JPH09227129A - Recovery method of ruthenium complex - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a method for recovering a ruthenium complex. A catalyst solution obtained by removing a target product and a reaction solvent from a reaction solution obtained by hydrogenating an organic carbonyl compound in the presence of a ruthenium complex having a tertiary organic phosphorus compound as a ligand is provided. , Extraction with water and a non-polar organic solvent at a temperature of 40 ° C. or higher, followed by phase separation into an organic solvent phase, an aqueous phase and an oil phase, followed by a non-polar organic solvent phase containing a ruthenium complex. The non-polar organic solvent is distilled off to separate and collect the ruthenium complex,
On the other hand, the oil phase is heat-treated to thermally decompose a part of the high-boiling substance to recover the active ingredient.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for recovering a ruthenium complex. Specifically, the present invention is a catalyst solution obtained from a hydrogenation reaction product liquid of an organic carbonyl compound using a ruthenium complex catalyst is subjected to extraction treatment under specific conditions to separate and recover the ruthenium complex, while The present invention relates to a method of heat-treating the obtained oil phase to recover an active ingredient.
The recovered ruthenium complex can be reused in the 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 withdraw a part of it from the reaction system continuously or intermittently.

As a matter of course, since the extracted liquid contains ruthenium, its treatment is necessary for discarding it. 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. Further, if the industrial waste treatment company is requested to perform the treatment, it will be economically disadvantageous if the treatment amount is large, because the cost is required for the mass of the treatment liquid.
Therefore, if the ruthenium in the treated extraction liquid 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 on the waste liquid treatment can be significantly reduced and the catalyst cost can be significantly reduced economically. Moreover, the absolute amount of ruthenium discharged is reduced, which is preferable from the viewpoint of preventing environmental pollution, and 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 VIII metal such as rhodium, for example, an extraction method using a strong acid (Japanese Patent Publication No.
6-43219) or a decomposition method using peroxide (US Pat. No. 3,547,964, JP-A-51).
-63388 gazette) etc. are proposed.

[0005]

However, each of the above methods has the problem of corrosion of the material of the equipment because it uses acid, and also has the problem of separating and recovering the catalyst in its active form. It was As a method for solving these problems, the present applicant has previously proposed in Japanese Patent Laid-Open No. 7-275716. In this method, a catalyst solution obtained by removing a reaction product and a reaction solvent from a reaction solution obtained by hydrogenating an organic compound using a ruthenium complex catalyst having a tertiary organic phosphorus compound as a ligand is used. It is a method of recovering a ruthenium complex by subjecting it to an extraction treatment with water and a non-polar organic solvent to phase-separate an organic solvent phase containing a ruthenium complex, an aqueous phase and an oil phase consisting of a high boiling point by-product. In this method, when phase-separating the organic solvent phase containing the ruthenium complex,
It is desirable to recover the active ingredient by treating the resulting oil phase consisting of high-boiling products by some method. An object of the present invention is to 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 carbonyl compound, and further recover the recovered ruthenium complex. The present invention is to provide a method for treating high-boiling substances in recycling a ruthenium complex while reusing hydrogen in a hydrogenation reaction.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above problems, and as a result, have found that a catalyst solution obtained by removing a desired product and a reaction solvent from a hydrogenation reaction product solution is obtained. By subjecting the ruthenium complex to a nonpolar organic solvent phase by extraction treatment with water and a nonpolar organic solvent at a specific temperature or higher,
A water-soluble organic compound is extracted and separated into an aqueous phase and an oil phase consisting of a high boiling point by-product, and the ruthenium complex is separated and recovered by distillation and the aqueous phase is circulated for extraction treatment, while the oil phase is heat treated. As a result, they have found that the high boiling point by-product can be decomposed and recovered as an active ingredient, and have completed the present invention. That is, the present invention is a catalyst obtained by removing a target product and a reaction solvent from a reaction solution obtained by hydrogenating an organic carbonyl compound in the presence of a ruthenium complex having a tertiary organic phosphorus compound as a ligand. The liquid is subjected to extraction treatment with water and a non-polar organic solvent at a temperature of 40 ° C. or higher, then phase-separated into three phases of an organic solvent phase, an aqueous phase and an oil phase, and subsequently a non-polar organic solvent containing a ruthenium complex. The ruthenium is characterized in that the non-polar organic solvent is distilled off from the phase to separate and recover the ruthenium complex, while the oil phase is heat-treated to thermally decompose a part of the high boiling point substance to recover the active ingredient. It is in the method of recovering the complex. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

