KR20070064335A - Method for Decomposing Ester Oligomers and Methods for Preparing Compounds with 4 C atoms - Google Patents

Abstract

Decomposition of by-product ester oligomers with the production of ester oligomers containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as components, in particular γbutyrolactone, furthermore the industrially advantageous C4 family In particular, a method for producing γ butyrolactone is provided.

Aqueous solutions of ester oligomers containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as constituents are contacted with a solid acid catalyst under heating to decompose into respective constituents, A method for decomposing an ester oligomer for converting butanediol to tetrahydrofuran and / or converting 4-hydroxybutyric acid to γ butyrolactone when it contains 4-hydroxybutyric acid as a component of the ester oligomer.

Description

METHODS OF DECOMPOSING ESTER OLIGOMER AND PROCESS FOR PRODUCING C4 COMPOUND}

The present invention relates to a method for decomposing an ester oligomer and a method for producing a compound having 4 carbon atoms.

The chemical family of four carbon atoms (C4 family) is an important intermediate group used for various solvents such as gamma butyrolactone, 1,4-butanediol, tetrahydrofuran, succinic acid and N-methylpyrrolidone and polymer raw materials. The demand is increasing. In particular, gamma butyrolactone is not only used as an excellent solvent itself, but also useful as an important intermediate of various substances such as pyrrolidones, and therefore, various manufacturing processes have been developed. For example, as shown in Unexamined-Japanese-Patent No. 3-26340 and Unexamined-Japanese-Patent No. 3-232874, the hydrogenation reaction of succinic anhydride and the dehydrogenation reaction of 1, 4- butanediol are developed. In addition, hydrogenation of succinic anhydride (Journal of catalysis 194, 188-197, 2000) and dehydrogenation of 1,4-butanediol (Japanese Laid-Open Patent Publication No. 2001-240595) are reported as using a ruthenium complex catalyst. Although many methods of producing these gamma butyrolactone proceed in a good yield, the high boiling point compound may be produced as a by-product, and the cost of succinic anhydride, succinic acid, 1,4-butanediol, maleic anhydride as raw materials Was pulling up. Therefore, if the raw material can be regenerated by decomposing these by-products of high boiling point compounds, a more efficient method for producing gamma butyrolactone can be established. Therefore, such a method has been required.

Patent Document 1: Japanese Patent Application Laid-Open No. 3-26340

Patent Document 2: Japanese Patent Application Laid-Open No. 3-232874

Patent Document 3: Japanese Unexamined Patent Publication No. 2001-240595

Non-Patent Document 1: Journal of catalysis 194, 188-197, 2000

Disclosure of the Invention

Problems to be Solved by the Invention

An object of the present invention is an ester oligomer (high boiling point compound) containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as a constituent, particularly a high boiling point compound produced by the method of producing gamma butyrolactone. It is to provide a method for decomposing (ester oligomer), and furthermore, to provide an industrially advantageous C4 family, in particular a method for producing gamma butyrolactone.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the high boiling point compound byproduced by C4 family, especially gamma-butyrolactone manufacture comprises succinic acid and / or 4-hydroxybutyric acid, and 1, 4- butanediol. It is discovered that it is an ester oligomer to contain as a component, and the aqueous solution containing this high boiling point compound (ester oligomer) is treated with a solid acid catalyst, and succinic acid and / or 4- which is a component of this high boiling point compound (ester oligomer) are found. It has been found to decompose (hydrolyzable) to an aqueous solution containing hydroxybutyric acid and 1,4-butanediol. However, it was also found that succinic acid (obtained by decomposing the high boiling point compound) and / or 4-hydroxybutyric acid and 1,4-butanediol coexisted to convert to a high boiling point compound (ester oligomer). When succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol are converted into a high boiling point compound (ester oligomer), each component cannot be separated and they cannot be used. Therefore, as a result of intensive studies to prevent the conversion of succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol into high boiling point compounds (ester oligomers), the high boiling point compounds (ester oligomers) are heated to a solid state. By contacting with an acid catalyst, it is decomposed into constituent components, and 1,4-butanediol can be converted into tetrahydrofuran, and when 4-hydroxybutyric acid is contained, 4-hydroxybutyric acid is converted into gamma buty. It was found that it could be converted to lactones. Succinic acid and / or 4-hydroxybutyric acid and tetrahydrofuran do not form a high boiling point compound (ester oligomer) even if they coexist, and even if gamma butyrolactone and 1,4-butanediol coexist, a high boiling point compound (ester oligomer) It was found that no silver was produced, and the present invention was completed. That is, the summary of this invention exists in following (1)-(15).

(1) Aqueous solutions of ester oligomers containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as constituents are contacted with a solid acid catalyst under heating to decompose into respective constituents, A method for decomposing an ester oligomer for converting 1,4-butanediol to tetrahydrofuran and / or converting 4-hydroxybutyric acid to gamma butyrolactone when it contains 4-hydroxybutyric acid as a component of the ester oligomer.

(2) Aqueous solutions of ester oligomers containing succinic acid and 1,4-butanediol as constituents are contacted with a solid acid catalyst under heating to decompose them into succinic acid and 1,4-butanediol and to dissolve 1,4-butanediol. A method of decomposing an ester oligomer which converts the compound into tetrahydrofuran.

(3) Aqueous solutions of ester oligomers containing 4-hydroxybutyric acid and 1,4-butanediol as constituents are contacted with a solid acid catalyst under heating to decompose into 4-hydroxybutyric acid and 1,4-butanediol. Decomposition method of the ester oligomer for converting 4-hydroxybutyric acid into gamma butyrolactone.

(4) The decomposition method of the ester oligomer in any one of said (1)-(3) whose heating is 80-200 degreeC and contact time with a solid acid catalyst is 1-20 hours.

(5) The decomposition method of the ester oligomer in any one of said (1)-(4) whose aqueous solution of an ester oligomer is the aqueous solution of 1 wtppm-400 wtppm of phosphorus concentration.

(6) Said (1)-(5) which is the aqueous solution of the high boiling point compound by-produced when the aqueous solution of ester oligomer produces a C4 compound by hydrogenation of dicarboxylic acid or an acid anhydride, or dehydrogenation of diol. The degradation method of the ester oligomer in any one of them.

(7) The method for decomposing an ester oligomer according to (6), wherein the compound having 4 carbon atoms is at least one of gamma butyrolactone, 1,4-butanediol, tetrahydrofuran, succinic acid, and succinic anhydride.

(8) The method for decomposing the ester oligomer according to (6), wherein the compound having 4 carbon atoms is gamma butyrolactone.

(9) The method for decomposing the ester oligomer according to any one of (1) to (8), wherein the solid acid catalyst is a cation exchange resin having a sulfone group.

(10) A method for producing succinic acid in which an aqueous solution of an ester oligomer containing succinic acid and 1,4-butanediol as a constituent is contacted with a solid acid catalyst while heating, and decomposed into succinic acid and tetrahydrofuran.

(11) Gamma butyro which is decomposed into gamma butyrolactone and tetrahydrofuran by bringing an aqueous solution of an ester oligomer containing 4-hydroxybutyric acid and 1,4-butanediol as a constituent into contact with a solid acid catalyst under heating. Process for the production of lactones.

(12) A method for producing a compound having 4 carbon atoms by hydrogenation of a dicarboxylic acid or an acid anhydride, wherein an aqueous solution containing a high-boiling compound that is a by-product when producing a compound having 4 carbon atoms is converted to succinic acid and tetrahydrofuran. A method for producing a compound having 4 carbon atoms which decomposes and introduces succinic acid into the hydrogenation reaction of dicarboxylic acid or acid anhydride.

