JP3386569B2 - Method for concentration separation and reuse of ruthenium complex - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for concentrating and separating a ruthenium complex from a hydrogenation reaction product solution of an organic compound using a ruthenium complex as a catalyst, and reusing the separated ruthenium complex in a hydrogenation reaction. is there. Specifically, the present invention uses a ruthenium complex having a tertiary organic phosphorus compound as a ligand as a catalyst to hydrogenate a dicarboxylic acid or a derivative thereof, and concentrates and separates a ruthenium complex from a reaction product solution of the dilute ruthenium complex. The present invention relates to a method of reusing hydrogen peroxide in a hydrogenation reaction.

[0002]

Ruthenium complexes having a tertiary organic phosphorus compound as a ligand are used for hydrogenation reactions of various carbonyl compounds by a homogeneous catalytic reaction. This ruthenium complex catalyst is chemically relatively stable, and the reaction product and the catalyst solution are separated by distillation, and the catalyst solution is circulated to the reaction zone for reuse, or the reaction product is gas stripped. Thus, it is possible to allow the catalyst solution to flow out of the reaction zone and be separated, and to carry out the reaction continuously while leaving the catalyst solution in the reaction zone. However, in these reactions, it is unavoidable that various high-boiling by-products are generated, and when these reactions are continuously carried out, the high-boiling substances accumulated in the catalyst liquid are removed to remove the catalyst liquid. It is necessary to continuously or intermittently withdraw a part of it from the reaction system.

As a matter of course, since the extracted liquid contains ruthenium, its treatment is required for disposal. However, when a liquid containing ruthenium is burnt, RuO _{4 which} is toxic and highly corrosive is formed, and therefore the incineration process is limited. In addition, when the industrial waste treatment company is requested to perform the treatment, it is costly because of the mass of the treatment liquid, so that it is economically disadvantageous when the treatment amount is large. Therefore, if ruthenium in the extracted liquid to be treated can be concentrated, its economic effect will be very large. Furthermore, if the ruthenium complex can be efficiently recovered from this extracted liquid and reused in the reaction, the burden of waste liquid treatment can be greatly reduced and the catalyst cost can be significantly reduced economically. Moreover, since the absolute amount of ruthenium discharged is reduced, it can be said that it is preferable from the viewpoint of preventing environmental pollution, but its effect is enormous. However, for that purpose, it is necessary to separate and collect the ruthenium complex catalyst from the reaction solution while keeping the active form.

Conventionally, as a method for separating and recovering a Group 8 metal such as rhodium, an extraction method using a strong acid (Japanese Patent Publication No. 46-4).
3219), a decomposition method using peroxide (US Patent No. 35).
No. 47964, JP-A No. 51-63388) and the like are known, but both methods involve the problem of corrosion of the material of the apparatus because an acid is used.

[Problems to be Solved by the Invention]

The present inventors economically and efficiently recover a ruthenium complex having a tertiary organic phosphorus compound as a ligand from a hydrogenation reaction product solution of an organic compound, and further recover this. As a result of diligent study on a method of reusing the ruthenium complex obtained in the hydrogenation reaction, it was found that the catalyst solution obtained by removing the desired product and the reaction solvent from the hydrogenation reaction product solution is treated with water and a nonpolar organic solvent. Due to
It has been found that the ruthenium complex can be extracted and recovered in the non-polar organic solvent phase. Further, it was found that the ruthenium complex thus recovered can be reused in the hydrogenation reaction, and the present invention has been accomplished. That is, the present invention is the third
Ruthenium complex is efficiently and economically recovered from the hydrogenation reaction product solution of an organic compound containing a ruthenium complex having a ruthenium complex as a ligand as a catalyst, and reused in the hydrogenation reaction as necessary. The purpose is to provide a method of doing.