1. Hydrogenation reaction The present invention concentrates and separates a ruthenium complex from a hydrogenation reaction product liquid of an organic carbonyl compound containing a ruthenium complex having at least one kind of a tertiary organic phosphorus compound as a ligand, and if necessary, The separated and recovered ruthenium complex is reused in the hydrogenation reaction. As the hydrogenation reaction, hydrogenation of a carbonyl compound, for example, aliphatic dicarboxylic acid, aliphatic dicarboxylic acid anhydride, aliphatic dicarboxylic acid diester, etc. The hydrogenation reaction of 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 the 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.

(Ruthenium Complex Catalyst) A ruthenium complex catalyst used in a hydrogenation reaction, particularly a catalyst for hydrogenating succinic anhydride to produce γ-butyrolactone is usually (i) ruthenium, (b) tertiary organic phosphine and ( C) pka
A ruthenium complex containing a conjugate base of an acid having a value of less than 2, and optionally a neutral ligand, and specific examples of each component used for its preparation are as follows.

(A) Ruthenium As ruthenium, both metal ruthenium and ruthenium compounds can be used. As the ruthenium compound, an oxide, a halide, a hydroxide, an inorganic acid salt, an organic acid salt or a complex compound of ruthenium is used, and specifically, for example, ruthenium dioxide, ruthenium tetroxide,
Ruthenium dihydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris (acetylacetone) ruthenium, sodium hexachlororuthenate, dipotassium tetracarbonyl ruthenate, pentacarbonyl ruthenium, cyclopentadienyl dicarbonyl ruthenium , Dibromotricarbonylruthenium, chlorotris (triphenylphosphine) hydridoruthenium, bis (tri-n-butylphosphine) tricarbonylruthenium, dodecacarbonyltriruthenium, tetrahydridodecacarbonyltetraruthenium, octadecacarbonylhexaruthenate dicesium, undeca Carbonyl hydridotriruthenate tetraphenylphosphonium and the like can be mentioned. The amount of these metal ruthenium and the ruthenium compound used is 0.0001 to 100 mmol, preferably 0.00, ruthenium in 1 liter of the hydrogenation reaction solution.
It is from 01 to 10 mmol.

(B) Tertiary organic phosphine It is considered that the organic phosphine contributes to controlling the electronic state of the 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. Such as triarylphosphines, alkylarylphosphines such as dimethylphenylphosphine, and polyfunctional phosphines such as 1,2-bis (diphenylphosphine) ethane. The amount of organic phosphine used is usually ruthenium 1
About 3 to 1000 moles, preferably 5 to moles
It is 100 mol. That is, it is considered that the organic phosphine is usually coordinated with 3 moles relative to 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 existing in the system. 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 The conjugate base of acid having pka value less than 2 acts as an additional promoter of the ruthenium catalyst, and the pka value may be increased during catalyst preparation or in the reaction system. As long as it produces a conjugate base of an acid having a value of less than 2, the supply form thereof is pk
Bronsted acids having a value 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 thereof used is 0.01 to 1000 with respect to 1 mol of ruthenium.
The range is 0.1 to 100 mol, 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.