(13) A method for producing a compound having 4 carbon atoms by hydrogenation of a dicarboxylic acid or an acid anhydride, wherein an aqueous solution containing a high boiling point compound which is by-produced when producing a compound having 4 carbon atoms is heated with a solid acid catalyst. And a high boiling point compound are decomposed into succinic acid and tetrahydrofuran, and water and tetrahydrofuran are distilled off, and the resulting aqueous succinic acid is introduced into a hydrogenation reaction of dicarboxylic acid or acid anhydride. Process for the preparation of the compound.

(14) The method for producing a compound having 4 carbon atoms by hydrogenation of dicarboxylic acid or acid anhydride or dehydrogenation of diol is any one of succinic anhydride, succinic acid and maleic anhydride using a homogeneous ruthenium complex catalyst, Or the method for producing a compound having 4 carbon atoms according to any one of (12) or (13), which is a method for producing gammabutyrolactone by a plurality of hydrogenation reactions or by dehydrogenation of 1,4-butanediol.

(15) A compound having 4 carbon atoms and a reaction solvent from a reaction solution in which an aqueous solution containing a high boiling point compound by-produced when producing a compound having 4 carbon atoms is obtained by hydrogenation of dicarboxylic acid or acid anhydride or dehydrogenation of diol. Preparation of the compound of C4 in any one of said (12)-(14) which is the water phase in the obtained multiple phase by adding and extracting water and a nonpolar solvent to the catalyst liquid containing the by-product high boiling point compound obtained by removing Way.

The present invention can be used in any of batch, semi-batch, and continuous systems. The details will be described below.

Effects of the Invention

According to the present invention, ester oligomers (high boiling point compounds) containing succinic acid and / or 4-hydroxybutyric acid, and 1,4-butanediol as constituents, in particular, high boiling point compounds (by-produced by a method for producing gamma butyrolactone) It is possible to provide a process for decomposing the ester oligomer), and furthermore, to provide an industrially advantageous C4 family, in particular a method for producing gammabutyrolactone.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the apparatus which carried out "hydrogenation reaction of succinic anhydride using a ruthenium trioctyl phosphine paratoluene sulfonic acid type catalyst" of a reference example.

Explanation of the sign

1: gas-liquid separator

2: distiller

3: catalyst vessel

4: extraction catalyst vessel

5: new catalyst container

6: compressor

7: raw material container

8: Autoclay

10: waste gas

11: lactone, water

To practice the invention  Best form for

In the decomposition method of the ester oligomer of the present invention, an aqueous solution of an ester oligomer containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as a constituent is contacted with a solid acid catalyst while heating. When decomposing into each constituent component and converting 1,4-butanediol to tetrahydrofuran and / or containing 4-hydroxybutyric acid as a component of the ester oligomer, 4-hydroxybutyric acid is gamma butyrolactone It characterized in that the conversion.

Moreover, the following (i)-(i) is mentioned as embodiment of this invention.

(i) A method for producing succinic acid in which an aqueous solution of an ester oligomer containing succinic acid and 1,4-butanediol as a constituent component is contacted with a solid acid catalyst while heating to decompose into succinic acid and tetrahydrofuran.

(Ii) a gamma butyro which is contacted with a solid acid catalyst while heating to contact an aqueous solution of an ester oligomer containing 4-hydroxybutyric acid and 1,4-butanediol as a constituent and decomposes it into gamma butyrolactone and tetrahydrofuran. Process for the production of lactones.

(Iii) A method for producing a C 4 compound by hydrogenation of a dicarboxylic acid or an acid anhydride, wherein an aqueous solution containing a high boiling point compound which is a byproduct when producing a C 4 compound is succinic acid and tetrahydrofuran. A method for producing a compound having 4 carbon atoms which decomposes and introduces succinic acid into the hydrogenation reaction of dicarboxylic acid or acid anhydride.

"Ester oligomer containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as a constituent component" in the present invention means that dehydration condensation of 1,4-butanediol, succinic acid and 4-hydroxybutyric acid Ester oligomers, which are crosslinked with ester bonds, and mixtures thereof. The ester oligomer consists of the structural unit derived from 1, 4- butanediol, succinic acid, and 4-hydroxybutyric acid, and the ester oligomer which consists of two or more and 20 or less structural units is preferable. If only one of these structural units is a monomer such as 1,4-butanediol, succinic acid, 4-hydroxybutyric acid, etc., it is not necessary to decompose. If too large, the reaction conditions for decomposing become severe and deterioration of the ion exchange resin due to high temperature reaction, Economical deterioration is achieved by the extension of the reactor and the extension of the reaction time. Moreover, in normal hydrogenation reaction, dehydrogenation reaction, etc., it is thought that the high boiling point compound whose structural unit exceeds 20 is not produced. The structural unit which comprises an ester oligomer is 2 or more types, and is 2-4 types normally.

Examples of these ester oligomers include high-boiling compounds produced by-products during the production of compounds having 4 carbon atoms, and specifically, are the following compound groups. However, it is not limited to these.

Method for producing gammabutyrolactone, 1,4-butanediol, tetrahydrofuran by hydrogenation of succinic acid or succinic anhydride using a solid catalyst, gammabutyrolactone, 1,4-butanediol by hydrogenation of maleic anhydride, Method for producing tetrahydrofuran, succinic acid, succinic anhydride, method for producing gammabutyrolactone by dehydrogenation of 1,4-butanediol, gammabutyrolactone by hydrogenation of succinic acid or succinic anhydride using a homogeneous complex catalyst, Carbon number 4 including a method for producing 1,4-butanediol, tetrahydrofuran, a hydrogenation reaction of maleic anhydride, or a method for producing gammabutyrolactone by dehydrogenation of 1,4-butanediol using a homogeneous complex catalyst, and the like The high boiling point compound by-produced by the manufacturing method of the compound, etc. are mentioned.

The method for producing the C 4 compound may be any of gas phase, liquid phase, solid catalyst, and complex catalyst. Examples of the compound having 4 carbon atoms include gamma butyrolactone, 1,4-butanediol, tetrahydrofuran, furan, dihydrofuran, succinic acid and succinic anhydride, and preferably gamma butyrolactone, 1,4-butanediol and tetra Hydrofuran, succinic acid and succinic anhydride, and particularly preferably gamma butyrolactone. The present invention is applicable to all of the above methods for producing a compound having 4 carbon atoms, but is preferably a method for producing gamma butyrolactone, 1,4-butanediol by hydrogenation of succinic acid or succinic anhydride using a solid catalyst, maleic anhydride. Method for preparing gammabutyrolactone by hydrogenation of hydrogen, 1,4-butanediol, Method for preparing gammabutyrolactone by dehydrogenation of 1,4-butanediol, Hydrogenation of succinic acid or succinic anhydride using homogeneous complex catalyst Of gamma-butyrolactone by the hydrogenation of maleic anhydride, method of producing gamma-butyrolactone, method of producing 1,4-butanediol, and gamma-butyrolactone by dehydrogenation of 1,4-butanediol It is a manufacturing method, Especially preferably, the manufacturing method of gamma-butyrolactone by the hydrogenation reaction of succinic acid or succinic anhydride using a solid catalyst, a homogeneous complex catalyst Of gamma -butyrolactone by hydrogenation of yonghan succinic acid or succinic anhydride by-product it is to a method of manufacturing a lactone.

