JPS6281350A - Circulating use of catalyst - Google Patents

Abstract

PURPOSE:To recover a catalyst at a high ratio, by separating the catalyst from a reaction product solution obtained by reacting a styrene with CO, alcohol and O2 in the presence of the catalyst containing Pd (compound) and a Cu compound as a solid and oxidizing the resultant catalyst in the presence of inorganic anions. CONSTITUTION:A styrene is reacted with CO, an alcohol and O2 in the presence of a catalyst containing metallic Pd or a compound thereof and a Cu compound to give a cinnamic acid ester. In the process, the reaction product solution is, as necessary, concentrated and the catalyst component is separated as a solid, oxidized in the presence of inorganic anions, e.g. fed as an inorganic acid or halogen molecules, using an oxidizing agent and repeatedly used for the reaction. The above-mentioned inorganic anions are preferably the same kinds as the anionic parts of the catalyst used for the first time in producing the cinnamic acid ester. EFFECT:The catalyst can be collectively recovered at a high ratio and also regenerated by simple oxidation treatment.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is a method for recycling a catalyst used in producing a corresponding cinnamic acid ester by reacting styrenes, carbon monoxide, alcohol, and oxygen. Regarding.

Cinnamic acid esters are widely used as fragrances or raw materials for fragrances due to their aromatic properties, and are also important compounds as raw materials for agricultural chemicals and photosensitive resins.

(Prior Art) Cinnamic acid has conventionally been produced on a small scale by a reaction using benzaldehyde and acetic acid derivatives as main raw materials, but this method uses expensive raw materials and is therefore not an industrially preferred method. Therefore, as a method using cheaper raw materials, several methods have been proposed in which styrenes, carbon monoxide, alcohol, and oxygen are reacted in the presence of a catalyst to produce cinnamic acid esters (for example, Kaisho 56-1
5242, JP-A-56-22749. Japanese Unexamined Patent Publication No. 57-70
836, JP-A-60-92242. Japanese Patent Publication No. 1986-169
441 etc.).

Most of these proposals use at least palladium metal or its compounds and copper or iron salts as catalysts, and not only use palladium, an expensive metal, but also use extremely large amounts of catalyst. Furthermore, disposing of large amounts of heavy metals poses problems in terms of pollution, industrial waste, and material disposal. Therefore, it is absolutely necessary from economic and environmental standpoints to recover and recycle the catalyst components after the reaction. However, the method of recycling the catalyst, which is essential for industrializing this production method, has hardly been studied so far. Very recently, reactions with limited catalytic systems,
A method characterized by heat-treating the separated and recovered catalyst together with an organic acid has been disclosed (Japanese Patent Laid-Open No. 169441/1989).
).

However, this method has not yet provided a sufficient solution to the recovery rate of each component of the catalyst, the activity of the recovered catalyst, the possibility of repeated use of the recovered catalyst, etc., which have a large impact on economic efficiency.

(Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing cinnamic acid esters by reacting styrenes, carbon monoxide, alcohol, and oxygen in the presence of a catalyst. It is an object of the present invention to provide a method in which a catalyst can be recovered and used repeatedly in reactions as a regenerated catalyst having an activity comparable to that of a new catalyst.

(Means for Solving the Problems) The present inventors have continued intensive studies to achieve the above object, and found that the catalyst component was separated from the reaction solution containing the cinnamic acid esters and the catalyst component, and then separated. The inventors have discovered that when a catalyst component is oxidized in the presence of an inorganic anion, a catalyst whose activity has been recovered can be easily obtained at a high recovery rate and can be used again in the reaction, and the present invention has been achieved.

That is, the present invention provides a method for producing cinnamic acid esters by reacting styrenes, carbon monoxide, alcohol, and oxygen in the presence of a catalyst containing (1) palladium metal or its compound and (2) a copper compound. This is a catalyst recycling method characterized by separating the catalyst component as a solid from a reaction product liquid containing the component, oxidizing the recovered catalyst component in the presence of an inorganic anion, and then repeatedly using it in the reaction.

The present invention will be explained in detail below.

In the present invention, the reaction product liquid containing a catalyst component refers to a corresponding cinnamic acid ester obtained by reacting styrenes, carbon monoxide, alcohol, and oxygen in the presence of a catalyst containing palladium metal or its compound and a copper compound. This is a reaction product liquid containing the cinnamic acid esters and a catalyst component, and is obtained by the following reaction method.