(Reaction Solvent) In the hydrogenation reaction using a ruthenium complex catalyst, the reaction can be carried out using the raw material itself as a solvent, but other than the raw material in consideration of the reactivity of the raw material and the treatment operation of the reaction system. It is advantageous to use the reaction solvent of As such a reaction solvent, for example,
Diethyl ether, anisole, tetrahydrofuran,
Ethers such as ethylene glycol diethyl ether, triethylene glycol dimethyl ether and dioxane; ketones such as acetone, methyl ethyl ketone and acetophenone; alcohols such as methanol, ethanol, n-butanol, benzyl alcohol, ethylene glycol and diethylene glycol; phenols; formic acid , Carboxylic acids such as acetic acid, propionic acid and toluic acid; esters such as methyl acetate, n-butyl acetate and benzyl benzoate; benzene, toluene, ethylbenzene,
Aromatic hydrocarbons such as tetralin; Aliphatic hydrocarbons such as n-hexane, n-octane and cyclohexane; Halogenated hydrocarbons such as dichloromethane, trichloroethane and chlorobenzene; Nitrated hydrocarbons such as nitromethane and nitrobenzene; N, N- Dimethylformamide, N, N
-Carboxylic acid amides such as dimethylacetamide and N-methylpyrrolidone; hexamethylphosphoric triamide, N,
Other amides such as N, N ', N'-tetraethylsulfamide; N, N'-dimethylimidazolidone, N,
Urea such as N, N, N-tetramethylurea; sulfones such as dimethyl sulfone and tetramethylene sulfone; sulfoxides such as dimethyl sulfoxide and diphenyl sulfoxide; lactones such as γ-butyrolactone and ε-caprolactone; Examples thereof include polyethers such as ethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), and 18-crown-6; nitriles such as acetonitrile and benzonitrile; and carbonic acid esters such as dimethyl carbonate and ethylene carbonate.

(Hydrogenation Reaction Method) 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 a reaction vessel,
Further hydrogen is passed. Hydrogen may be diluted with a reaction-inert gas such as nitrogen or carbon dioxide.
The reaction temperature is usually 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 in industrial practice.
/ Cm ² , 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. If necessary, the residue after separation is constantly tested for the concentration of the catalyst composition contained therein, so that the concentration of the organic phosphine in the liquid is always maintained at the above-mentioned predetermined concentration, so that the concentration of the organic phosphine is appropriately adjusted in the circulation process. And circulate 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. The residual reaction solvent is concentrated to 5% by weight or less. In the hydrogenation reaction of succinic anhydride, the reaction solvent is distilled off after separating it from the reaction solution of water formed together with the target product, γ-butyrolactone. When the solvent is distilled off from the reaction solution, the liquid separation property into the three phases in the subsequent extraction treatment often becomes good. Distillation of the reaction solvent from the reaction solution can be performed by ordinary distillation, and vacuum distillation may be adopted 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.

2. Extraction treatment Next, 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 the oil phase composed of the by-produced high-boiling substance is separated.

(Non-polar organic solvent) As the organic solvent used together with water, a relatively low-polarity, that is, non-polar solvent which separates from water is used. As a non-polar organic solvent, 20 ℃
Having a dielectric constant (ε) of 6 or less, preferably 4 or less and a boiling point of 50 to 200 ° C., preferably 50 to 150 ° C., specifically, hexane, heptane, octane and decane. Such as aliphatic hydrocarbons, benzene, toluene, xylene, diethylbenzene, isopropylbenzene (cumene) and other aromatic hydrocarbons, diethyl ether, propyl ether, butyl ether, ethyl phenyl ether, methyl phenyl ether (anisole) and other ethers, 1,4-dioxane, 1,3
Examples include oxane such as 5-trioxane, alicyclic hydrocarbon such as cyclohexane and methylcyclohexane, halogenated hydrocarbon such as dichloromethane, trichloroethane and chlorobenzene.

(Extraction method) There is no particular restriction on the order of treatment when the concentrated solution is extracted with water and a non-polar organic solvent, 1) the concentrated solution is first extracted with water, and then the aqueous phase is extracted. Is separated and the oil phase (residue) is subjected to extraction treatment with a non-polar organic solvent, 2) water and a non-polar organic solvent are simultaneously added to the concentrated liquid, and the extraction treatment is carried out. Will be implemented. The above extraction treatment is carried out in combination with the following separation treatment by a method used in a usual liquid-liquid extraction treatment, for example, a batch or continuous method, a cocurrent or countercurrent contact, and a combination of any one-step or multi-step method. To be done.

The temperature for the extraction treatment of the concentrated liquid with water and the non-polar organic solvent is 40 to 120 ° C., preferably 50 to 120 ° C.
The temperature is in the range of 100 ° C, and the extraction time is 10 minutes to
It is in the range of 5 hours, preferably 30 minutes to 3 hours. If the extraction treatment temperature is lower than 40 ° C., the extraction efficiency is poor and the extraction time becomes significantly long, which is not industrial. In the above extraction treatment, stirring may be performed in order to increase the contact efficiency of the concentrated liquid with water and the nonpolar organic solvent. The amount of water and the nonpolar organic solvent used in the above extraction treatment is usually 1: 0.2 to 1 in terms of the weight ratio of the concentrated liquid / water / nonpolar organic solvent.
It is used within the range of 0: 0.2-10.