[Means for Solving the Problems]

The present invention is a catalyst obtained by hydrogenating an organic compound in the presence of a ruthenium complex having a tertiary organic phosphorus compound as a ligand, and removing a target product and a reaction solvent from the obtained reaction solution. The liquid is subjected to an extraction treatment with water and a nonpolar organic solvent, a nonpolar organic solvent phase containing a ruthenium complex is separated, and the nonpolar organic solvent is distilled off from the nonpolar organic solvent phase to obtain a residue, The gist of the present invention is a method for concentrating and separating and reusing the ruthenium complex, which comprises treating the residue thus obtained with an acid, if necessary, and then subjecting it to a hydrogenation reaction.

The present invention will be described in detail below. The present invention provides a ruthenium complex which is concentrated and separated from a hydrogenation reaction product liquid of an organic compound containing a ruthenium complex having at least one kind of a tertiary organic phosphorus compound as a ligand, and separated and recovered as necessary. The complex is reused in the hydrogenation reaction, and the hydrogenation reaction includes hydrogenation of a carbonyl compound, for example, hydrogenation reaction of an aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid anhydride, an aliphatic dicarboxylic acid diester, etc. Is mentioned. In particular, a ruthenium complex having a tertiary organophosphorus compound as a ligand is used as a homogeneous catalyst, and the ruthenium complex is concentrated and separated from a reaction solution for hydrogenating succinic anhydride to produce γ-butyrolactone, and then hydrogenation is performed again. It is effective when used in the chemical reaction.

A ruthenium complex catalyst used in a hydrogenation reaction,
In particular, a catalyst for hydrogenating succinic anhydride to produce γ-butyrolactone usually contains (i) ruthenium, (ii) a tertiary organic phosphine and (iii) a conjugate base of an acid having a pka value of less than 2, Is a ruthenium complex containing a neutral ligand, and specific examples of each component used for its preparation are as follows.

(A) Ruthenium; As ruthenium,
Both metallic ruthenium and ruthenium compounds can be used. As the ruthenium compound, an oxide of ruthenium, a halide, a hydroxide, an inorganic acid salt, an organic acid salt or a complex compound is used, and specifically, for example, ruthenium dioxide, ruthenium tetraoxide, ruthenium dihydroxide,
Ruthenium chloride, ruthenium bromide, ruthenium iodide,
Ruthenium nitrate, ruthenium acetate, tris (acetylacetone) ruthenium, sodium hexachlororuthenate, dipotassium tetracarbonylruthenate, pentacarbonylruthenium, cyclopentadienyldicarbonylruthenium, dibromotricarbonylruthenium, chlorotris (triphenylphosphine) hydridoruthenium, bis (Tri-n-butylphosphine) tricarbonylruthenium, dodecacarbonyltriruthenium, tetrahydridodecacarbonyltetraruthenium,
Octadecacarbonyl dicesium hexaruthenate,
Examples include undecacarbonyl hydrido tetraphenylphosphonium triruthenate and the like. The amount of the metal ruthenium and the ruthenium compound used is 0.0001 to 10 as ruthenium in 1 liter of the hydrogenation reaction solution.
It is 0 mmol, preferably 0.001 to 10 mmol.

(B) Tertiary organic phosphine: It is considered that the organic phosphine contributes to controlling the electronic state of ruthenium of (a) which is the main catalyst and stabilizing the active state of ruthenium. Specific examples of the organic phosphine include trialkylphosphines such as tri-n-octylphosphine, tri-n-butylphosphine and dimethyl-n-octylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, triphenylphosphine. Triarylphosphines, such as
Alkylarylphosphines such as dimethylphenylphosphine, 1,2-bis (diphenylphosphino)
Included are polyfunctional phosphines such as ethane. The amount of organic phosphine used is usually about 3 to 1000 mol, preferably 5 to 100 mol, per 1 mol of ruthenium. That is, it is considered that the organic phosphine is usually coordinated with 3 moles per 1 mole of ruthenium, but in the present invention, it is preferable to use the organic phosphine in a mole number or more necessary for the coordination. The existence form of this excess organic phosphine in the reaction system is not always clear, but it is presumed that it has some bond with the substrate or the like present in the system. Further, the organic phosphine can be supplied to the hydrogenation reaction system by itself or in the form of a complex with a ruthenium catalyst.

