol)}
× 100 (%) / unsaturated cyclic ether conversion rate (%)] × 100
Similarly, the selectivity of by-products such as saturated cyclic ether was also determined, and the total selectivity of diol and saturated cyclic ether, the selectivity of monool, and the production ratio of diol to saturated cyclic ether were calculated.
These results are shown in Table 1.

As shown in Table 1, when a ZSM5 (Si / Al = 75) -supported 2% Ni-0.5% Re catalyst was used, unsaturated cyclic ether (furan) conversion in a hydrogenation hydration reaction for 300 minutes. The rate was 98% and the diol (1,4-butanediol) selectivity was 43%. Similarly, the saturated cyclic ether (THF) selectivity was 54% and the molar ratio of diol / saturated cyclic ether was 0.80. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Example 2: Hydrogenation hydration reaction with ZSM5 (Si / Al = 800) supported 2% Ni-0.5% Re catalyst]
Using a commercially available proton-type MFI zeolite (ZSM5, Si / Al = 800, specific surface area = 360 m ² / g, Na ₂ O content 0.05% by mass or less) powder as a carrier, in the same manner as in Example 1, A ZSM5 (Si / Al = 800) -supported 2% Ni-0.5% Re catalyst was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction product was analyzed in the same manner. It was shown to.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 120 minutes was 99%, and the diol (1,4-butanediol) selectivity was 30%. Similarly, the saturated cyclic ether (THF) selectivity was 68% and the molar ratio of diol / saturated cyclic ether was 0.44. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Example 3: Hydrogenation hydration reaction with USY (Si / Al = 23) supported 2% Ni-0.5% Re catalyst]
Using a commercially available proton-type FAU zeolite (USY, Si / Al = 23, specific surface area = 720 m ² / g, Na ₂ O content 0.03 mass%) powder as a carrier, USY in the same manner as in Example 1. A (Si / Al = 23) supported 2% Ni-0.5% Re catalyst was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction product was analyzed in the same manner. Indicated.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the 240-minute hydrogenation hydration reaction was 94%, and the diol (1,4-butanediol) selectivity was 50%. Similarly, the saturated cyclic ether (THF) selectivity was 42% and the molar ratio of diol / saturated cyclic ether was 1.19. The selectivity of monool (butanol) produced by hydrocracking was 1%.

[Example 4: Hydrogenation hydration reaction using BEA (Si / Al = 75) -supported 2% Ni-0.5% Re catalyst]
Using a commercially available proton-type BEA zeolite (Si / Al = 75, specific surface area = 500 m ² / g, Na ₂ O content 0.03% by mass or less) powder as a carrier, BEA (Si / Al = 75, Na 2 O content 0.03 mass% or less) was used in the same manner as in Example 1. Si / Al = 75) A supported 2% Ni-0.5% Re catalyst was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction product was analyzed in the same manner. The results are shown in Table 1. It was.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction at 210 minutes was 100%, and the diol (1,4-butanediol) selectivity was 48%. Similarly, the saturated cyclic ether (THF) selectivity was 50% and the molar ratio of diol / saturated cyclic ether was 0.96. The selectivity of monool (butanol) produced by hydrocracking was 1%.