Hereinafter, the said reaction is demonstrated. Their reactions can be categorized into four formats regardless of product. That is, 1) hydrogenation using a solid catalyst, 2) dehydrogenation using a solid catalyst, 3) hydrogenation using a complex catalyst, and 4) dehydrogenation using a complex catalyst. Each is demonstrated. In the case of the hydrogenation reaction using a solid catalyst, solid catalysts of copper-chromium, copper-zinc, copper-aluminum and copper-metal oxides are preferred, and reaction conditions in liquid or gas phase are employed, in particular maleic anhydride. , Maleic acid, succinic anhydride, succinic acid, and preferred for the hydrogenation of gamma butyrolactone, and the products obtained are succinic anhydride, succinic acid, gamma butyrolactone, 1,4-butanediol and the like. This reaction is normally performed under the hydrogen pressure of 1 MPa-10 MPa, and reaction temperature is 150 degreeC-300 degreeC. After the reaction, the product is purified from the liquid by distillation, crystallization, absorption with a solvent and the like. On the other hand, the dehydrogenation reaction using a solid catalyst is also the same, and a solid catalyst of copper-chromium, copper-zinc, copper-aluminum, and copper-metal oxide type is preferable, and reaction conditions in a gas phase are usually employed, and 1,4-butanediol is employed. It is suitable for a method for producing gamma butyrolactone by dehydrogenation of. The present reaction is usually carried out under a pressure of 0.01 MPa to 1 MPa, and is carried out under a hydrogen atmosphere produced by reaction. The reaction temperature is 150 ° C to 300 ° C, and the product is purified by distillation from the liquid after the reaction. The hydrogenation reaction using the complex catalyst is preferably a ruthenium complex catalyst, and usually contains a phosphorus compound as a ligand. Liquid phase reaction conditions are employed, and are particularly preferred for the method for producing gamma butyrolactone by hydrogenation of succinic anhydride and succinic acid. The reaction temperature is carried out under hydrogen pressure of 100 ° C to 250 ° C and 1 MPa to 5 MPa. The product is purified from the liquid after this reaction by distillation, crystallization, absorption with a solvent and the like. In addition, the dehydrogenation reaction using the complex catalyst is also the same, and a ruthenium complex catalyst is preferable, and usually contains a phosphorus compound as a ligand. Liquid phase reaction conditions are employed, and are particularly preferred for the method for producing gamma butyrolactone by dehydrogenation of 1,4-butanediol. The present reaction is usually carried out under a pressure of 0.01 MPa to 1 MPa, and is carried out under a hydrogen atmosphere produced by reaction. Reaction temperature is 150 degreeC-300 degreeC, and a product is refine | purified by distillation from the liquid after reaction.

The high-boiling point compound which by-produces by a hydrogenation reaction, a dehydrogenation reaction, etc. is contained in the liquid after reaction in the manufacturing process of a C4 compound, such as gamma-butyrolactone, and is produced by-product when manufacturing a C4 compound in this invention. Aqueous solution containing this by-produced high boiling point compound is mentioned as an aqueous solution of said high boiling point compound. Specifically, after the reaction, water is added to the liquid, or from the reaction solution, a C4 compound such as gamma butyrolactone, and a C4 compound such as gamma butyrolactone, In the case, what added water to what removed the reaction solvent can be used, Preferably it is the latter.

In the present invention, "the ester oligomer contains two kinds of succinic acid and 1,4-butanediol as its structural unit", or "the ester oligomer containing succinic acid as its structural unit, and 1,4-butanediol as a structural unit A mixture of ester oligomers to contain ”, or“ the ester oligomer contains three kinds of succinic acid, 4-hydroxybutyric acid and 1,4-butanediol as its structural unit ”or“ ester oligomer containing succinic acid as its structural unit. And a mixture of an ester oligomer containing 4-hydroxybutyric acid as a structural unit and an ester oligomer containing 1,4-butanediol as a structural unit, or "the ester oligomer is 4-hydroxybutyric acid and 1 as its structural unit. 2 esters of 4-butanediol, or " Ester oligomer containing 4-hydroxybutyric acid as a structural unit, " It is a mixture of the ester oligomer containing 1, 4- butanediol as a structural unit. " Said ester oligomer may have another structural unit, respectively.

In this invention, even if it is the aqueous solution containing only 1 type of these ester oligomers, it is applicable also to the aqueous solution containing many types of oligomers. In the aqueous solution of the ester oligomer (high boiling point compound) used by this invention, the aqueous solution containing 1 weight%-80 weight% of this ester oligomer (high boiling point compound) can be used, Preferably it is 3 weight%-30 weight %, Especially preferably, it is 5 weight%-20 weight% of aqueous solution. When the content of the high boiling point compound is too small, the efficiency of hydrolysis decreases, which is industrially disadvantageous. When the content of the high boiling point compound is too high, the rate of hydrolysis decreases, while the high boiling point compound does not completely dissolve in water, resulting in a solid-liquid mixed liquid, which is blocked. Etc. Problems occur in the process.

Moreover, it is preferable to contain 10 weight% or more of water, More preferably, the water composition in aqueous solution is 30 to 95 weight%, Especially preferably, it is 50 to 90 weight%. When the content of water is too small, the rate of hydrolysis when the ester oligomer (high boiling point compound) is brought into contact with the solid acid catalyst decreases, and problems such as blockage occur in the process due to precipitation of the high boiling point compound. The yield of hydrolysis product per unit volume of the reactor is lowered.

Moreover, even if it contains other components other than the by-product high boiling point compound, the hydrolysis of this invention advances without difficulty, and especially contains succinic acid, succinic anhydride, 1, 4- butanediol, 4-hydroxybutyric acid, and gamma butyrolactone. It is also possible to use the aqueous solution of the said high boiling point compound. The case where the esters containing alcohols and acids which are by-produced in the gamma butyrolactone production process are mixed can also be used in the present invention. For example, the alcohols and acids produced by a small amount by-produced by gamma-butyrolactone reaction are alcohols and acids having 2 to 10 carbon atoms, and preferably 1-octanol, 2-octanol, 1-hexanol and 2- Hexanol, 1-butanol, 2-butanol, ethanol, methanol, diethylene glycol monomethyl ether, ethylene glycol, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol, formic acid, acetic acid, propionic acid, butyric acid, and the like. Moreover, especially preferably, it is diethylene glycol monomethyl ether and triethylene glycol monomethyl ether, and even if it contains 10 weight ppm-5 weight% of these by-product alcohols and acids, it does not interfere. These are by-products produced in small amounts in reaction solvents, catalyst components, gamma butyrolactone, 1,4-butanediol, succinic acid, succinic anhydride, maleic anhydride and the like. Moreover, in the case of the manufacturing method using the complex catalyst which uses a phosphorus compound as a ligand, a phosphorus compound may be contained in the aqueous solution of this ester oligomer. As a result of intensive studies by the present inventors, it was found that the phosphorus compound can be a substance causing deterioration of the solid acid catalyst, and it was found that it is preferably contained in the aqueous solution of the ester oligomer as low as possible. That is, the concentration of phosphorus atoms is preferably 0 wtppm to 1 wt%, particularly preferably 1 wtppm to 200 wtppm.

In the present invention, an ester oligomer (high boiling point compound) containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as a constituent component using a solid acid catalyst is decomposed into constituent components, and 1 If 4-hydroxybutyric acid is converted to tetrahydrofuran, and / or contains 4-hydroxybutyric acid as a component of the ester oligomer, 4-hydroxybutyric acid is converted to gamma butyrolactone, but the solid acid catalyst used here As a cation exchange resin, a metal oxide, a zeolite, activated clay, a metal sulfur oxide, etc. are mentioned, Preferably it is a cation exchange resin. As the cation exchange resin, a strongly acidic cation exchange resin is preferable, and particularly one having a sulfone group is particularly preferable. For example, sulfonated styrene-divinylbenzene copolymers can be used. This sulfonated styrene-divinylbenzene copolymer is not specifically limited, A commercial item can be used. The type of the structure is not particularly limited, but any type of gel, MR type, macroscopic type, porous type, or hypousic type can be used.