Specifically, the styrenes used in this reaction include styrene, α-methylstyrene, β-methylstyrene, and α-methylstyrene.
-ethylstyrene, β-ethylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, m
- Alkyl derivatives of styrene such as ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, β-methyl-p-isopropylstyrene, or p-chlorostyrene, p-methoxystyrene, 3,4-dimethoxystyrene, etc. Examples include styrene derivatives having a substituent on the aromatic ring that does not inhibit the reaction.

Alcohols include methanol, ethanol, propatool, butanol, pentanol, octatool, cyclopentanol, cyclohexanol, phenol,
These are alcohols such as benzyl alcohol, ethylene glycol, polyethylene glycol, and propylene glycol, and they may have a substituent such as a halogen or an alkoxy group that does not inhibit the reaction.

Further, the gaseous raw materials used in the reaction are carbon monoxide and oxygen. Air may be used as the oxygen source. Carbon monoxide and oxygen can be diluted with an inert gas such as nitrogen or argon to avoid explosive range. Further, carbon dioxide may also be present. These carbon monoxide, oxygen, or other gases may be charged into the reactor in the required amount all at once, but the necessary gases may be added continuously or intermittently, or continuously or intermittently. It may be distributed to

In this reaction, the raw alcohol can essentially be used as a solvent. Further, other solvents can also be used as long as they do not inhibit the reaction. Examples of such solvents include ethers such as diethyl ether, dipropyl ether, methyl ethyl ether, phenylethyl ether, diphenyl ether, tetrahydrofuran, dioxane, ethylene glycol diethyl ether, and tetraethylene glycol dimethyl ether, and ketones such as acetone, methyl ethyl ketone, and acetophenone. methyl acetate,
Esters such as ethyl acetate and methyl propionate, aromatic hydrocarbons or substituted compounds thereof such as benzene, toluene, p-xylene, ethylbenzene, chlorobenzene, and dichlorobenzene, and aliphatic compounds such as n-hexane, n-pentane, and cyclohexane. Or alicyclic hydrocarbons, carbonates such as propylene carbonate and dimethyl carbonate, nitriles such as acetonitrile and benzyl-IJ, aromatic nitro compounds such as nitrobenzene, amide compounds such as dimethylformamide, sulfolane, etc. Examples include sulfone compounds.

In addition, if the produced water inhibits the reaction, a dehydrating agent such as molecara sieve, silica gel, methyl orthoformate, acetic anhydride, etc. can also be used.

Examples of the palladium metal or its compound which is the first component of the catalyst in this reaction include activated carbon, silica gel, alumina, silica alumina, diatomaceous earth, magnesia, and eaves stone.

Palladium metals such as palladium black, palladium dibenzylidene acetone complexes of palladium, zero-valent palladium complexes such as tetrakis(triphenylphosphine) palladium, palladium sulfate, palladium chloride, phosphorous Palladium acid, inorganic acid salts of palladium such as palladium nitrate, organic acid salts such as palladium acetate, palladium propionate or palladium benzoate, palladium bis(acetylacetonato), cyclooctadiene dichloropalladium, palladium chloride benzonitrile complex or Examples include divalent palladium compounds such as palladium complexes such as palladium chloride amine complexes, and it is also possible to use regenerated catalysts containing palladium compounds recovered and oxidized by the method of the present invention. can.

The palladium compound contained in the regenerated catalyst may be different from that used in the initial reaction.

Examples of the copper compound which is the second component of the catalyst include copper inorganic acid salts such as copper carbonate, copper chloride, copper bromide, copper nitrate, and copper phosphate, steel acetate, and copper propionate.

Examples include salts of aliphatic or aromatic carboxylic acids of copper such as copper stearate, copper cinnamate, and copper benzoate, salts of organic anions of copper such as copper acetylacetonate, and the like. These copper compounds may be used alone or in combination of two or more. Furthermore, a regenerated catalyst containing a copper compound recovered by the method of the present invention and obtained by oxidation treatment can be used. The copper compound contained in the regenerated catalyst may be different from that used in the initial reaction.

Further, in this reaction, a co-catalyst can also be used in order to improve the catalytic activity and reaction results.