When the extraction treatment is carried out simultaneously with the concentrated liquid and water and the organic solvent, after stirring, the content liquid in an emulsion state is separated into an organic solvent phase, an aqueous phase and an oil phase insoluble therein. It Among these, the ruthenium complex is distributed to the non-polar organic solvent phase, the water-soluble organic compound is distributed to the water phase, and the by-product high-boiling product is distributed to the oil phase. The ruthenium complex in the concentrated liquid is mainly distributed to the nonpolar organic solvent phase by the extraction treatment, and the ruthenium complex distributed to 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. In the aqueous phase, among 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 of these substances are contained. To be extracted. The separation treatment of the extract after the above-mentioned extraction treatment is carried out by a usual oil-water separation treatment, for example, a method such as static separation or centrifugation. The non-polar organic solvent phase obtained by the oil-water separation then separates the organic solvent and the ruthenium complex by distillation or the like, for example, the organic solvent is distilled off, and the ruthenium complex is concentrated to an oily state. A residue is obtained.

(Acid treatment) Since this residue contains a ruthenium complex in a high concentration, it is industrially very useful if this ruthenium complex can be reused in the hydrogenation reaction. By the way, the ruthenium complex thus obtained, which is concentrated to a high concentration, contains a substance that liberates an organic phosphine when placed under a high-temperature hydrogenation reaction condition. 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, both 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 the preparation of the above-mentioned catalyst can be used, but 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 varies depending 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.
In treating the residue with an acid, it is effective to dissolve the residue in the reaction solvent used for the hydrogenation reaction and then 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 acid is usually 20 to 300 ° C., preferably 10
It is preferably carried out in the range of 0 to 250 ° C., and the treatment is preferably carried out in 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 reaction system substrate and The concentration of the organic phosphine becomes low, and the reaction inhibition as in the batch reaction does not occur.

(Recirculation of Water Phase) On the other hand, the water phase obtained by the oil-water separation after the above extraction treatment is recycled and reused in the above extraction treatment step. The above water-soluble organic compounds (carboxylic acids, water-soluble esters and water-soluble polyesters of their polymers, etc.) that accumulate in the water phase by recycling the water phase, unreacted raw materials (eg succinic anhydride) It is desirable to separate and collect active ingredients such as or reaction products (for example, γ-butyrolactone) by a separation means such as distillation separation.

(Heat Treatment of Oil Phase) In addition, the oil phase obtained by the oil-water separation is heat treated, for example, 20
Heat-treating at a temperature of 0 ° C or higher, preferably 250 to 300 ° C for at least 30 minutes or longer, preferably 1 to 10 hours to thermally decompose a part of the high boiling point by-product into a component having a lower boiling point,
The thermal decomposition product is subjected to a distillation treatment to separate and recover active ingredients (for example, a raw material (succinic anhydride etc.) and a product (γ-butyrolactone etc.) from the high boiling substance. It is mounted in a heat treatment tank provided, and a thermal decomposition accelerator such as an alkali or an acid may be added to the heat treatment.

[0026]

EXAMPLES The present invention will be described in more detail below with reference to examples and reference examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Reference Example 1 A hydrogenation reaction of succinic anhydride using a ruthenium-trioctylphosphine-paratoluenesulfonic acid type 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. 0.
056% by weight tris (acetylacetone) ruthenium, 0.51% by weight trioctylphosphine, 0.2
Dissolve 2% by weight of paratoluenesulfonic acid in triglyme (triethylene glycol dimethyl ether),
Heat treatment was performed at 200 ° C. for 2 hours in a nitrogen atmosphere, and the mixture was placed in a new catalyst container 5 to obtain a new feed catalyst liquid. 100 parts of this catalyst solution
It is supplied to an autoclave (reactor) 8 having an internal volume of 2 liters at a flow rate of 0 ml / hour, and after gas-liquid separation by the gas-liquid separator 1,
It was recovered as a bottom product of the distillation column 2 and was recycled. on the other hand,
0.6 Nm ³ / hr of hydrogen gas was sent from the hydrogen compressor 6 to the autoclave and adjusted to 20 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 continuously supplied at a flow rate of 125 g / hour. After cooling the reaction solution to 140 ° C,
After gas-liquid separation at atmospheric pressure, the product water and γ-butyrolactone are separated from the catalyst liquid in the distillation column, and the catalyst liquid is returned to the catalyst container, but as a part of the flow from 7 days after the start of the reaction. The catalyst solution was withdrawn at a flow rate of 8.67 g / hour, and the withdrawn catalyst container 4 was stored. The composition of the extracted catalyst liquid was as follows. Succinic anhydride + succinic acid 7% by weight γ-butyrolactone 1% by weight Triglyme 33% by weight High boiling point substance 60% by weight Ru concentration 160 ppm