The ester oligomer (high boiling point compound) containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as a component by a solid acid catalyst was decomposed into each component, and 1,4-butanediol was dissolved in tetra When converting into hydrofuran and / or containing 4-hydroxybutyric acid as a component of the ester oligomer, when converting 4-hydroxybutyric acid to gammabutyrolactone, the ester oligomer is heated to contact with a solid acid catalyst. The temperature to be heated (reaction temperature) is preferably at least 50 ° C, more preferably at least 60 ° C, particularly preferably at least 80 ° C, preferably at most 300 ° C, more preferably at most 200 ° C, particularly Preferably it is 150 degrees C or less. If the reaction temperature is too low, the rate of hydrolysis decreases and the reaction efficiency deteriorates. If the reaction temperature is too high, deterioration of a solid acid catalyst such as an ion exchange resin is accelerated.

The contact time with the solid acid catalyst and the reactor residence time in the continuous case are preferably 10 minutes or more, more preferably 1 hour or more, particularly preferably 2 hours or more, preferably 100 hours or less, More preferably, it is 40 hours or less, Especially preferably, it is 20 hours or less. If the reactor residence time is too short, the progress of hydrolysis will be incomplete, and if too long, the reactor will be unnecessarily lengthened, resulting in an inefficient process.

The ester oligomer containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as constituents is decomposed into constituents by a solid acid catalyst, and 1,4-butanediol is converted into tetrahydrofuran. When 4-hydroxybutyric acid is contained as a component of conversion and / or ester oligomer, 4-hydroxybutyric acid is converted into gamma butyrolactone.

Since 1,4-butanediol coexists with succinic acid and / or 4-hydroxybutyric acid, it forms an ester oligomer, but tetrahydrofuran does not form ester oligomer even when coexisted with succinic acid and / or 4-hydroxybutyric acid. When the 4-butanediol is converted into tetrahydrofuran, the state in which the ester oligomer is decomposed can be maintained. When 1,4-butanediol is converted into tetrahydrofuran, the amount of succinic acid and / or 4-hydroxybutyric acid corresponding to the amount of the converted 1,4-butanediol can be separated without forming an ester oligomer. That is, in the present invention, when 1,4-butanediol is converted to tetrahydrofuran even in a small amount, the converted nutrient can decompose the ester oligomer and each component can be separated. The ratio of converting 1,4-butanediol to tetrahydrofuran is usually 10% or more, preferably 30% or more, and more preferably 60% or more. If the ratio of converting 1,4-butanediol to tetrahydrofuran is too small, separation from other components such as succinic acid becomes difficult. The higher the conversion ratio is, the higher the decomposition ratio is. However, from the viewpoint of economics, such as when the reactor is enlarged, the amount of catalyst is increased, and the proportion of constituents is largely biased, 1,4-butanediol must be largely tetrahydrofuran. It is not limited even if it is necessary to convert | transform into, and may be 30% or less.

Moreover, since gamma butyrolactone does not form ester oligomer even if it coexists with 1, 4- butanediol, when 4-hydroxybutyric acid is converted into gamma butyrolactone, the state which decomposed ester oligomer can be maintained. When 4-hydroxybutyric acid is converted into gamma butyrolactone, 1,4-butanediol in an amount corresponding to the amount of converted 4-hydroxybutyric acid can be separated without forming an ester oligomer. That is, in the present invention, even when a small amount of 4-hydroxybutyric acid is converted to gamma butyrolactone, the converted nutrient can decompose the ester oligomer, and each component can also be separated. The ratio of converting 4-hydroxybutyric acid to gamma butyrolactone is usually 10% or more, preferably 30% or more, and more preferably 60% or more. If the ratio of converting 4-hydroxybutyric acid to gamma butyrolactone is too small, separation with 1,4-butanediol becomes difficult. The higher the conversion ratio is, the higher the decomposition ratio is. However, from the viewpoint of economics, such as when the reactor is enlarged, the amount of the catalyst is increased, and the proportion of the constituent components is largely biased, 4-hydroxybutyric acid must be largely gamma-butyrolactone. It is not limited even if it is necessary to convert | transform into, and may be 30% or less.

Specific examples of the decomposition method of the ester oligomer include the following (a) to (c).

(A) In the case of an ester oligomer containing succinic acid and 1,4-butanediol as constituents, the ester oligomer is hydrolyzed into succinic acid and 1,4-butanediol by a solid acid catalyst, and 1,4-butanediol Converted to tetrahydrofuran. The ratio which converts 1, 4- butanediol into tetrahydrofuran is 30 to 100% normally, Preferably it is 60 to 100%. After carrying out the above operation, succinic acid can be obtained by distilling off water and tetrahydrofuran. The obtained succinic acid can be effectively used by introducing into the hydrogenation reaction of dicarboxylic acid or an acid anhydride in the method of manufacturing a C4 compound by the hydrogenation reaction of dicarboxylic acid or acid anhydride. If the ester oligomer containing succinic acid and 1,4-butanediol as a constituent component is a high boiling point compound which is a by-product in the process for producing a compound having 4 carbon atoms by hydrogenation of dicarboxylic acid or acid anhydride, The yield can be improved by introducing into the hydrogenation reaction of the leic acid or acid anhydride.

Distillation for separating water and tetrahydrofuran from succinic acid by distillation can remove water and tetrahydrofuran by monostillation or multistage distillation under atmospheric pressure or reduced pressure conditions. In that case, it is also possible to extract the component containing much tetrahydrofuran from a tower | column part, and to extract water which hardly contains tetrahydrofuran from a side flow part. Preferably the column static pressure is 40 mmHg-760 mmHg, More preferably, it is 200 mmHg-760 mmHg, The number of steps is 1-40, Preferably it is 1-20, Especially preferably, it is the range of 1-10 steps. to be.

(B) For ester oligomers containing succinic acid, 4-hydroxybutyric acid and 1,4-butanediol as constituents, the ester oligomers are succinic acid, 4-hydroxybutyric acid and 1,4-butanediol by solid acid catalysts. And 4-hydroxybutyric acid is converted to gamma butyrolactone and 1,4-butanediol to tetrahydrofuran, respectively. The ratio of converting 4-hydroxybutyric acid to gamma butyrolactone is usually 30% to 100%, preferably 60% to 100%. Moreover, the ratio which converts 1, 4- butanediol into tetrahydrofuran is 30%-100% normally, Preferably they are 60%-100%. Succinic acid can be obtained by distilling water, tetrahydrofuran and gammabutyrolactone after performing the above operation. The obtained succinic acid can be effectively used by introducing into the hydrogenation reaction of dicarboxylic acid or an acid anhydride in the method of manufacturing a C4 compound by the hydrogenation reaction of dicarboxylic acid or an acid anhydride. Alternatively, succinic acid containing gamma butyrolactone can be obtained by distilling off water and tetrahydrofuran. If the ester oligomer containing succinic acid, 4-hydroxybutyric acid, and 1,4-butanediol as a component is a high boiling point compound which is a by-product in the process for producing a compound having 4 carbon atoms by hydrogenation of dicarboxylic acid or acid anhydride. The yield can be improved by applying the obtained succinic acid to the hydrogenation reaction of dicarboxylic acid or acid anhydride.

Distillation for separating water and tetrahydrofuran and gamma butyrolactone from succinic acid by distillation removes water, tetrahydrofuran, and gamma butyrolactone by monostillation or multistage distillation under atmospheric pressure or under reduced pressure. can do. At that time, a component containing a large amount of tetrahydrofuran is extracted from the tower portion, water containing almost no tetrahydrofuran is extracted from the first side flow portion closer to the top of the column, and gamma-buti is extracted from the second side flow portion closer to the bottom. It is also possible to extract rockactone. Alternatively, a component containing a large amount of tetrahydrofuran can be extracted from the tower portion, water containing almost no tetrahydrofuran can be extracted from the side flow section, and succinic acid containing gamma butyrolactone can be obtained. Preferably the column static pressure is 40 mmHg-760 mmHg, More preferably, it is 200 mmHg-760 mmHg, The number of steps is 1-40, Preferably it is 1-20, Especially preferably, it is the range of 1-10 steps. to be.