Examples of these promoters include (1) compounds of alkali metals and alkaline earth metals, (2) organic acid salts of aluminum metal, (3) tertiary amines, (4) nitriles,
(5) rare earth compounds; (6) from Groups 4A, 5A, ZA, 8A iron, 1B, or 2B of the periodic table according to the International Union of Pure and Applied Chemistry (hereinafter simply referred to as the periodic table); Examples include compounds of selected metals, (7) compounds of halogens, and (8) cocatalysts having activity when included in the regenerated catalyst obtained by the method of the present invention. These may be used alone or in combination of two or more. Furthermore, a combination of compounds that can be produced within the reaction system may be used.

These co-catalysts are specifically (1) alkali metals,
As alkaline earth metal compounds, compounds such as sodium, potassium, rubidium, cerium, magnesium, calcium, strontium, and barium are used.
These inorganic acid salts such as hydroxides, carbonates, and hydrochlorides; aliphatic or aromatic monovalent or polyvalent carboxylates such as acetates, propionates, butyrates, caproates, and phthalates; , or acetylacetone, propionylacetone, imbutyrylacetone, caproylacetone, benzoylacetone, dibenzoylmethane, acetoacetic acid,
Examples include β-diketones, β-keto esters, and β-keto acid complexes with acetoacetic esters.

In addition, as the organic acid salt of aluminum metal (2),
Aluminum acetate, basic aluminum acetate.

Examples include aluminum propionate, aluminum stearate, and aluminum benzoate.

(3) Tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, tri-secondary propylamine, diethylmethylamine,
Examples include aliphatic tertiary amines having 3 to 20 carbon atoms, such as dimethylpropylamine, allyldiethylamine, dimethylbutylamine, diethylpropylamine, benzyldimethylamine, dicyclohexylethylamine, and dimethylcyclohexylamine.

Examples of the nitriles in (4) include fatty nitriles such as acetonitrile, propionitrile, succinonitrile, geltalonitrile, and adiponitrile, and aromatic nitriles such as benzonitrile, tolnitrile, and phthalonitrile. .

Examples of the rare earth compound (5) include compound oxides or salts of oxides of a total of 17 elements, scandium and yttrium of group 3A, and lanthanides from lanthanum to rutium. Specifically, the oxide is CeO2s
Examples include basic oxides such as pr6o, . Examples of salts include inorganic acid salts such as hydrochloride and nitrate, and organic acid salts such as acetate.

(6) Compounds of metals selected from group 4A, group 5A, group ZA, iron group 8A, group 1B or group 2B of the periodic table include titanium, zirconium, vanadium, niobium, manganese, rhenium, iron, cobalt, nickel, silver,
Oxides, hydroxides, halides, carbonates of metals such as gold, zinc, cadmium, mercury, etc., or 1 such as acetic acid, propionic acid, stearic acid, succinic acid, or phenylacetic acid.
Examples include complex compounds such as valent or polyvalent aliphatic carboxylates, acetylacetonate complexes, and cyclopentagenyl complexes.

Examples of the halogen compound in (7) include halogen molecules such as 1 chlorine, 1 bromine, or iodine, and solutions thereof, hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, and solutions thereof, and tert-butyl Organic halides that easily generate halogen ions, such as tertiary alkyl halides such as chloride and tert-butyl bromide, or acid halides such as acetyl chloride and benzoyl bromide; carbonic acid derivatives containing halogens such as phosgene and methyl chloroformate; Phosphorus halides such as phosphorus chloride, phosphorus pentachloride, phosphorus tribromide, and phosphorus pentabromide; phosphorus oxyhalides such as phosphoryl trichloride and phosphoryl tribromide; thionyl halides such as thionyl chloride and thionyl bromide; , tellurium halides such as tellurium tetrachloride and tellurium tetrabromide, group 4A such as titanium and zirconium, group 5A such as vanadium and tantalum, group 6A such as chromium and molybdenum, group 7A such as manganese, iron, cobalt and Halides or oxyhalogens according to the valence of metals in the 8A iron group such as nickel, the 1B group such as copper, the 2B group such as zinc and cadmium, or the 4B group such as germanium and tin, and the 5B group such as antimony and bismuth. Examples include phosphorus.

The active co-catalysts included in the regenerated catalyst obtained by the method of the present invention (8) are as follows. Originally, the purpose of the method of the present invention is to recover, regenerate, and reuse palladium metal or its compound and copper compound, which are the main components of the catalyst components.