(C) Conjugate base of acid having pka value less than 2; Conjugate base of acid having pka value less than 2 acts as an additional promoter of the ruthenium catalyst, and can be used in preparation of the catalyst or in the reaction system. Any acid can be used as long as it produces a conjugate base of an acid having a value smaller than 2.
Bronsted acids having a pka value of less than 2 or various salts thereof are used. Specifically, for example, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, perchloric acid, phosphoric acid, borofluoric acid, hexafluorophosphoric acid, tungstic acid, phosphomolybdic acid, phosphotungstic acid, silicon tungstic acid, polysilicic acid, fluorosulfone. Inorganic acids such as acids, organic acids such as trichloroacetic acid, dichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, laurylsulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, or ammonium of these acids Examples thereof include salts and phosphonium salts. Further, the same effect can be obtained even if the conjugate base of these acids is added in the form of an acid derivative, such as an acid halide, an acid anhydride, an ester or an acid amide, which is considered to be produced in the reaction system. The amount of these acids or salts used is 0.01 to 1 with respect to 1 mol of ruthenium.
The amount is in the range of 000 mol, preferably 0.1 to 100 mol, and more preferably 0.5 to 20 mol.

In addition to the above-mentioned components (a), (b) and (c), as a neutral ligand which may be optionally contained, hydrogen; ethylene, propylene, butene, cyclopentene, cyclohexene, butadiene, Olefins such as cyclopentadiene, cyclooctadiene, norbonadiene; carbon monoxide, diethyl ether, anisole, dioxane, tetrahydrofuran, acetone, acetophenone, benzophenone, cyclohexanone, propionic acid, caproic acid, butyric acid, benzoic acid, ethyl acetate, allyl acetate , Oxygen-containing compounds such as benzyl benzoate and benzyl stearate; nitric oxide, acetonitrile, propionitrile, benzonitrile, cyclohexylisonitrile,
Butylamine, aniline, toluidine, triethylamine, pyrrole, pyridine, N-methylformamide, acetamide, 1,1,3,3-tetramethylurea, N-
Nitrogen-containing compounds such as methylpyrrolidone, caprolactam and nitromethane; carbon disulfide, n-butyl mercaptan,
Sulfur-containing compounds such as thiophenol, dimethyl sulfide, dimethyl disulfide, thiophene, dimethyl sulfoxide, diphenyl sulfoxide; tributylphosphine oxide, ethyldiphenylphosphine oxide, triphenylphosphine oxide, diethylphenylphosphinate, diphenylmethylphosphinate, diphenylethylphosphinate , O, o-Dimethylmethylphosphonothiolate, triethyl phosphite, triphenyl phosphate, triethyl phosphate, triphenyl phosphate, hexamethylphosphoric triamide, and other phosphorus-containing compounds other than organic phosphines.

In the hydrogenation reaction using a ruthenium complex catalyst, the reaction can be carried out using the raw material itself as a solvent. However, in consideration of the reactivity of the raw material and the treatment operation of the reaction system, other reaction solvent may be used in addition to the raw material. It is advantageous to use. Examples of such a reaction solvent include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol diethyl ether, triethylene glycol dimethyl ether, dioxane; ketones such as acetone, methyl ethyl ketone, acetophenone, methanol, ethanol, n-butanol. , Benzyl alcohol, ethylene glycol, diethylene glycol, and other alcohols; phenols; formic acid, acetic acid, propionic acid, toluic acid, and other carboxylic acids; methyl acetate, n-butyl acetate, benzyl benzoate, and other esters; benzene, toluene, Aromatic hydrocarbons such as ethylbenzene and tetralin; Aliphatic hydrocarbons such as n-hexane, n-octane and cyclohexane; Dichloromethane, trichloroethane, chlorobenze Halogenated hydrocarbons such as nitromethane, Nitrohydrocarbons such as nitrobenzene; Carboxamides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Hexamethylphosphoric triamide, N, N, N Other amides such as', N'-tetraethylsulfamide; ureas such as N, N'-dimethylimidazolidone, N, N, N, N-tetramethylurea; sulfones such as dimethyl sulfone and tetramethylene sulfone Kind;
Sulfoxides such as dimethyl sulfoxide and diphenyl sulfoxide; lactones such as γ-butyrolactone and ε-caprolactone; polyethers such as triglyme (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether) and 18-crown-6; Nitriles such as acetonitrile and benzonitrile; carbonic acid esters such as dimethyl carbonate and ethylene carbonate.