[Example 5: Hydrogenation hydration reaction using BEA (Si / Al = 75) -supported 2% Ni-2% Re catalyst]
Using a commercially available proton-type BEA zeolite (Si / Al = 75, specific surface area = 500 m ² / g, Na ₂ O content 0.03% by mass or less) powder as a carrier, BEA (Si / Al = 75, Na 2 O content 0.03% by mass or less) was used in the same manner as in Example 1. A 2% Ni-2% Re catalyst supported by Si / Al = 75) was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction products were analyzed in the same manner. The results are shown in Table 1.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 120 minutes was 99%, and the diol (1,4-butanediol) selectivity was 45%. Similarly, the saturated cyclic ether (THF) selectivity was 44% and the molar ratio of diol / saturated cyclic ether was 1.02. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Example 6: ZSM5 (Si / Al = 75) supported 1% Ni-0.5% Re-catalyzed hydrogenation hydration reaction]
Using a commercially available proton-type MFI zeolite (ZSM5, Si / Al = 75, specific surface area = 410 m ² / g, Na ₂ O content 0.05% by mass) powder as a carrier, ZSM5 in the same manner as in Example 1. A (Si / Al = 75) supported 1% Ni-0.5% Re catalyst was prepared. Using 4 g of this catalyst, the hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 1 except that the reaction temperature was set to 165 ° C., and the reaction products were analyzed in the same manner, and the results are shown in Table 1. ..
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction at 270 minutes was 99%, and the diol (1,4-butanediol) selectivity was 60%. Similarly, the saturated cyclic ether (THF) selectivity was 35% and the molar ratio of diol / saturated cyclic ether was 1.71. The selectivity of monool (butanol) produced by hydrocracking was 3%.

[Example 7: Hydrogenation hydration reaction using ZSM5 (Si / Al = 75) -supported 2% Ni catalyst]
As a carrier, a commercially available proton-type MFI zeolite (ZSM5, Si / Al = 75, specific surface area = 410 m ² / g, Na ₂ O content 0.05% by mass) powder and an aqueous solution of Ni nitrate are used in the same manner as in Example 1. Then, a ZSM5 (Si / Al = 75) -supported 2% Ni catalyst was prepared, and the hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 1 except that the hydrogen pressure of the reactor was adjusted to 5 MPa. The reaction products were analyzed and the results are shown in Table 1.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the 180-minute hydrogenation hydration reaction was 88%, and the diol (1,4-butanediol) selectivity was 34%. Similarly, the saturated cyclic ether (THF) selectivity was 65% and the molar ratio of diol / saturated cyclic ether was 0.52. The selectivity of monool (butanol) produced by hydrocracking was 1%.

[Example 8: Hydrogenation hydration reaction with USY (Si / Al = 100) supported 2% Ni-0.5% Re catalyst]
Using a commercially available proton-type FAU zeolite (USY, Si / Al = 100, specific surface area = 630 m ² / g, Na ₂ O content 0.05% by mass) powder as a carrier, USY in the same manner as in Example 1. A (Si / Al = 100) supported 2% Ni-0.5% Re catalyst was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction product was analyzed in the same manner. Indicated.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 150 minutes was 94%, and the diol (1,4-butanediol) selectivity was 29%. Similarly, the saturated cyclic ether (THF) selectivity was 68% and the molar ratio of diol / saturated cyclic ether was 0.43. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Example 9: Hydrogenation hydration reaction using BEA (Si / Al = 20) -supported 4% Ni-1% Re catalyst]
A commercially available proton-type BEA zeolite (Si / Al = 20, specific surface area = 500 m ² / g, Na ₂ O content 0.05% by mass) powder was used as a carrier, and BEA (Si) was used in the same manner as in Example 1. / Al = 20) A supported 4% Ni-1% Re catalyst was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction product was analyzed in the same manner, and the results are shown in Table 1.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 120 minutes was 100%, and the diol (1,4-butanediol) selectivity was 51%. Similarly, the saturated cyclic ether (THF) selectivity was 43% and the molar ratio of diol / saturated cyclic ether was 1.19. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Example 10: Hydrogenation hydration reaction with ZSM5 (Si / Al = 75) supported 2% Ni-0.5% Re catalyst]
Using a commercially available proton-type MFI zeolite (ZSM5, Si / Al = 75, specific surface area = 410 m ² / g, Na ₂ O content 0.05% by mass) powder as a carrier, ZSM5 in the same manner as in Example 1. A (Si / Al = 75) supported 2% Ni-0.5% Re catalyst was prepared. Using 0.5 g of this catalyst, the hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 1 except that the hydrogen pressure in the reactor was adjusted to 3 MPa, and the reaction product was analyzed in the same manner. Shown in 1.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction at 330 minutes was 59%, and the diol (1,4-butanediol) selectivity was 50%. Similarly, the saturated cyclic ether (THF) selectivity was 41% and the molar ratio of diol / saturated cyclic ether was 1.22. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Comparative Example 1: Hydrogenation hydration reaction with 2% Ni-0.5% Re catalyst supported by MOR (Si / Al = 112)]
As a carrier, a commercially available proton-type MOR (mordenite) zeolite (Si / Al = 112, specific surface area = 450 m ² / g, Na ₂ O content 0.05% by mass or less) powder was used in the same manner as in Example 1. , MOR (Si / Al = 112) -supported 2% Ni-0.5% Re catalyst was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction product was analyzed in the same manner. Shown in 1.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the 240-minute hydrogenation hydration reaction was 45%, and the diol (1,4-butanediol) selectivity was 8%. Similarly, the saturated cyclic ether (THF) selectivity was 52% and the molar ratio of diol / saturated cyclic ether was 0.15. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Comparative Example 2: Hydrogenation hydration reaction using BEA (Si / Al = 75) -supported 2% Ni-4% Re catalyst]
Using a commercially available proton-type BEA zeolite (Si / Al = 75, specific surface area = 500 m ² / g, Na ₂ O content 0.03% by mass or less) powder as a carrier, BEA (Si / Al = 75, Na 2 O content 0.03% by mass or less) was used in the same manner as in Example 1. A 2% Ni-4% Re catalyst supported by Si / Al = 75) was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction products were analyzed in the same manner. The results are shown in Table 1.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the 240-minute hydrogenation hydration reaction was 43%, and the diol (1,4-butanediol) selectivity was 22%. Similarly, the saturated cyclic ether (THF) selectivity was 33% and the molar ratio of diol / saturated cyclic ether was 0.67. The selectivity of monool (butanol) produced by hydrocracking was 1%.