Therefore, it is not necessarily necessary to recover and reuse the cocatalyst component. However, metal-containing co-catalysts and the like may be recovered together with the catalyst components and regenerated so as to exhibit a co-catalyst effect and included in the regenerated catalyst. Such a regenerated catalyst can be used in a reaction as a catalyst containing a co-catalyst. The promoter component contained in the regenerated catalyst may be different from the compound used in the initial reaction, but such a component may be used.

The reaction product liquid containing a catalyst component referred to in the present invention is a reaction liquid containing a cinnamic acid ester and a catalyst component obtained by the method described above. However, the reaction conditions are not limited to the raw materials, catalysts, and other substances described above, and the reaction conditions may be any conditions as long as they meet the purpose of the reaction, including reaction conditions described in known literature. I do not care.

In the method of the present invention, the catalyst component is separated as a solid from the reaction product liquid obtained as described above, and the recovered catalyst component is oxidized and regenerated in the presence of inorganic anions.

A conventional solid-liquid separation method can be used to separate the catalyst component from the reaction liquid. For example, in the reaction solution obtained as described above, the catalyst components are often precipitated as solids after the reaction, even if they are uniform at the time of preparation.In this case, these solid catalyst components are filtered. It can be easily separated by solid-liquid separation operations such as , centrifugation or decantation. If the amount of catalyst component precipitated is insufficient, add more reaction solution to precipitate more.

It can also be separated after concentration. The particles of the precipitated catalyst component are usually sufficiently large and can be easily separated by the separation procedure described above, but if the particles are too thin and difficult to manipulate, a filter aid such as activated carbon, zeolite, or diatomaceous earth may be used. You can also do it. The operating temperature during separation must be within a temperature range at which the precipitated catalyst component and the cinnamic acid ester or its solution can be separated as solid and liquid. Normal -10
-200°C, preferably 0-150°C.

The solid components obtained by the above separation operation include, in addition to the main catalyst component, co-catalyst components used and recovered as necessary, solid dehydrating agents, filter aids, etc. This mainly includes cinnamic acid esters, high boiling point liquid components, and low boiling point liquid components remaining depending on the degree of concentration.

Cinnamic acid esters are separated from this liquid by a commonly used method.
Can be purified.

The melting medium component recovered as a solid may undergo changes during the reaction and is not necessarily in the same form as it was charged before the initial reaction. The form of each component contained in the recovered catalyst component is not clear, but the components are at least palladium and copper metals, and anions or coordinated compounds bonded to these metals. Furthermore, there is a cocatalyst metal used in the reaction and recovered, and an anion or a coordinating compound bound to the metal.

If organic substances such as cinnamic acid esters or by-products are attached to the recovered catalyst component, in order to reduce the loss of the cinnamic acid esters and to avoid contaminating the regenerated catalyst finally obtained. As the solvent used for the solid, it is preferable to use an organic solvent that does not dissolve the catalyst component as much as possible and easily dissolves deposits such as cinnamic acid esters. Such solvents include, for example, benzene, toluene, p-xylene, 0-xylene, ethylbenzene, chlorobenzene,
Examples include aromatic hydrocarbons such as dichlorobenzene or substituted compounds thereof, aliphatic or alicyclic hydrocarbons such as n-hexane, n-pentane, and cyclohexane.

A major feature of the method of the present invention is that there is no need to separate and recover the catalyst palladium and copper metals using special methods, but they can be recovered all at once and subjected to subsequent processing as is. Not only is it extremely simple, but the recovery rate of catalyst components is also extremely high.

The catalyst components recovered as described above are directly subjected to the next oxidation treatment. The oxidation treatment is an operation in which the recovered catalyst component is oxidized in the presence of inorganic anions.

Examples of the inorganic anions used in the method of the present invention include halogen ions such as chloride ions, bromide ions, and iodide ions, nitrate ions, sulfate ions, and phosphate ions. These inorganic anions can be provided as inorganic acids or halogen molecules, for example gaseous hydrogen halides such as hydrogen chloride, hydrogen bromide or hydrogen iodide and their solutions in water or organic solvents, nitric acid, sulfuric acid, Inorganic acids such as phosphoric acid or halogen molecules such as chlorine, bromine, and iodine are used. These are usually used alone, but two or more types can also be used simultaneously.