In order to carry out this hydrogenation reaction, a catalyst liquid containing the above-mentioned catalyst components in which the concentrations of the raw material and the organic phosphine are adjusted in advance is introduced into the reaction vessel, and hydrogen is further introduced. Hydrogen may be diluted with a reaction inert gas such as nitrogen or carbon dioxide. The reaction temperature is generally 50 to 250 ° C, preferably 100 to 200 ° C. The hydrogen partial pressure in the reaction system is not particularly limited, but is usually 0.1 to 100 kg / cm ² in industrial practice,
It is preferably 1 to 50 kg / cm ² . The target product is separated from the reaction product solution by a usual separation means such as distillation or extraction. The residue after separation is constantly checked for the catalyst composition concentration contained therein, if necessary, so that the concentration of the organic phosphine in the liquid is always maintained at the above-mentioned predetermined concentration,
In the circulation process, organic phosphine is appropriately replenished and circulated in the reactor.

In the method of the present invention, the ruthenium complex is concentrated and separated from the hydrogenation reaction product solution as described above. First, the target product is separated from the reaction product solution, and the reaction solvent used in the reaction is distilled off and concentrated. To do. In the hydrogenation reaction of succinic anhydride, the reaction solvent is distilled off after separating the water produced together with the target product γ-butyrolactone from the reaction solution. If the solvent is distilled off from the reaction solution, the liquid separation property in the subsequent extraction treatment often becomes good. Especially in the hydrogenation reaction, when a solvent compatible with oil and water is used, good separation may not be achieved unless an extraction treatment is carried out after distilling off the solvent in advance. Therefore, it is preferable to perform the extraction treatment after removing the reaction solvent as much as possible, and the amount of the remaining reaction solvent is 0 to 20% by weight, preferably 0 to 10% by weight, and more preferably 0 to 5% by weight. The solvent is distilled off.

Distillation of the reaction solvent from the reaction solution can be carried out by ordinary distillation, and vacuum distillation may be employed depending on the type of solvent. In any of these methods, in order to prevent modification of the ruthenium complex existing in the liquid, it is preferable to carry out while maintaining the column bottom temperature during distillation at 220 ° C or lower. Then, water and a non-polar organic solvent are added to the obtained concentrated reaction solution for extraction treatment. By this treatment, the water-soluble organic compound is distributed to the aqueous phase, while the ruthenium complex is extracted into the organic solvent phase, and this organic solvent phase is separated. In the aqueous phase, of the organic compounds contained in the reaction solution, for example, carboxylic acid or water-soluble ester of the substrate itself, and water-soluble high-boiling substances such as water-soluble polyester which is a polymer thereof are extracted. To be done.

As the organic solvent used together with water, a relatively low-polarity, that is, non-polarity solvent which separates from water is used. Specifically, hexane, heptane, aliphatic hydrocarbons such as octane, benzene, toluene, xylene, aromatic hydrocarbons such as cumene, diethyl ether, ethers such as anisole, methyl isobutyl ketone, ketones such as acetophenone, Examples include halogenated hydrocarbons such as dichloromethane, trichloroethane and chlorobenzene.

There is no particular restriction on the order of treatment when the concentrated reaction solution is treated with water and a non-polar organic solvent. 1) The concentrated solution is first treated with water, the aqueous phase is removed, and the residue is treated with organic matter. Either extraction with a solvent or 2) simultaneous extraction with water and an organic solvent in the concentrated liquid can be employed. The temperature at which the concentrated solution is treated with water and an organic solvent is
Usually, it is selected in the range of 0 to 150 ° C, preferably 20 to 100 ° C. The stirring time when treating the concentrated liquid with water and the organic solvent is preferably until the distribution is completed,
In particular, there is no problem if it is discontinued in the middle. In particular,
A range of 10 minutes to 10 days applies.