(C) In the case of ester oligomers containing 4-hydroxybutyric acid and 1,4-butanediol as constituents, the ester oligomers are hydrolyzed to 4-hydroxybutyric acid and 1,4-butanediol by solid acid catalysts. In addition, 4-hydroxybutyric acid is partially converted to gamma butyrolactone and 1,4-butanediol to tetrahydrofuran, respectively. The ratio of converting 4-hydroxybutyric acid to gamma butyrolactone is usually 30% to 100%, preferably 60% to 100%. Moreover, the ratio which converts 1, 4- butanediol into tetrahydrofuran is 0%-100% normally, Preferably they are 0%-50%. 1,4-butanediol can be obtained by distilling water, tetrahydrofuran, and gammabutyrolactone after performing the above operation. The obtained 1,4-butanediol is effectively introduced into the dehydrogenation reaction of 1,4-butanediol in the method for producing a compound having 4 carbon atoms, particularly gamma butyrolactone by dehydrogenation of 1,4-butanediol. It is available. 1,4-butanediol obtained as long as the ester oligomer containing 4-hydroxybutyric acid and 1,4-butanediol as a constituent is a by-product of high boiling point in the process for producing a compound having 4 carbon atoms by dehydrogenation of diol. The yield can be improved by introducing into the dehydrogenation reaction.

Distillation for separating water and tetrahydrofuran and gammabutyrolactone from 1,4-butanediol by distillation is carried out by monostillation or multistage distillation under atmospheric pressure or under reduced pressure, water, tetrahydrofuran, and gamma. Butyrolactone can be removed. At that time, a component containing a large amount of tetrahydrofuran is extracted from the tower portion, water containing almost no tetrahydrofuran is extracted from the first side flow portion closer to the top of the column, and gamma-buti is extracted from the second side flow portion closer to the bottom. It is also possible to extract rockactone. Alternatively, a component containing a large amount of tetrahydrofuran can be extracted from the tower portion, water containing almost no tetrahydrofuran can be extracted from the side flow section, and 1,4-butanediol containing gamma butyrolactone can be obtained. Preferably the column static pressure is 40 mmHg-760 mmHg, More preferably, it is 200 mmHg-760 mmHg, The number of steps is 1-40, Preferably it is 1-20, Especially preferably, it is the range of 1-10 steps. to be.

In addition, the reactor type can use both a batch and a continuous, and can use both a fully mixed and a tubular reactor. Preferably the tubular reactor in continuous. From the viewpoint of avoiding blockage by solids in the reactor filled with a solid ion exchange resin, the aqueous solution is preferably a uniform liquid phase before introducing the aqueous solution of the by-product high boiling point compound into the reactor. The raw material bath temperature is preferably 40 ° C or higher, 200 ° C or lower, more preferably 60 ° C or higher and 150 ° C or lower.

In the present invention, it is essential that the 1,4-butanediol produced by the hydrolysis of the ester oligomer (produced high boiling point compound) is dehydrated with tetrahydrofuran in a reactor having a solid acid catalyst (ion exchange resin). Tetrahydrofuranization of part or all of the produced 1,4-butanediol is carried out. In the same manner, 4-hydroxybutyric acid produced by hydrolysis of an ester oligomer (produced high boiling point compound) is converted to gamma butyrolactone. In this case, it is also possible to dehydrate and cyclize 1,4-butanediol to tetrahydrofuran and 4-hydroxybutyric acid to gammabutyrolactone in the same reactor as hydrolysis, but through tetrahydrofuran, Dehydration cyclization by multistage reactor with gamma butyrolactone is also not impeded. In addition, the solid acid catalyst for dehydrating and cyclizing 1,4-butanediol produced by hydrolysis of a high boiling point compound with tetrahydrofuran and 4-hydroxybutyric acid with gamma butyrolactone is preferably an ion exchange resin, furthermore, a strongly acidic acid. More preferred are cation exchange resins. For example, sulfonated styrene-divinylbenzene copolymers can be used. This sulfonated styrene divinylbenzene copolymer is not specifically limited, A commercial item can be used. The type of the structure is not particularly limited, but any type of gel, MR type, macroscopic type, porous type, or hypousic type can be used.

In the reaction with a cation exchange resin having a sulfone group or the like, an ionic substance derived from an acid such as sulfate ion may elute in the reactor effluent, and the ionic substance derived from this acid may adversely affect the process such as corrosion. . Therefore, it is also possible to provide a packing tube of anion exchange resin after the reactor in which the cation exchange resin is filled. This anion exchange resin is not specifically limited, A commercial item can be used. The type of the structure is not particularly limited, but any type of gel, MR type, macroscopic type, porous type, or hypousic type can be used.

As for the manufacturing method of the compound which consists of C4 in this invention, especially the hydrogenation reaction of succinic acid or succinic anhydride using a homogeneous ruthenium complex catalyst is especially preferable. The supply form of ruthenium which is a catalyst in this manufacturing method is not specifically limited, What is necessary is just a metal or a ruthenium compound. As the ruthenium compound used in the present invention, for example, an oxide, a hydroxide, an inorganic acid salt, an organic acid salt or a complex compound is used. Specific examples thereof include ruthenium dioxide, ruthenium tetraoxide, ruthenium dioxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris (acetylacetonate) ruthenium, sodium hexachlororuthenate, and the like. Are ruthenium chloride, tris (acetylacetonate) ruthenium, ruthenium acetate.

As the organophosphorus compound, an organophosphorus compound containing at least one aryl group such as triphenylphosphine, diphenylmethylphosphine and dimethylphenylphosphine and its degradation product can be used, but is preferably trialkyl. Preferably trialkyls constituted by primary alkyl groups, and their degradation products.

Preferred organophosphorus compounds are, for example, tridecylphosphine, trinonylphosphine, trioctylphosphine, triheptylphosphine, trihexylphosphine, tripentylphosphine, tributylphosphine, tripropylphosphine, tri Ethylphosphine, trimethylphosphine, dimethyloctylphosphine, dioctylmethylphosphine, dimethylheptylphosphine, diheptylmethylphosphine, dimethylhexylphosphine, dihexylmethylphosphine, dimethylbutylphosphine, dibutylmethylphosphine Pin, tricyclohexylphosphine, tribenzylphosphine, dimethylcyclohexylphosphine, dicyclohexylmethylphosphine, 1,2-bis (dimethylphosphino) ethane, 1,3-bis (dimethylphosphino) propane, 1,4-bis (dimethylphosphino) butane, 1,2-bis (dioctylphosphino) ethane, 1,3-bis (dioctylphosphino) propane, 1,4-bis (dioctylphosphino) butane , 1,2-bis (dihexylphosphino) ethane, 1,3-bis (dihexylphosphino) propane, 1,4-bis (dihexylphosphino) part , 1,2-bis (dibutylphosphino) ethane, 1,3-bis (dibutylphosphino) propane, 1,4-bis (dibutylphosphino) butane, 1,3-dimethylphosphorinane, 1 Single, return, cyclic, such as 4-dimethylphosphorinane, 8-methyl-8-phosphabicyclo [3.2.1] octane, 4-methyl-4-phosphatetracyclooctane, 1-methylphosphoran, And alkyl phosphines having a substituent on the alkyl group. The alkyl group of the trialkyl phosphorus used for this reaction may be a normal body, an isoform, and a mixture thereof. The usage-amount of these phosphine ligands is 0.1-1000 mol with respect to 1 mol of ruthenium metals, Preferably it is 1-100 mol, Especially preferably, it is the range of 1-10 mol.