It is generally preferred that these inorganic anions be of the same type as the anionic portion of the initial catalyst used to form the cinnamate ester. The amount of these inorganic anions used is usually 0.0 per gram atom of total metal in the recovered catalyst components.
It is 1 equivalent or more, preferably 0.01 to 500 equivalents.

An oxidizing agent is required to oxidize the recovered catalyst component in the presence of inorganic anions. Examples of oxidizing agents include oxygen,
Oxygen such as air and ozone, and their dilutions with inert gases such as nitrogen and argon, peracids such as performic acid, peracetic acid, perbenzoic acid, and perphthalic acid, hydrogen peroxide, and tertiary-butyl peroxide. , peroxides such as acetyl peroxide and benzoyl peroxide, nitric acid and nitrogen oxides such as nitric acid, dinitrogen pentoxide, dinitrogen trioxide, and dinitrogen oxide, and halogen molecules such as chlorine and bromine. These oxidizing agents can also be used as aqueous or suitable organic solutions. These can be used alone, or two or more kinds can be used simultaneously or sequentially. Furthermore, when a halogen or nitric acid is used as a source of inorganic anions, it can also serve as an oxidizing agent. Further, compounds of metals in a highly oxidized state such as ferric chloride, vanadium pentachloride, potassium permanganate, or potassium dichromate can also be used.

The amount of these oxidizing agents used varies depending on the amount of metal to be oxidized and the amount of change in its valence, but is usually 0.01 per gram atom of all metals in the recovered catalyst component. mol or more is used, preferably in the range of 0.01 to 1000 mol.

Which oxidizing agent and inorganic anion are used for oxidation treatment? Any method may be used as long as it can effectively bring the solid recovered catalyst component into contact with the inorganic anion and the oxidizing agent to carry out the desired oxidation treatment, although it may vary depending on the properties of the source.

The recovered catalyst component is subjected to the oxidation treatment reaction either as a solid or dissolved or suspended in a solvent.

When using a solvent, the solvent to be used is water, alcohols such as methanol, ethanol, propatool, butanol, pentanol, octatool, cyclohexanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene gelicol, diethyl, etc. ether, cyfropyl ether, methyl ethyl ether,
Ethers such as phenylethyl ether, diphenyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, acetophenone, esters such as methyl acetate, ethyl acetate, methyl propionate, benzene, toluene, xylene, ethylbenzene, Aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, styrene or substituted compounds thereof, n-hexane, n-pentane,
Examples include aliphatic or alicyclic hydrocarbons such as cyclohexane, and particularly preferred are water and alcohols such as methanol and ethanol.

If the sources of the oxidizing agent and inorganic anions are both gases, these gases may be supplied in the required amount all at once to the processing vessel containing the recovered catalyst components, but they may also be supplied continuously or intermittently. may be supplied to

Alternatively, the recovered catalyst components can be packed in a column and these gases can be passed through.

When one of the sources of the oxidizing agent and the inorganic anion is a gas and the other is a liquid, the gaseous component can be supplied to the place where the liquid component and the recovered catalyst component are mixed in the same manner as in the above method. can. If the oxidizing agent is a gas such as air,
The oxidation treatment can be sufficiently progressed by simply treating the recovered catalyst components and inorganic anions in that atmosphere.

If the sources of the oxidizing agent and the inorganic anion are both in liquid form, they may be added to the recovered catalyst component at once, or both or either of them may be added continuously or intermittently to the recovered catalyst component. It's okay.

These oxidation treatments will proceed more efficiently if performed under stirring. The oxidation treatment conditions vary depending on the type of treatment reaction, the type and properties of the oxidizing agent and inorganic anion source used, the presence or absence of a solvent, etc., but the temperature of the oxidation treatment is usually between 0 and 0.
The temperature is 200°C, preferably 20-150°C. The processing pressure may be reduced pressure, normal pressure, or increased pressure, but is preferably 0.1 to 200 atm (absolute pressure, the same applies hereinafter), and more preferably 1 to 50 atm. Processing time is 1
Within 0 hours, preferably between 1 minute and 5 hours.

The oxidation treatment solution obtained as described above can be reacted as it is (in some cases, it can be reused, but usually the excess oxidizing agent, inorganic anions, or The changed substances, as well as the solvent used, are distilled off, and the regenerated catalyst is separated as a solid.Also, it is separated as a solution or suspension, with a portion of the solvent remaining.