When the concentrated solution is treated with water and an organic solvent at the same time, after stirring, the content liquid which was an emulsion is converted into three phases of an organic solvent phase, an aqueous phase and an oil phase insoluble therein, or with an organic solvent phase. It is found to separate into two aqueous phases. Among these, the ruthenium complex is mainly distributed in the organic solvent phase. On the other hand, the amount of ruthenium complex distributed in the water phase and the oil phase is very small. Typically, 80% or more of the ruthenium complex will partition into the organic solvent phase. By distilling off the organic solvent from the obtained organic solvent phase, an oily residue in which ruthenium is concentrated to a high concentration can be obtained.

Since the ruthenium complex is contained in a high concentration in this residue, it is industrially extremely useful if it can be reused in the hydrogenation reaction. By the way, the ruthenium thus obtained is concentrated to a high concentration in the residue,
It contains substances that liberate organic phosphines when subjected to high temperature hydrogenation reaction conditions. It is considered that this substance was not present in the hydrogenation reaction solution and was produced by modifying the ruthenium complex with the organic phosphine derivative in the process of treating and concentrating and separating the ruthenium complex with water. Therefore, when the recovered ruthenium complex is used as the main catalyst in the batch reaction, a large amount of free organic phosphine is present in the reaction system, which adversely affects the hydrogenation reaction. That is, when both the organic phosphine and the substrate succinic anhydride are present at a high concentration, they react easily and the hydrogenation reaction is hindered.

In such a case, it is preferable to treat the residue containing the recovered ruthenium complex with an acid before reuse in the hydrogenation reaction. By this acid treatment, the organic phosphine is converted into a reaction product with an acid, and even if it is subjected to a hydrogenation reaction, it has no adverse effect in the reaction system. As the acid to be used, any acid having a pka value of less than 2 used in preparing the above-mentioned catalyst can be used, and among these, methanesulfonic acid, trifluoromethanesulfonic acid, laurylsulfonic acid, etc. Aryl sulfonic acids such as alkyl sulfonic acid, benzene sulfonic acid and p-toluene sulfonic acid are preferable, and p-toluene sulfonic acid is particularly preferable.

The amount of acid used depends on the type of acid,
Usually, it is equivalent to the organic phosphine liberated under the reaction conditions contained in the residue (as the amount of free acid) or more. When treating the residue with an acid, it is effective to dissolve the residue in the reaction solvent used for the hydrogenation reaction and to treat the residue. The amount of the reaction solvent used is not particularly limited, but it is preferable to make it approximately equal to the solvent concentration under the hydrogenation reaction conditions. The treatment with an acid is generally carried out at 20 to 300 ° C., preferably 100 to 250 ° C., and it is preferable to carry out the treatment under an inert atmosphere such as nitrogen or argon. The solution containing the ruthenium complex recovered by acid treatment as described above can be subjected to a hydrogenation reaction by adding a substrate such as succinic anhydride to the solution, and the reaction activity thereof is the same as that of a newly prepared catalyst. It is equivalent and is effectively recovered as a catalyst. In the case of a typical continuous reaction, since the substrate and the recovered ruthenium catalyst are introduced into a mixture of a circulating liquid and a reaction product liquid that are circulated in a large amount, the substrate in the reaction system is Also, the concentration of the organic phosphine becomes low, and the reaction inhibition as in the batch reaction does not occur.

【The invention's effect】

According to the method of the present invention, a ruthenium complex having a tertiary organic phosphorus compound as a ligand is economically and efficiently concentrated and separated from a hydrogenation reaction product liquid, and the obtained separated liquid is hydrogenated. It is a method that is industrially useful because it enables reuse in the reaction.