In addition to organic phosphines having trialkyl phosphorus or aromatic substituents, coordinating organic compounds containing other phosphorus atoms can also be used as ligands, for example, phosphite, phosphinate, phosphine oxide, Aminophosphine, phosphinic acid, etc. can also be used.

In addition, the ruthenium complex catalyst of the present invention can also be used for reaction in the form of a cationic complex using a conjugated base of an acid having a pKa of less than 2, and the conjugated base can be used in several ways, such as improving the activity and stabilizing the catalyst. The use of is effective.

As a conjugated base of an acid having a pKa of less than 2, it is sufficient to form such a conjugated base in the catalyst preparation or in the reaction system, and as the supply form, brendsted acid having a pKa of less than 2 or various salts thereof is used. Specifically, inorganic acids such as nitric acid, perchloric acid, hydrofluoric acid, hexafluorophosphoric acid, fluorosulfonic acid, trichloroacetic acid, dichloroacetic acid, trifluoroacetic acid, dodecylsulfonic acid, octadisylsulfonic acid, trifluoromethanesulfonic acid Alkali metal salts, alkaline earth metal salts, ammonium salts of Brenstead acid or their acids, such as organic acids such as benzene sulfonic acid, paratoluene sulfonic acid, tetra (pentafluorophenyl) boronic acid, sulfonated styrene-divinylbenzene copolymer, Silver salts; and the like.

The conjugated base of the acid may be added in the form of an acid derivative that is considered to form in the reaction system. For example, the same effect can be expected even if it is added to the reaction ³³ in the form of acid halide, acid anhydride, ester, acid amide and the like.

The usage-amount of these acids or its salt is 0-1000 mol with respect to ruthenium metal, Preferably it is the range of 0-100 mol. Especially preferably, it is the range of 0-10 mol.

The method for producing gamma butyrolactone of the present invention is particularly preferably carried out without a solvent, i.e., a reaction raw material and the product itself, or a by-product high boiling point compound as a solvent, but solvents other than the reaction raw material may be used. For example, ethers, such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether, dioxane, alcohols, such as methanol, ethanol, n-butanol, benzyl alcohol, phenol, ethylene glycol, diethylene glycol Carboxylic acids such as formic acid, acetic acid, propionic acid and toluic acid, esters such as methyl acetate, butyl acetate and benzyl benzoate, aromatic carbon such as benzene, toluene, ethylbenzene and tetraine, n-hexane, n-octane, Aliphatic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as dichloromethane, trichloroethane and chlorobenzene, nitro compounds such as nitromethane and nitrobenzene, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl Carboxylic acid amides such as pyrrolidone, hexamethyl phosphate triamide and other amides, ureas such as N, N-dimethylimidazolidinone, sulfones such as dimethyl sulfone, dimethyl sulfone Sulfoxides such as seeds, lactones such as gamma butyrolactone and caprolactone, polyethers such as tetraglyme and triglyme, carbonate esters such as dimethyl carbonate and ethylene carbonate, and the like, and preferably ethers. , Polyethers, and reaction raw materials, and gamma butyrolactone of the product. Reaction temperature is 20-350 degreeC normally, Preferably it is 100-250 degreeC, More preferably, it is 150-220 degreeC. The reaction can be carried out in both batch and continuous mode.

In addition, the present invention relates to a catalyst liquid obtained by removing gamma butyrolactone and a reaction solvent from a reaction solution containing a gamma butyrolactone and a by-product high boiling point compound (the reaction solution after the hydrogenation reaction of gamma butyrolactone). Extraction treatment using a non-polar solvent such as water and water, separating into a non-polar solvent phase containing a lot of ruthenium catalyst and an aqueous phase containing a lot of the high boiling point compound, the water phase is distributed to a reactor containing a cation exchange resin It is also possible. The catalyst solution obtained by removing the gamma butyrolactone and the reaction solvent was extracted and treated with a nonpolar solvent such as heptane and water to form a nonpolar solvent phase, an aqueous phase, and an oil phase insoluble to the nonpolar solvent and water. It is also possible to isolate | separate and distribute the water phase to the reactor filled with the ion exchange resin.

As a nonpolar solvent used here, an aliphatic hydrocarbon compound, an alicyclic hydrocarbon compound, an aromatic hydrocarbon compound, etc. are mentioned. Moreover, you may have a substituent as these nonpolar solvents. Specific examples include pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, diethylbenzene, isopropylbenzene, and the like, in particular pentane, hexane, Aliphatic hydrocarbon compounds having 5 to 8 carbon atoms such as heptane and octane are preferable.

The weight ratio of the catalyst liquid / water / nonpolar solvent in the extraction treatment is used within the range of 1 / 0.2 to 10 / 0.2 to 10. Moreover, extraction processing temperature is 20-150 degreeC normally, Preferably it is 40 degreeC-100 degreeC. However, in order to reduce the phosphorus concentration in an aqueous phase, it is necessary to make process temperature into 70 degreeC or less and 50 degreeC or more. This extraction time is 10 minutes-5 hours, Preferably it is the range of 30 minutes-3 hours. In addition, according to the composition of the catalyst liquid, the extraction separation using a nonpolar solvent and water is performed by separating the two phases into a nonpolar solvent phase containing a large amount of ruthenium catalyst, an aqueous phase containing a lot of high boiling point compounds, and a large amount of ruthenium catalyst. There are cases where the non-polar solvent phase, the water phase containing a lot of high boiling point compounds, and the non-polar solvent and the oil phase insoluble in water may be separated into three phases. It contains a lot and can hydrolyze by the reactor filled with the ion exchange resin. In addition, the dehydration cyclization of 1,4-butanediol to tetrahydrofuran obtained by hydrolysis also does not interfere with both the two-phase separation and the three-phase separation.

In addition, the catalyst solution obtained by removing gamma butyrolactone and the reaction solvent from the reaction solution containing "gammabutyrolactone obtained by the hydrogenation reaction and a by-product high boiling point compound, was prepared using a nonpolar solvent such as heptane and water. Extraction treatment, a water phase obtained by separating into a nonpolar solvent phase containing a large amount of ruthenium catalyst and an aqueous phase containing a lot of high boiling point compounds, and a reaction containing "gammabutyrolactone obtained by hydrogenation reaction and a byproduct high boiling point compound. The catalyst liquid obtained by removing the gamma butyrolactone and the reaction solvent from the liquid is extracted and treated with a nonpolar solvent such as heptane and water, and a nonpolar solvent phase containing a lot of ruthenium catalyst, an aqueous phase containing a lot of high boiling point compound, and a nonpolar The water phase obtained by separating into three phases of an insoluble oil phase with respect to a solvent and water, It corresponds to the boiling point of an aqueous solution of compound ".

Hereinafter, although an Example demonstrates this invention still in detail, it is not limited to a following example, unless the summary of this invention is exceeded. In the following examples, the analysis of tetrahydrofuran, 1,4-butanediol, and gammabutyrolactone was carried out by gas chromatography (GC-14B manufactured by Shimadzu Corporation) and analysis of succinic acid by an internal standard method. Shimadzu Corporation column CA-10S, detector SPD-10A), and water analysis were performed by the Karl Fischer method (Mitsubishi Chemical Corporation Mitsubishi Moisture: CA-20). In addition, the high boiling point by-products of Reference Examples 1-4 were fractionated by GPC (Tosoh GPC column TSKgel G-1000HXL & 2000HXL 7.8φx300 mm), and the fractionated sample was LC-MS (apparatus: Micromass Q-Tof, It analyzed by ESI Positive, Negative ionization method, and NMR (Unity Plus400 by Varian). As a result, it was found that it was a mixture of the following ester oligomers.