Furthermore, solids can also be separated from the concentrate.

The oxidized catalyst component can be further subjected to appropriate treatment to further enhance its activity as a catalyst.

The carrier of the palladium metal-supported catalyst or the solid dehydrating agent used in the first reaction may be sent as is to the next reaction together with the regenerated catalyst, but may be removed if necessary.

The regenerated catalyst does not need to be in exactly the same form as that used in the first reaction; it is important that it exhibits catalytic activity in the next reaction. The catalyst components regenerated by the method of the present invention are metal components of palladium and copper, and the anions bonded to these metals are the same as those contained in the original catalyst.
It may be donated from the inorganic anion used in the oxidation treatment, or it may be a mixture of both. Co-catalysts may also be recovered if used.

By the method of the present invention, the main catalyst components are recovered at a high rate,
The recovered and regenerated catalyst can be used repeatedly for the next reaction. When reusing, the recovered regenerated catalyst can be used alone or in combination with a new catalyst and/or a separately obtained regenerated catalyst.

As described above, by repeatedly using the catalyst used in the reaction, recovered, and regenerated in the next reaction, it is possible to recycle the catalyst.

(Operation and Effects of the Invention) According to the method of the present invention, in the method for producing cinnamic acid esters from styrenes, carbon monoxide, alcohol, and oxygen, the catalyst used is recovered from the reaction liquid at a high rate. In addition, it can be regenerated by oxidation treatment using a simple method and used for repeated reactions. In other words, an extremely industrially advantageous method for producing cinnamic acid esters is provided.

(Example) Next, the method of the present invention will be explained in more detail with reference to Examples and Reference Examples.

Example 1 Styrene 10.4. ! i' (100 mmol), palladium chloride 3.6 mg (o, 020 mmol), and cupric chloride 672 (5,00 mm IJ mol) were added, and methanol was further added to bring the total volume to 50 ml. In this autoclave, the mixing ratio of carbon monoxide, oxygen and nitrogen is 10.5.
: 5.2 : 84.3 volume of mixed gas is maintained at a total pressure of 50 atm (absolute pressure, the same shall apply hereinafter) and transported for 400 m at the outlet.
Constantly circulated for 17 minutes (standard condition) and heated to 100°C.
The mixture was allowed to react for 6 hours. The outlet gas was discharged through a reflux condenser. After the reaction is completed, the autoclave is cooled down, and after the pressure is released,
When the reaction solution was taken out and analyzed by high performance liquid chromatography, the yield of methyl cinnamate was 199I (12.3 mmol), and the amount of the reaction solution obtained was 52.41
It was 9. At this time, the reaction solution was blue-green, but a blue-white precipitate had formed at the bottom.

This reaction solution was transferred to a glass 200++tA' eggplant flask and concentrated using an evaporator to reduce the liquid volume to 9,6
．． It was set as 9. At this time, a large amount of catalyst components precipitated and the liquid state became a slurry.

This liquid was filtered while hot through a glass filter while keeping it at 50°C to separate the catalyst component, and the toluene was 101n7! Washed three times using

After drying the obtained catalyst component under reduced pressure at 50°C for 5 hours,
The mixture was transferred to a 00ml eggplant flask, 20rnl of a 30% by weight aqueous hydrochloric acid solution was added thereto, and the mixture was stirred at 60°C for 10 minutes while blowing oxygen into the liquid for oxidation treatment, and the liquid became a blue-green homogeneous solution.

This liquid was heated again at 80°C for 15 m using an evaporator.
The mixture was sufficiently concentrated to dryness at mHg to obtain a regenerated catalyst of 0.65.9. When the amount of palladium and copper was analyzed by atomic absorption spectrometry, and the amount of chlorine was analyzed by ion chromatography, the results were 1.68 for palladium and 292.2 for copper.
, chlorine was 348.7 cm, and the recovery rates were 78 cm, 92 cm, and 98 cm, respectively, based on the charges.

This regenerated catalyst was used again in the reaction as it was.

That is, in place of the palladium chloride and steel chloride used in the first reaction, this regenerated catalyst 0.58.9 was used, 10.4 f9 of styrene was added, and methanol was further added to bring the total volume to 50 ml. When the other conditions were the same as the first reaction, the yield of methyl cinnamate was 1.77.9 (10,9
mmol).