[Comparative Example 3: Hydrogenation and hydration reaction using BEA (Si / Al = 75) -supported 2% Re catalyst>
As a carrier, a commercially available proton-type BEA zeolite (Si / Al = 75, specific surface area = 500 m ² / g, Na ₂ O content 0.03% by mass or less) powder and a Re ₂ O ₇ aqueous solution were used as the carrier, and the same as in Example 1. Similarly, a BEA (Si / Al = 75) -supported 2% Re catalyst was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction product was analyzed in the same manner. The results are shown in Table 1. It was.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the 240-minute hydrogenation hydration reaction was 8%, and the diol (1,4-butanediol) selectivity was 20%. Similarly, the saturated cyclic ether (THF) selectivity was 28% and the molar ratio of diol / saturated cyclic ether was 0.71. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Comparative Example 4: Hydrogenation and hydration reaction using a 20% Ni catalyst supported by ZSM5 (Si / Al = 800)]
As a carrier, a commercially available proton-type MFI zeolite (ZSM5, Si / Al = 800, specific surface area = 360 m ² / g, Na ₂ O content 0.05% by mass or less) powder and an aqueous solution of Ni nitrate were used as the carrier, and the same as in Example 1. Similarly, a ZSM5 (Si / Al = 800) -supported 20% Ni catalyst was prepared, the hydrogenation and hydration reaction of furan was carried out in the same manner, and the reaction product was analyzed in the same manner. The results are shown in Table 1. It was.
As shown in Table 1, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 60 minutes was 99%, and the diol (1,4-butanediol) selectivity was 12%. Similarly, the saturated cyclic ether (THF) selectivity was 85% and the molar ratio of diol / saturated cyclic ether was 0.14. The selectivity of monool (butanol) produced by hydrocracking was 2%.