EXAMPLES Next, the present invention will be explained more specifically with reference to examples and reference examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Reference Example 1 A hydrogenation reaction of succinic anhydride using a ruthenium-trioctylphosphine-paratoluenesulfonic acid catalyst was carried out as follows. The reaction was carried out using a gas-liquid separator (1) and a circulation device equipped with a distillation column (2) shown in FIG. In the catalyst container (3), 0.056 wt% tris (acetylacetone) ruthenium, 0.51 wt% trioctylphosphine, 0.
22% by weight of paratoluene sulfonic acid was dissolved in triglyme (triethylene glycol dimethyl ether) and heat-treated at 200 ° C. for 2 hours in a nitrogen atmosphere and put in a new catalyst container (5) to prepare a new feed catalyst solution. This catalyst solution was added at 3500 ml / h. Was supplied to an autoclave (8) having an internal volume of 0.2 liters, and after gas-liquid separation in the gas-liquid separator (1), it was recovered and recycled as bottoms of the distillation column (2).

On the other hand, from the hydrogen compressor (6), 7.9 Nm ³ /
h. Was sent to the autoclave and adjusted to 40 atm. The temperature of the autoclave was raised to 205 ° C., and a raw material liquid consisting of 80% by weight of succinic anhydride and 20% by weight of γ-butyrolactone was added at 375 g / h. Was continuously supplied at a flow rate of. The reaction solution is cooled to 60 ° C., and is then subjected to gas-liquid separation at atmospheric pressure in a gas-liquid separator (1), and then the product water and γ-butyrolactone and the catalyst solution are separated in a distillation column (2), and the catalyst solution Is returned to the catalyst container (3), but from 7 days after the start of the reaction
9 g / h. The catalyst liquid was extracted at a flow rate of and was stored in the extracted catalyst container (4).

29 g / h.m. Corresponding to the extracted amount The new catalyst was replenished from the new catalyst container (5) at a flow rate of. The reaction is 3
It was run for 0 consecutive days, but stable results were obtained after the 7th day. The quantitative determination of the reaction liquid, the raw material, the product, and the high boiling point substance in the product liquid was performed by gas chromatography and GPC. The reaction results after the 7th day were as follows on average. Succinic anhydride conversion rate 99.5% γ-butyrolactone 97.5% B. Conversion rate 2.5% Further, the composition of the withdrawn catalyst liquid was as follows. Succinic anhydride + succinic acid 4% by weight γ-butyrolactone 4% by weight Triglyme 65% by weight High boiling point substance 26% by weight Ru concentration 92 ppm

Reference Example 2 The extracted catalyst liquid obtained in Reference Example 1 above was concentrated as follows. 878.1 g of the extracted catalyst solution was put into a jacket type reactor equipped with a vacuum distillation apparatus, and triglyme as a solvent was distilled off by vacuum distillation. At this time, the degree of pressure reduction is 70 mmHg to 5 so that the liquid temperature is maintained at 160 ° C or lower.
Control was performed in the range of mmHg. After distilling off the solvent, 295.75 g of a concentrated reaction solution was obtained, and the concentration ratio of this mass was 3
It was 3.68%.

Example 1 5 g of the concentrated reaction solution obtained in Reference Example 2, 14 g of demineralized water, and 6 g of toluene were placed in a sealable sample bottle and allowed to stand at room temperature for 5 hours.
Shake for a minute. Then, after standing still, the number of days required for separating into three phases of a toluene phase, an aqueous phase and an oil phase insoluble in both was about 7 days. As a result of measuring the ruthenium content of the toluene phase by IPC, 80% or more of the charged ruthenium was distributed to the toluene phase.

Comparative Example 1 An experiment similar to that of Example 1 was performed, except that the concentrated reaction solution obtained in Reference Example 2 was replaced with the triglyme-containing reaction solution obtained in Reference Example 1. As a result, after shaking,
Even when it was left standing, it only became cloudy and the content liquid was not separated at all.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a circulation reaction system in which a hydrogenation reaction of succinic anhydride shown in Reference Example 1 is carried out.