Examples 2-4 The reaction was carried out in the same manner as in Example 1 except that the first preparation in Example 1 was further added with the type and amount of co-catalyst shown in Table 1, followed by one recovery and oxidation treatment. I did it. All of the regenerated catalysts were used in the second reaction, except for a very small amount used for analysis. In Examples 2 and 3, the regenerated catalyst was used as it was, and in Example 4, new triethylamine 7, O
A second reaction was carried out in the same manner as in Example 1 by adding mol of IJ.

The results are shown in Table 1 together with those of Example 1.

Example 5 Styrene 10.4 was added to the autoclave in Example 1.
11 (100 mmol), palladium chloride 3.6 mg (
0,020 mmol), cupric chloride 672,111 g (
5,00 mmol), manganese chloride 944■ (7,
5 mm IJ mol) and further methanol to bring the total volume to 5
It was set to 0+nl. The reaction was carried out under the same conditions as the first reaction in Example 1, and the yield of methyl cinnamate was 3.
．． The amount was 99 g (24.6 mmol). The obtained reaction solution was concentrated, and the slurry solution was filtered while hot through a glass filter while being maintained at 50° C. to separate the catalyst component into solid and liquid.

The catalyst component thus recovered was transferred as it was to a 100 ml eggplant-shaped flask, 20 ml of a 30% aqueous hydrochloric acid solution was added, and the mixture was stirred at 50° C. for 1 hour while blowing air into the liquid for oxidation treatment.

This liquid was heated again using an evaporator at 80°C for 15 tn.
The mixture was sufficiently concentrated to dryness at mHg to obtain a regenerated catalyst. Weight 1.79
．． 9, and the recovery and regeneration rates of palladium, copper, and manganese were 80%, 96%, and 99%, respectively.

A reaction was carried out in the same manner as the first reaction using 1.68 g of this regenerated catalyst and 10.4 # of styrene. The yield of methyl cinnamate was 4.08.9 (25.11 J mol).

Example 6 After reacting in the same manner as in Example 5, it was concentrated and solid-liquid separated in the same manner. 100mA from the recovered catalyst components! Transfer to an eggplant-shaped flask, add 20 ml of 30% aqueous hydrochloric acid solution, add 1 ml of 40% by weight hydrogen peroxide solution, and heat at 50°C.
The mixture was stirred for 5 minutes to carry out oxidation treatment. After this, Example 5
The regenerated catalyst was separated and used in the reaction in the same manner.

The results are shown in Table 2 along with other results.

Example 7 The reaction, recovery, oxidation treatment, and reuse were carried out in the same manner as in Example 5 except that oxygen was used instead of air in Example 5. The results are shown in Table 2.

Comparative example 1 A reaction was carried out in the same manner as in Example 5 to obtain a recovered catalyst.

Transfer this to an ioomg eggplant flask in a nitrogen stream, add 20 ml of a 30% aqueous hydrochloric acid solution that has been sufficiently replaced with nitrogen, and heat the mixture at 50°C.
The mixture was stirred for 50 minutes. This liquid was sufficiently concentrated to dryness at 80° C. and 15 mmHg using an evaporator in a nitrogen stream to obtain a solid component.

This was used in the second reaction in the same manner as in Example 5.

The reaction did not proceed sufficiently and the yield of cinnamic acid ester was extremely low.

The recovery rate of the catalyst component and the yield of cinnamic acid ester in the second reaction are shown in Table 2 together with other results.

Example 8 A reaction was carried out in the same manner as in Example 5 to obtain a recovered catalyst. This is 10
0m/ after transferring to an eggplant flask and adding 20m/ of water, 7
Oxidation treatment was carried out by blowing chlorine gas as a source of inorganic anions and an oxidizing agent for 30 minutes while stirring at 0°C.

This liquid was sufficiently concentrated to dryness at 80° C. and 15 mmHg to obtain a regenerated catalyst. This was used in the second reaction in the same manner as in Example 5. The results are shown in Table 2.

Example 9 In the same manner as in Example 2, after the first reaction, the catalyst components were recovered and oxidized to obtain a regenerated catalyst.