From Example 1-6 and Comparative Example 1, Ni immobilized on a proton-type (acidic) high silica zeolite having a pore diameter of 10-membered ring or more and a three-dimensional pore structure such as ZSM5 (MFI), USY (FAU), and BEA. It can be seen that the catalyst gives the diol compound with high selectivity in the hydrogenation hydration reaction of unsaturated cyclic ethers. From Examples 4 and 5 and Comparative Examples 2 and 3, the amount of Re is smaller than that of Ni in terms of the ratio of the amount of Ni, which is an active catalyst metal, to Re, which is a modification aid. It can be seen that both activity and selectivity are excellent in the sum reaction. Further, from Examples 1, 6 and 7 and Comparative Example 4, when the amount of Ni, which is an active catalyst metal, based on the whole catalyst is less than 20%, the diol has a higher selectivity in the hydrogenation hydration reaction of the unsaturated cyclic ether. It can be seen that it gives a compound.

[Example 11: _{Hydrogenation hydration reaction with amorphous SiO 2-} Al ₂ O ₃ supported 2% Ni-0.5% Re catalyst]
As a carrier, a commercially available amorphous SiO _2- Al ₂ O ₃ (specific surface area = 560 m ² / g, pore volume = 0.73 ml / g, Si / Al = 4.5) powder is used in the same manner as in Example 1. A 2% Ni-0.5% Re catalyst supported on _{SiO 2-} Al ₂ O _{3 was prepared.} Using the obtained catalyst, a hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 1 except that the reactor hydrogen pressure was set to 3 MPa, and the reaction product was analyzed in the same manner, and the results are shown in Table 2. It was shown to.
As shown in Table 2, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 360 minutes was 74%, and the diol (1,4-butanediol) selectivity was 57%. Similarly, the saturated cyclic ether (THF) selectivity was 37% and the molar ratio of diol / saturated cyclic ether was 1.54. The selectivity of monool (butanol) produced by hydrocracking was 2%.

Example 12: Amorphous _Al 1.5 PO _n hydrogen Kamizu hydration reaction by carrying 2% Ni-0.5% Re catalyst]
Generate precipitates dropwise aluminum nitrate and slowly 28% NH ₃ water mixed aqueous solution of phosphoric acid, filtered after aging overnight, and washed with water. The resulting cake was dried 12 hours at 120 ° C. in an oven, to obtain an amorphous _Al 1.5 PO _n powder was ground in a mortar after firing 4 hours at 400 ° C..
The resulting _Al 1.5 PO _n powder is used as a carrier was prepared in the same manner as _Al 1.5 PO _n carrying 2% Ni-0.5% Re catalyst Example 1. Using this catalyst, the hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 1 except that the hydrogen pressure of the reactor was set to 5 MPa, and the reaction products were analyzed in the same manner. Indicated.
As shown in Table 2, the unsaturated cyclic ether (furan) conversion rate in the 180-minute hydrogenation hydration reaction was 71%, and the diol (1,4-butanediol) selectivity was 42%. Similarly, the saturated cyclic ether (THF) selectivity was 55% and the molar ratio of diol / saturated cyclic ether was 0.76. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Example 13: Hydrogenation hydration reaction using a niobate-supported 4% Ni catalyst]
A hydrous niobium powder (HY340, specific surface area of 150 m ² / g) manufactured by CBMM was calcined at 300 ° C. for 2 hours to dehydrate it. Using an aqueous solution of Ni nitrate, the obtained niobium (hydrous-containing niobium) was impregnated with Ni by the incipient-wetness method. After removing water in a hot water bath, it is dried at 120 ° C. for 6 hours, fired at 300 ° C. for 3 hours in air, and then reduced at 320 ° C. for 2 hours under a hydrogen stream to carry 4% niobate. Obtained a catalyst. Using the obtained catalyst, a hydrogenation hydration reaction of furan was carried out in the same manner as in Example 1 except that the reactor hydrogen pressure was set to 5 MPa, and the reaction product was analyzed in the same manner. The results are shown in Table 2. It was shown to.
As shown in Table 2, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 300 minutes was 70%, and the diol (1,4-butanediol) selectivity was 43%. Similarly, the saturated cyclic ether (THF) selectivity was 50% and the molar ratio of diol / saturated cyclic ether was 0.86. The selectivity of monool (butanol) produced by hydrocracking was 1%.