Reference Example 2 The extracted catalyst liquid obtained in Reference Example 1 above was concentrated as follows. 665.6 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 was adjusted within the range of 20 to 40 mmHg so that the liquid temperature was maintained at 190 ° C or lower. After the solvent was distilled off, the concentrated catalyst solution was added to 486.2.
g was obtained. The mass concentration rate was 71.25%.

Example 1 477.2 g of the catalyst concentrate obtained in Reference Example 2 and water 13
72.3 g and heptane 547.1 g were put into an extraction tank equipped with a stirrer, and shaken at an internal temperature of 70 ° C. for 1 hour. When left to stand, in about 90 minutes, the solution was separated into three phases, a heptane phase, an aqueous phase, and an oil phase insoluble in any of heptane and water. The three phases were separated from each other, and their mass and Ru content were quantified by ICP analysis, and the following results were obtained. Mass Ru concentration Heptane phase 526.22 g 174 ppm Aqueous phase 1633.74 g 0 ppm Oil phase 204.22 g 72 ppm At this time, the distribution ratio of ruthenium to heptane phase / water phase / oil phase was 86/0/14. The heptane in the heptane phase was distilled off by evaporation to obtain 10.83 g of a residue. This means that the catalyst solution was concentrated to 2.3% based on the charged catalyst solution. 200 g of the oil phase obtained above
Was heat-treated at 260 ° C. for 3 hours, and then simple distilled under reduced pressure of 20 mmHg to obtain 40 g of distillate. The distillate contained active ingredients such as succinic anhydride and γ-butyrolactone, and 20% of the oil phase could be recovered as the active ingredient.

Comparative 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 at room temperature.
Shake at 5 ° C for 5 minutes. 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.

[0031]

According to the method of the present invention, a ruthenium complex having a tertiary organic phosphorus compound as a ligand is economically and efficiently recovered from a hydrogenation reaction product solution, and the recovered ruthenium complex is hydrogenated. The active ingredient can be recovered by reusing it in the reaction and heat-treating the oil phase consisting of the high boiling point by-product obtained during the recovery of the complex.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing an embodiment of the present invention.

[Explanation of symbols] 1 gas-liquid separator 2 distillation column 3 catalyst container 4 extraction catalyst container 5 new catalyst container 6 hydrogen compressor 7 raw material container 8 reactor

Claims (3)

[Claims] 1. A catalyst liquid obtained by removing a target product and a reaction solvent from a reaction liquid obtained by hydrogenating an organic carbonyl compound in the presence of a ruthenium complex having a tertiary organic phosphorus compound as a ligand. Is subjected to extraction treatment with water and a non-polar organic solvent at a temperature of 40 ° C. or higher, then phase-separated into three phases of an organic solvent phase, an aqueous phase and an oil phase, and subsequently a non-polar organic solvent phase containing a ruthenium complex. From the non-polar organic solvent by distillation to separate and collect the ruthenium complex,
On the other hand, a method for recovering a ruthenium complex, characterized in that an oil phase is heat-treated to thermally decompose a part of a high-boiling substance to recover an active ingredient. 2. The method for recovering a ruthenium complex according to claim 1, wherein the oil phase is heat-treated at a temperature of 200 ° C. or higher for at least 30 minutes or longer. 3. The method for recovering a ruthenium complex according to claim 1, wherein the aqueous phase is recycled to the extraction treatment step and reused.