[Explanation of symbols]

1 gas-liquid separator 2 distillation tower 3 catalyst container 4 Extraction catalyst container 5 New catalyst container 6 compressor 7 Raw material container 8 reactor (autoclave)

Continuation of front page (56) Reference JP-A-3-112972 (JP, A) JP-A-3-204870 (JP, A) JP-A-3-141273 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) B01J 21/00-38/34 C01G 55/00 C07D 307/00

Claims (15)

(57) [Claims] 1. A catalyst liquid obtained by removing a target product and a reaction solvent from a reaction liquid obtained by hydrogenating an organic compound in the presence of a ruthenium complex having a tertiary organic phosphorus compound as a ligand. , Treated with water and a non-polar organic solvent,
Separating the non-polar organic solvent phase containing the ruthenium complex,
A method for concentrating and separating a ruthenium complex, which comprises distilling off a nonpolar organic solvent from the nonpolar organic solvent phase. 2. Hydrogenating an organic compound in the presence of a ruthenium complex having a tertiary organic phosphorus compound as a ligand,
The catalyst solution obtained by removing the target product and the reaction solvent from the obtained reaction solution is subjected to extraction treatment with water and a non-polar organic solvent, and the non-polar organic solvent phase containing the ruthenium complex is separated to obtain the non-polar organic solvent. A method for reusing a ruthenium complex, which comprises distilling a non-polar organic solvent from a solvent phase to obtain a residue, treating the residue with an acid if necessary, and then subjecting the residue to a hydrogenation reaction. 3. The method according to claim 1, wherein the organic compound is selected from an aliphatic dicarboxylic acid, an aliphatic dicarboxylic acid anhydride and an aliphatic dicarboxylic acid diester. 4. The method according to claim 3, wherein the organic compound is succinic anhydride. 5. The method according to claim 1, wherein the tertiary organic phosphorus compound is trialkylphosphine. 6. The method according to claim 5, wherein the tertiary organophosphorus compound is trioctylphosphine. 7. The non-polar organic solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, halogenated hydrocarbons and mixtures thereof, according to any one of claims 1 to 6. The method described in crab. 8. The method of claim 7, wherein the non-polar organic solvent is toluene. 9. The method according to claim 2, wherein the acid is an alkyl sulfonic acid or an aryl sulfonic acid. 10. The method of claim 9, wherein the acid is paratoluene sulfonic acid. 11. The method according to claim 1, wherein the reaction solvent is distilled off from the reaction solution at a temperature of 220 ° C. or lower. 12. The method according to claim 2, wherein the residue is dissolved in a reaction solvent and treated with an acid. 13. The method according to claim 2, wherein the amount of the acid used is equal to or more than the equivalent amount of the tertiary organic phosphine (as a free acid) contained in the residue. 14. A reaction product obtained by hydrogenating succinic anhydride in a triglyme solvent in the presence of a ruthenium complex having a trialkylphosphine as a ligand, removes γ-butyrolactone and water, and then triglyme is distilled in a distillation column. The catalyst liquid is obtained by distilling off while maintaining the column bottom temperature at 200 ° C. or below, and water and toluene are added to at least a part of the catalyst liquid for extraction treatment, and the formed ruthenium complex-rich toluene phase is extracted with water. The method according to claim 1, characterized in that it is separated from the oil phase and the oil phase. 15. Hydrogenation of succinic anhydride in a triglyme solvent in the presence of a ruthenium complex having a trialkylphosphine as a ligand to remove γ-butyrolactone and water from the reaction product, and then triglyme in a distillation column. Distilling off while maintaining the temperature below 200 ° C to obtain the catalyst liquid,
Water and toluene are added to at least a part of the catalyst solution for extraction treatment, the formed ruthenium complex-rich toluene phase is separated from the water phase and the oil phase, and toluene is distilled off from the separated toluene phase to obtain a residue. 3. The method according to claim 2, wherein triglyme is added to the obtained product, followed by treatment with paratoluenesulfonic acid and subjecting the treated catalyst liquid to a hydrogenation reaction.