[Example 14: Hydrogenation hydration reaction using a niobate-supported 8% Ni catalyst]
A niobate-supported 8% Ni catalyst was obtained in the same manner as in Example 13. Using the obtained catalyst, a hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 13, and the reaction products were analyzed in the same manner, and the results are shown in Table 2.
As shown in Table 2, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction at 105 minutes was 77%, and the diol (1,4-butanediol) selectivity was 28%. Similarly, the saturated cyclic ether (THF) selectivity was 69% and the molar ratio of diol / saturated cyclic ether was 0.41. The selectivity of monool (butanol) produced by hydrocracking was 1%.

[Comparative Example 5: Hydrogenation and hydration reaction using 20% Ni-catalyzed niobate]
A 20% Niobate-supported Ni catalyst was obtained in the same manner as in Example 13. Using the obtained catalyst, a hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 13, and the reaction products were analyzed in the same manner, and the results are shown in Table 2.
As shown in Table 2, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 45 minutes was 77%, and the diol (1,4-butanediol) selectivity was 17%. Similarly, the saturated cyclic ether (THF) selectivity was 79% and the molar ratio of diol / saturated cyclic ether was 0.22. The selectivity of monool (butanol) produced by hydrocracking was 2%.

[Comparative Example 6: Hydrohydration reaction with 1% Ni catalyst supported by zirconia]
Zirconium hydride powder (Z999) manufactured by Nippon Kinzoku Co., Ltd. was calcined at 500 ° C. for 3 hours to dehydrate it. The obtained zirconia powder (specific surface area 90 m ² / g) was impregnated with Ni by the incipient-wetness method. After removing water in a hot water bath, it is dried at 120 ° C. for 6 hours, further calcined in air at 500 ° C. for 3 hours, and then reduced at 300 ° C. for 2 hours under a hydrogen stream to obtain a zirconia-supported 1% Ni catalyst. Obtained. Using the obtained catalyst, the hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 1 except that the reactor hydrogen pressure was set to 5 MPa, and the reaction products were analyzed in the same manner. Indicated.
As shown in Table 2, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 180 minutes was 74%, and the diol (1,4-butanediol) selectivity was 14%. Similarly, the saturated cyclic ether (THF) selectivity was 83% and the molar ratio of diol / saturated cyclic ether was 0.17. The selectivity of monool (butanol) produced by hydrocracking was 3%.

[Comparative Example 7: Hydrogenation and hydration reaction using a titania-supported 2% Ni catalyst]
A titania-supported 2% Ni catalyst was obtained in the same manner as in Comparative Example 6 using a powder obtained by crushing ^{titania (specific surface area 50 m 2} / g) having a crystal structure of anatas type, which was produced from a titanium chloride raw material as a carrier. .. Using the obtained catalyst, the hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 1 except that the reactor hydrogen pressure was set to 5 MPa, and the reaction products were analyzed in the same manner. Indicated.
As shown in Table 2, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 60 minutes was 73%, and the diol (1,4-butanediol) selectivity was 1% or less. .. Similarly, the saturated cyclic ether (THF) selectivity was 96% and the molar ratio of diol / saturated cyclic ether was 0.01 or less. The selectivity of monool (butanol) produced by hydrocracking was 4%.

[Comparative Example 8: Hydrogenation and hydration reaction with alumina-supported 1% Ni-0.5% Re catalyst]
Using a powder obtained by crushing commercially available γ-Al ₂ O ₃ (specific surface area 166 m ² / g, pore volume 0.37 ml / g) as a carrier, alumina-supported 1% Ni-0. A 5% Re catalyst was obtained. Except for using 4 g of this catalyst and setting the reactor hydrogen pressure to 3 MPa, the hydrogenation and hydration reaction of furan was carried out in the same manner as in Example 1, and the reaction products were analyzed in the same manner. Indicated.
As shown in Table 2, the unsaturated cyclic ether (furan) conversion rate in the hydrogenation hydration reaction for 60 minutes was 62%, and the diol (1,4-butanediol) selectivity was 1% or less. .. Similarly, the saturated cyclic ether (THF) selectivity was 93%, and the molar ratio of diol / saturated cyclic ether was 0.01 or less. The selectivity of monool (butanol) produced by hydrocracking was 6%.