Reference Example 1

Hydrogenation reaction of succinic anhydride using a ruthenium trioctylphosphine paratoluene sulfonic acid catalyst was carried out as follows. The reaction was carried out using a circulation apparatus equipped with the gas-liquid separator 1 and the distillation column 2 shown in FIG. 1. 0.056% by weight of tris (acetylacetone) ruthenium, 0.51% by weight of trioctylphosphine and 0.22% by weight of paratoluenesulfonic acid were dissolved in triglyme (triethylene glycol dimethyl ether) in the catalyst vessel (3). It heat-processed at 200 degreeC under 2 hours, it put into the new catalyst container 5, and made this the feed catalyst liquid. This catalyst liquid was supplied to the autoclave 8 at a flow rate of 3500 mL / h, and was recovered and recycled as a effluent of the distillation column after gas-liquid separation.

On the other hand, the hydrogen gas of 7.9 Nm <3> / h was sent to the autoclave from the hydrogen compressor 6, and it adjusted to 20 atmospheres. The autoclave was heated to 200 ° C., and a raw material solution composed of 80% by weight of succinic anhydride and 20% by weight of gamma butyrolactone was continuously supplied at a flow rate of 375 g / h. After the reaction solution was cooled to 60 ° C, gas-liquid separation was conducted at atmospheric pressure, the product water, gamma butyrolactone, and catalyst solution were separated in a distillation column, and the catalyst solution was returned to the catalyst vessel 3. After some days, the catalyst liquid was extracted at a flow rate of 29 g / h at a portion of the flow thereof, and was added to the extraction catalyst (4).

The new catalyst was replenished to the autoclave from the new catalyst liquid 5 at a flow rate of 29 g / h corresponding to the extraction. The reaction was conducted continuously for 30 days, but stable results were obtained after 7 days. The composition of the extraction catalyst liquid was as follows.

Succinic acid anhydride + succinic acid 4 wt% Gamma butyrolactone 4 wt% Triglyme 65 wt% High boiling point compound 26% by weight Ruthenium metal concentration 92 ppm

Reference Example 2

The extraction catalyst liquid obtained in the reference example 1 was concentrated as follows. 878.1 g of extraction catalyst liquid was put into the jacketed reactor equipped with the vacuum distillation apparatus, and the triglyme which is a solvent was distilled off by vacuum distillation. At this time, the pressure reduction degree was controlled in the range of 70 mmHg-5 mmHg so that the temperature of a liquid may be kept at 160 degrees C or less. After solvent distillation, 295.75 g of concentrated catalyst solution was obtained. The composition of the obtained concentrated catalyst liquid was as follows.

Triglyme 0.3 wt% Succinic anhydride + succinic acid 19.7 wt% High boiling point compound 80.0% by weight Gamma butyrolactone 0.0 wt%

Reference Example 3

90.3g of water and 28.0g of heptane were added to 39.8g of the concentrated catalyst liquid obtained by the said Reference Example 2, and it stirred at 80 degreeC for 1 hour. When left at 80 ° C., the heptane phase, the aqueous phase, the heptane phase and the aqueous phase were separated into three phases of an insoluble oil phase. The aqueous phase was separated from these 3 phases to obtain 114.1 g of the aqueous phase. The composition of this water phase was as follows. The following Example was implemented using this award. In addition, the analysis of ICP showed that the phosphorus concentration in the aqueous phase was 498 wtppm.

moisture 72.8% by weight Succinic Acid + Succinic Anhydride 9.0 wt% High boiling point compound 18.2% by weight 1,4-butanediol 0.0 wt% Gamma butyrolactone 0.0 wt% Tetrahydrofuran 0.0 wt%

Reference Example 4

86.5g of water and 28.0g of heptane were added to 39.8g of the concentrated catalyst liquid obtained by the said Reference Example 2, and it stirred at 80 degreeC for 1 hour, and cooled and left still at 65 degreeC for 1 hour. As a result, the heptane phase, the water phase, the heptane phase, and the water phase were separated into three phases of an insoluble oil phase from above. The aqueous phase was separated from these 3 phases to obtain 113.2 g of the aqueous phase. The composition of this water phase was as follows. The following Example was implemented using this award. In addition, the analysis of ICP showed that the phosphorus concentration in the aqueous phase was 59 wtppm.

moisture 71.5 wt% Succinic Acid + Succinic Anhydride 6.5 wt% High boiling point compound 21.9% by weight 1,4-butanediol 0.0 wt% Gamma butyrolactone 0.1 wt% Tetrahydrofuran 0.0 wt%

Example 1

An aqueous phase obtained in Reference Example 3 (80 weights of ion-exchange resin (Mitsubishi Chemical Corporation: SK1B-H)) was filled in 80 mL of stainless steel reaction tubes (inner diameter 10 mm), and diluted 2 times with demineralized water (high-boiling point compound 9.1 weight). %) Was passed through at 10 mL / h and 100 ° C (retention time 8h). The reaction tube was heated to 100 degreeC by the heater. As a result of analyzing the reaction tube outlet liquid, the composition was as Table 5 below.

Example 2

The aqueous phase obtained by the reference example 3 diluted by 2 weight times in demineralized water (9.1 weight% of a high boiling point compound) was carried out similarly to Example 1 except having passed through 20 mL / h and 100 degreeC (retention time 4h). As a result of analyzing the reaction tube outlet liquid, the composition was shown in Table 4.

Example 3

The water phase obtained in Reference Example 3 diluted 2 weights in demineralized water (9.1 wt% of high boiling point compound) was passed through at 10 mL / h and 110 ° C (retention time 8h), except that the heating temperature of the reaction tube was 110 ° C. It carried out similarly to Example 1. As a result of analyzing the reaction tube outlet liquid, the composition was as Table 5 below.

Example 4

The aqueous phase (9.1 wt% of high boiling point compound) obtained in Reference Example 3 diluted 2 times by weight in demineralized water was passed through at 10 mL / h and 80 ° C (retention time 8h), except that the heating temperature of the reaction tube was changed to 80 ° C. It carried out similarly to Example 1. As a result of analyzing the reaction tube outlet liquid, the composition was as Table 5 below.

Example 5

Into a 50 mL glass flask, agitator, 5.0 g of an aqueous phase (19.2 wt% of high boiling point compound) obtained in Reference Example 3, and 2.1 g of ion exchange resin (SK1B-H manufactured by Mitsubishi Chemical Corporation) were added thereto, followed by 5 h heating and stirring at 100 ° C. Carried out. As a result of analyzing the reaction solution, 39.1 wt% of the high boiling point compound converted to succinic acid + succinic anhydride, 12.3 wt% converted to 1,4-butanediol, and 2.5 wt% converted to tetrahydrofuran.

Example 6

Into a 50 mL glass flask, agitator, 2.0 g of an aqueous phase (19.2 wt% of high boiling point compound) obtained in Reference Example 3, 3.1 g of demineralized water, and 2.1 g of ion exchange resin (SK1B-H manufactured by Mitsubishi Chemical Corporation) were added thereto at 100 ° C. 5h heat stirring was performed. As a result of analyzing the reaction solution, 52.6 wt% of the high boiling point compound converted to succinic acid + succinic anhydride, 15.8 wt% converted to 1,4-butanediol, and 1.5 wt% converted to tetrahydrofuran.