The yield of methyl cinnamate and the recoveries of palladium, copper, zinc and chlorine are shown in Table 3. In order to match the insufficient amounts of palladium, copper, and zinc to the amounts charged in the first reaction, palladium chloride, cupric chloride, and zinc chloride were added to the regenerated catalyst in the amounts shown in Table 3, and the reaction was repeated in the same manner as in Example 2. The second reaction was performed.

After the second reaction, the catalyst components were recovered and oxidized again, the amount of catalyst was adjusted in the same way, and the reaction was performed again, a total of 4 operations.
Repeatedly. The results are shown in Table 3.

No matter how many times the recovery and regeneration operation is performed, the yield of methyl cinnamate remains almost constant, and no decrease in catalytic activity is observed.

Example 10 In a glass cylindrical container, 8.0% palladium chloride was added as a catalyst.
87 mg (0.05 mmol), cupric chloride 0.40 g
(s, o mmol), cupric acetate monohydrate 1.68.9
(12.5 mmol) was weighed out, a small amount of methanol was added thereto, styrene 26.04F (250.0 mmol) was added, and methanol was further added to bring the total amount to 12.0 mmol.
5mA! And so. This glass container was placed in a 500 ml autoclave. In this autoclave, the partial pressure ratio of carbon monoxide:oxygen:nitrogen was 9.8:5 at a total pressure of 50 atm.
．． 2: Continue stirring while passing the mixed gas of 85.0 to 1.2 liters/min (standard condition) at the outlet 1
The reaction was carried out at 00°C for 3 hours. The outlet gas was discharged through a reflux condenser. After the reaction was completed, the reaction solution was cooled, depressurized, and taken out and analyzed. The yield of methyl cinnamate was 19.4 M (1
20.0 mmol), and the amount of reaction liquid was 113.82 g.

The reaction solution was transferred to a glass H5DO ml eggplant flask and concentrated under reduced pressure with stirring. 70℃ at the end, 15m
It was carried out for 30 minutes at mHg. The liquid volume after concentration was 26.21. At this time, a large amount of catalyst components precipitated, and the liquid became a slurry. This liquid was separated into solid and liquid in the same manner as in Example 1,
After washing with hexane soml, it was dried under reduced pressure to obtain a recovered catalyst component.

This was transferred to a 200 ml eggplant-shaped flask, 50 liters of 5% aqueous hydrochloric acid solution was added, and the mixture was stirred in air at 70° C. for 10 minutes to carry out oxidation treatment. This solution was heated to 70°C and 15 mm thick.
The mixture was concentrated to dryness with Hg to obtain a green regenerated catalyst 2.21'.

The recoveries of palladium and copper relative to the charge were 7 each.
7% and 92%.

This regenerated catalyst was used as a catalyst at 0.5.9. The reaction was carried out in the same manner as the first reaction except that 8.87 mmol of fresh palladium chloride (O, OS mmol) and 1.68.9 mmol of cupric acetate monohydrate (12.5 mmol!Jmol) were used. The second reaction was carried out using
125.2 mmol).

Example 11 A reaction was carried out in the same manner as in Example 10 to obtain a solid recovered catalyst component. Transfer this to a 200ml eggplant-shaped flask, add 50ml of 60% nitric acid aqueous solution, and heat at 80°C while blowing oxygen.
Oxidation treatment was carried out by stirring for hours.

This liquid was concentrated to dryness at 70° C. and 15 mmHg to obtain a solid. Add iog acetate to this, stir at 80°C for 30 minutes, and then concentrate to dryness. The procedure was repeated 5 times. 2.39
,! A regenerated i+ catalyst was obtained. The recoveries of palladium and copper based on the charges were 78 and 93 inches, respectively.

Catalyst 2.14.9 thus regenerated was used as a catalyst, and the reaction was otherwise carried out in the same manner as in the first reaction. The yield of methyl cinnamate was 167 g (1030 mmol).

Claims (1)

[Claims] 1) [1] Palladium metal or its compound and [2
] In the presence of a catalyst containing a copper compound, styrenes,
When producing cinnamic acid esters by reacting carbon monoxide, alcohol, and oxygen, the catalyst component is separated as a solid from the reaction product liquid containing the catalyst component, and the recovered catalyst component is oxidized in the presence of inorganic anions. A method for recycling a catalyst, which is characterized in that the catalyst is then used repeatedly in a reaction.