Comparative Example 6-8 to Example 11-14, amorphous _SiO 2 _-Al 2 _{O 3,} amorphous _Al 1.5 PO _n, Ni catalyst immobilized on niobate (hydrous niobium oxide) is an unsaturated cyclic ether It can be seen that the diol compound is given with a high selectivity in the hydrogenation hydration reaction. From Examples 13 and 14 and Comparative Example 5, when the amount of Ni, which is an active catalyst metal, based on the whole catalyst is less than 20%, the diol compound is given with a high selectivity in the hydrogenation hydration reaction of the unsaturated cyclic ether. I understand.

[Hydrogenation and hydration reactions of other unsaturated cyclic ethers]
[Example 16: Hydrogenation hydration reaction of 2,3-DHF with ZSM5 (Si / Al = 75) supported 2% Ni-0.5% Re catalyst]
As a raw material for the hydrogenation hydration reaction, a commercially available reagent 2,3-DHF (dihydrofuran) was used without any particular purification. The purity of this 2,3-DHF was 98% or more.
Using the ZSM5-supported 2% Ni-0.5% Re catalyst prepared in Example 1, the amount of 2,3-DHF charged was 35 g, and the reactor hydrogen pressure was adjusted to 3 MPa in the same manner as in Example 1. Then, a hydrogenation hydration reaction of 2,3-DHF was carried out, and the reaction products were analyzed in the same manner, and the results are shown in Table 3.
As shown in Table 3, the unsaturated cyclic ether (2,3-DHF) conversion rate in the hydrogenation hydration reaction for 150 minutes is 100%, and the diol (1,4-butanediol) selectivity is 91%. Met. Similarly, the saturated cyclic ether (THF) selectivity was 7% and the molar ratio of diol / saturated cyclic ether was 13.00. The selectivity of monool (butanol) produced by hydrocracking was 1%.

[Example 17: Hydrogenation and hydration reaction of 2,3-DHF with ZSM5 (Si / Al = 75) -supported 2% Co-0.5% Re catalyst]
Using Co nitrate instead of Ni nitrate, a ZSM5 (Si / Al = 75) -supported 2% Co-0.5% Re catalyst was obtained in the same manner as in Example 1. Using the obtained catalyst, a hydrogenation hydration reaction of 2,3-DHF was carried out in the same manner as in Example 16, and the reaction products were analyzed in the same manner, and the results are shown in Table 3.
As shown in Table 3, the unsaturated cyclic ether (2,3-DHF) conversion rate in the 240-minute hydrogenation hydration reaction was 37%, and the diol (1,4-butanediol) selectivity was 49%. Met. Similarly, the saturated cyclic ether (THF) selectivity was 44% and the molar ratio of diol / saturated cyclic ether was 1.11. The selectivity of monool (butanol) produced by hydrocracking was 6%.

[Example 18: Hydrogenation hydration reaction of 2,5-DHF with ZSM5 (Si / Al = 75) -supported 2% Ni-0.5% Re catalyst]
As a raw material for the hydrogenation hydration reaction, a commercially available reagent 2,5-DHF (dihydrofuran) was used without any particular purification. The purity of this 2,5-DHF was 98% or more.
Using the ZSM5 (Si / Al = 75) -supported 2% Ni-0.5% Re catalyst prepared in Example 1, a hydrogenation hydration reaction of 2,5-DHF was carried out in the same manner as in Example 16. The reaction products were analyzed in the same manner, and the results are shown in Table 3.
As shown in Table 3, the unsaturated cyclic ether (2,3-DHF) conversion rate in the hydrogenation hydration reaction for 150 minutes is 100%, and the diol (1,4-butanediol) selectivity is 66%. Met. Similarly, the saturated cyclic ether (THF) selectivity was 32% and the molar ratio of diol / saturated cyclic ether was 2.06. The selectivity of monool (butanol) produced by hydrocracking was 1%.