Example 7

80 mL of a stainless steel reaction tube (inner diameter 10 mm) was charged with 80 mL of ion exchange resin (Mitsubishi Chemical Corporation: SK1B-H), and the aqueous phase obtained in Reference Example 3 (19.2 wt% of high boiling point compound) was not diluted in demineralized water. It flowed through at 20 mL / h and 100 degreeC, without (residence time 8h). The reaction tube was heated to 100 degreeC by the heater. As a result of analyzing the reaction tube outlet liquid, the composition was as Table 5 below.

Example 8

80 mL of a stainless steel reaction tube (inner diameter 10 mm) was charged with 80 mL of ion exchange resin (Mitsubishi Chemical Corporation: SK1B-H), and the aqueous phase obtained in Reference Example 4 (21.9 wt% of high boiling point compound, phosphorus concentration of 59 wtppm) was added thereto. It did not dilute in demineralized water, and it passed through at 10 mL / h and 110 degreeC for 400 hours (retention time 8h). The reaction tube was heated to 110 ° C. in a heater. As a result of analyzing the reaction tube outlet liquid, compared with after 8 hours, the amount of succinic acid produced after 400 hours was 99.8% (vs. ratio to the amount produced after 8 hours), and no activity deterioration was confirmed.

Comparative Example 1

It carried out similarly to Example 6 except not having used ion exchange resin. As a result of analyzing the reaction liquid, 2 weight% of the high boiling point compound converted into succinic acid + succinic anhydride, and 1 weight% converted to 1,4-butanediol. Tetrahydrofuran was not produced.

Comparative Example 2

It carried out similarly to Example 4 except not having used ion exchange resin. As a result of analyzing the reaction tube outlet liquid, the composition was as Table 5 below.

Example 9

80 mL of a stainless steel reaction tube (inner diameter 10 mm) was charged with 80 mL of ion exchange resin (Mitsubishi Chemical Corporation: SK1B-H), and the aqueous phase obtained in Reference Example 3 (18.2 wt% of high boiling point compound, phosphorus concentration 498 wtppm) was added thereto. It did not dilute in demineralized water, and it passed through at 10 mL / h and 110 degreeC for 400 hours (retention time 8h). The reaction tube was heated to 110 degreeC by the heater. As a result of analyzing the reaction tube outlet liquid, the amount of succinic acid produced after 400 hours fell to 85.1% (vs. ratio after 8 hours) compared with after 8 hours.

Composition after reaction Ingredient Name Example 1 Example 2 Example 3 Example 4 Example 7 Comparative Example 2 High boiling point compound wt% 3.0 2.8 0.90 4.2 10.0 7.7 Succinic anhydride + succinic acid wt% 12 13 13 11 14 11 1,4-butanediol wt% 1.0 1.5 0.0 2.1 1.3 0.5 Tetrahydrofuran wt% 2.5 1.6 4.4 0.70 5.9 0.0 Moisture wt% 80 80 81 81 67 80 Gamma Butyrolactone wt% 0.26 0.25 0.25 0.26 0.25 0.15

The present invention provides a more efficient, industrially advantageous method for decomposing high-boiling compounds produced as by-products in the production of C4 family such as gamma butyrolactone and regenerating raw materials. It is widely applicable to the manufacturing method of the.

In addition, all the content of the JP Patent application 2004-299577, the claim, drawing, and the abstract for which it applied on October 14, 2004 is referred here, and it takes in as an indication of the specification of this invention.

Claims (15)

Aqueous solutions of ester oligomers containing succinic acid and / or 4-hydroxybutyric acid and 1,4-butanediol as constituents are contacted with a solid acid catalyst under heating to decompose into respective constituents, A method for decomposing an ester oligomer for converting butanediol to tetrahydrofuran and / or converting 4-hydroxybutyric acid to gamma butyrolactone when it contains 4-hydroxybutyric acid as a constituent of the ester oligomer. Aqueous solutions of ester oligomers containing succinic acid and 1,4-butanediol as constituents are brought into contact with a solid acid catalyst under heating to decompose into succinic acid and 1,4-butanediol, and 1,4-butanediol is tetrahydro Process for the decomposition of ester oligomers converted to furan. An aqueous solution of an ester oligomer containing 4-hydroxybutyric acid and 1,4-butanediol as a constituent is contacted with a solid acid catalyst under heating to decompose into 4-hydroxybutyric acid and 1,4-butanediol, and 4 -Decomposition method of the ester oligomer which converts hydroxybutyric acid to gamma butyrolactone. The method according to any one of claims 1 to 3, The decomposition method of the ester oligomer whose heating is 80-200 degreeC and whose contact time with a solid acid catalyst is 1-20 hours. The method according to any one of claims 1 to 4, A method for decomposing an ester oligomer, wherein the aqueous solution of the ester oligomer is an aqueous solution having a phosphorus concentration of 1 wtppm to 400 wtppm. The method according to any one of claims 1 to 5, A method for decomposing an ester oligomer, wherein the aqueous solution of an ester oligomer is an aqueous solution of a high boiling point compound which is a byproduct when a compound having 4 carbon atoms is produced by hydrogenation of dicarboxylic acid or acid anhydride or dehydrogenation of diol. The method of claim 6, The method for decomposing an ester oligomer, wherein the compound having 4 carbon atoms is at least one of gamma butyrolactone, 1,4-butanediol, tetrahydrofuran, succinic acid, and succinic anhydride. The method of claim 6, A method for decomposing an ester oligomer, wherein the compound having 4 carbon atoms is gamma butyrolactone. The method according to any one of claims 1 to 8, A method for decomposing an ester oligomer, wherein the solid acid catalyst is a cation exchange resin having a sulfone group. A method for producing succinic acid in which an aqueous solution of an ester oligomer containing succinic acid and 1,4-butanediol as a constituent component is brought into contact with a solid acid catalyst under heating to decompose into succinic acid and tetrahydrofuran. Preparation of gamma butyrolactone decomposed into gamma butyrolactone and tetrahydrofuran by contacting a solid acid catalyst with an aqueous solution of an ester oligomer containing 4-hydroxybutyric acid and 1,4-butanediol as components. Way. A method of producing a compound having 4 carbon atoms by hydrogenation of a dicarboxylic acid or an acid anhydride, wherein an aqueous solution containing a high-boiling compound by-produced when producing a compound having 4 carbon atoms is decomposed into succinic acid and tetrahydrofuran, A method for producing a compound having 4 carbon atoms, which introduces succinic acid into the hydrogenation reaction of dicarboxylic acid or acid anhydride. A method of producing a compound having 4 carbon atoms by hydrogenation of dicarboxylic acid or acid anhydride, wherein an aqueous solution containing a high-boiling compound by-produced when producing a compound having 4 carbon atoms is brought into contact with a solid acid catalyst under heating. And decomposing the high boiling point compound into succinic acid and tetrahydrofuran, distilling off water and tetrahydrofuran, and introducing the obtained aqueous succinic acid solution into the hydrogenation reaction of dicarboxylic acid or acid anhydride. Manufacturing method. The method according to claim 12 or 13, The method for producing a compound having 4 carbon atoms by hydrogenation of dicarboxylic acid or acid anhydride or dehydrogenation of diol is carried out using a homogeneous ruthenium complex catalyst, succinic anhydride, succinic acid, maleic anhydride, or a plurality of compounds. A method for producing a compound having 4 carbon atoms, which is a method for producing gamma butyrolactone by hydrogenation or by dehydrogenation of 1,4-butanediol. The method according to any one of claims 12 to 14, The aqueous solution containing the high boiling point compound by-produced when producing the C4 compound removes the C4 compound and the reaction solvent from the reaction solution obtained by hydrogenation of dicarboxylic acid or acid anhydride or dehydrogenation of diol. The manufacturing method of a C4 compound which is an aqueous phase in the multiple phase obtained by adding and extracting water and a nonpolar solvent to the catalyst liquid containing the by-product high boiling point compound obtained by this.

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