[Example 19: Hydrogenation hydration reaction of 3,4-2H-DHP with ZSM5 (Si / Al = 800) supported 2% Ni-0.5% Re catalyst]
As a raw material for the hydrogenation hydration reaction, a commercially available reagent 3,4-2H-DHP (dihydropyran) was used without any particular purification. The purity of this 3,4-2H-DHP was 96% or more.
Same as Example 16 except that the amount of 3,4-2H-DHP charged was 42 g using the ZSM5 (Si / Al = 800) -supported 2% Ni-0.5% Re catalyst prepared in Example 2. Then, the hydrogenation and hydration reaction of 3,4-2H-DHP was carried out, and the reaction products were analyzed in the same manner, and the results are shown in Table 3.
As shown in Table 3, the unsaturated cyclic ether (3,4-2H-DHP) conversion rate in the hydrogenation hydration reaction for 150 minutes is 100%, and the diol (1,5-pentanediol) selectivity is It was 97%. Similarly, the saturated cyclic ether (THP: tetrahydropyran) selectivity was 2% and the molar ratio of diol / saturated cyclic ether was 48.50. The selectivity of monool (pentanol) produced by hydrocracking was 1% or less.

From Examples 16-19, it can be seen that the catalyst in which Ni and Co are immobilized on a solid acid gives a diol compound with a high selectivity in the hydrogenation hydration reaction of various unsaturated cyclic ethers.

Claims (9)

In a method for producing a diol compound by hydrogenating and hydrating an unsaturated cyclic ether compound raw material with a catalyst in the presence of hydrogen and water.
The catalyst is a supported catalyst in which at least one metal element selected from Ni and Co is immobilized on a solid acid , and the amount of the metal element supported is 0.5% by mass or more based on the total mass of the catalyst. A method for producing a diol compound using a catalyst having a mass% or less.
A method for producing a diol compound , wherein the solid acid is the following (1) or (2).
(1) An acidic high-silica zeolite having a three-dimensional pore structure, not having an 8-membered ring pore size, and having a pore diameter of 10-membered ring or more, and the Si / Al ratio of the zeolite is 10 or more and 1000 or less. Solid acid
(2) A solid acid which is at least one selected from an oxide containing niobium, a hydrous oxide containing niobium, a phosphate, and _{a composite oxide containing SiO 2.} The method for producing a diol compound according to claim 1, wherein a water-soluble acid is not used as a reaction aid. The method for producing a diol compound according to claim 1 or 2, wherein the solid acid is an oxide containing niobium or a hydrous oxide containing niobium. The catalyst is a supported catalyst in which Ni and / or Co is supported on the solid acid and one or more of Mn, Re and W are supported as modification aids, and the amount of the modification aids supported is Ni and / or. The method for producing a diol compound according to any one of claims 1 to 3 , wherein the content is 100% by mass or less with respect to the mass of Co. The invention according to any one of claims 1 to 4 , wherein the molar ratio of water to the unsaturated cyclic ether compound (water / unsaturated cyclic ether compound) to be subjected to the reaction is 0.5 or more and 8 or less. Method for producing a diol compound. The method for producing a diol compound according to any one of claims 1 to 5 , wherein the hydrogen pressure in the hydrogenation hydration reaction is 1 MPa or more and 5 MPa or less. The diol compound according to any one of claims 1 to 6 , wherein the diol compound produced by the hydrogenation hydration reaction has a molar ratio of 0.4 or more to the saturated cyclic ether compound produced as a by-product. Manufacturing method. The diol compound according to any one of claims 1 to 7 , wherein a reduction treatment is carried out in which the catalyst is brought into contact with a reducing gas at a temperature of 320 ° C. or higher prior to being subjected to the hydrogenation hydration reaction. Manufacturing method. The method for producing a diol compound according to any one of claims 1 to 8 , wherein the unsaturated cyclic ether compound is a dihydrofuran ring compound or a dihydropyran ring compound.