CN1426384A - Process for producing ketals and/or acetals - Google Patents

Abstract

The object of the present invention is the production of ketals and/or acetals starting from olefins with high conversion and high selectivity. The present invention provides a process for producing ketals and/or acetals by reacting an olefin having at least one olefinic double bond with oxygen and a polyol in the presence of a catalyst, the process comprising (a) palladium, (b) The reaction is carried out in the presence of at least one non-palladium metal of Group 8, 9, 10 and 14 of the Periodic Table of Elements and (c) halogen as a catalyst, and the present invention also relates to the ketal and/or ketal prepared by the above method Process for the hydrolysis of aldehydes in the presence of acid catalysts to produce ketones and/or aldehydes.

Description

Process for producing ketals and/or acetals

technical field

The present invention relates to a process for the production of ketals and/or acetals by oxidizing alkenes with molecular oxygen.

Background technique

The corresponding aldehydes or ketones produced by the oxidation of alkenes with oxygen molecules are industrially useful compounds, and they have been synthesized by various catalytic reactions for a long time. Particularly useful among methods is the reaction commonly known as the Wacker reaction. That is, a method has been used in industry to produce acetaldehyde from ethylene and acetone from propylene by oxidation of oxygen molecules using an aqueous solution containing _PdCl2 and _CuCl2 as a catalyst. However, in this traditional Volcker reaction, the aqueous solution is under strong acid conditions and highly corrosive hydrochloric acid exists, so considering that the reactor and peripheral devices require advanced materials and the reactants are limited to lower hydrocarbons such as ethylene and propylene, this Not always an industrially advantageous approach.

As a reaction similar to the traditional Wacker reaction, the ketone-forming reaction of olefins (JP-A-57-156428 (corresponding to U.S. Patent No. 4,400,544), JP-A-60-92236, JP-A-61-60621; as used herein, "JP-A" means "examined and published Japanese patent application"). In this reaction, a monohydric alcohol such as methanol or ethanol is used as the reaction medium instead of water used in the traditional Volcker reaction, while Pd and metal salts of Cu and/or Fe are used as catalysts, but as an industrial process, the reaction exists However, fatal disadvantages such as low selectivity of product ketones or aldehydes and precipitation of Pd metal occur when the reaction conditions are shifted to the high temperature side. The above documents describe that the cocatalyst Cu and Fe have equivalent effects.

Also, J.Org.Chem. Vol. 34, 3949 (1969) points out that 1,4-dioxaspiro[4,5]decane can be obtained by using PdCl ₂ and CuCl ₂ as a catalyst and using such as ethylene glycol or Polyhydric alcohols such as glycerol are used as reaction solvents to produce high yields from cyclohexene, however details such as yields are not given in the text. This document does not mention the use of iron salts as catalyst components, nor does it disclose any solution to the fatal flaw of Pd precipitation as an industrial process.

As described above, the current status is that an industrially effective method for synthesizing the corresponding aldehyde or ketone from an olefin has not been found.

In particular, cyclohexanone useful as a caprolactam precursor is produced by oxidation of cyclohexane in the presence of a catalyst, as the case may be, followed by dehydrogenation of a cyclohexanone-cyclohexanol mixture, or by cyclohexanone Hexene is hydrated to obtain cyclohexanol, and cyclohexanol undergoes dehydrogenation reaction. However, since the products of the former reaction are susceptible to subsequent oxidation during the oxidation of cyclohexane, it is necessary to keep the conversion at a rather low level and to recycle a large amount of excess unreacted cyclohexane, rendering this process a energy inefficient method. The latter method is also problematic in that the yield of the hydration reaction is insufficient, and a large amount of energy is then expended in the extraction and separation of cyclohexene from benzene-cyclohexane, which has a very close boiling point, or in the extraction and separation of cyclohexene from benzene-cyclohexane, which has a very high boiling point. In the process of separating cyclohexanone alone from an approximately equimolar cyclohexanone-cyclohexanol mixture.

It can be seen that if there is a highly selective and efficient synthetic method for preparing aldehydes or ketones, especially cyclohexanone, from corresponding alkenes such as cyclohexene, its significance will be considerable.

In order to solve these problems involved in olefin oxidation reactions, the present inventors conducted intensive research and found that Pd precipitation, an industrially fatal phenomenon, can be prevented and the decline in catalyst selectivity can be suppressed, simply by combining olefins with oxygen. In the process of reacting with polyols to form ketals and/or acetals, in addition to (a) palladium and (c) halogens, (b) 8, 9, 10 and 14 belonging to the periodic table of elements are also used as catalysts group of at least one non-palladium metal, thus completing the present invention.

Summary of the invention

In summary, the gist of the present invention lies in the following aspects:

(1) A process for producing ketals and/or acetals by reacting an olefin having at least one olefinic double bond with oxygen and a polyhydric alcohol in the presence of a catalyst, the process comprising (a) palladium, (b) belonging to the periodic element The reaction is carried out in the presence of at least one metal other than palladium from groups 8, 9, 10 and 14 of the table and (c) a halogen as catalyst.

(2) The method for producing ketal and/or acetal as described in (1), wherein the reaction is carried out in a liquid phase in which a catalyst is dissolved.

(3) The method for producing ketal and/or acetal as described in (1) and (2), which further comprises copper as a catalyst.

(4) The method for producing ketals and/or acetals as described in (3), wherein the catalyst compound used as the copper source is at least one of cuprous chloride and cupric chloride.

(5) The method for producing ketals and/or acetals as described in (3) or (4), wherein the amount of copper used is (b) at least one of Groups 8, 9, 10 and 14 of the Periodic Table of Elements 0.1 to 100 times that of a non-palladium metal, in moles.

(6) The method for producing ketals and/or acetals as described in any one of (1) to (5), wherein (b) belongs to at least one of Groups 8, 9, 10 and 14 of the Periodic Table of Elements Non-palladium metals are selected from iron, cobalt, nickel and tin.

(7) The method for producing ketals and/or acetals as described in (6), wherein (b) at least one non-palladium metal belonging to Groups 8, 9, 10 and 14 of the periodic table is iron.

(8) The method for producing a ketal and/or acetal as described in any one of (1) to (7), wherein (c) the halogen is chlorine.

(9) The method for producing ketal and/or acetal as described in any one of (1) to (8), wherein the concentration of palladium in the reaction solution is 0.001 to 10% by weight.

(10) The method for producing ketal and/or acetal as described in any one of (1)～(9), wherein in the reaction solution (b) belongs to Group 8, 9, 10 and 14 of the Periodic Table of Elements The molar ratio of at least one non-palladium metal to palladium is 0.1-100.

(11) The method for producing ketal and/or acetal as described in any one of (1) to (10), wherein the molar ratio of (c) halogen to palladium in the reaction solution is 0.1 to 100.

(12) The method for producing ketals and/or acetals as described in any one of (1) to (11), wherein the catalyst compound used as the source of (a) palladium is palladium chloride.

(13) The method for producing ketals and/or acetals as described in any one of (1) to (12), wherein the catalyst compound used as the source of (a) palladium is a compound of divalent palladium.

(14) The method for producing ketal and/or acetal as described in any one of (1) to (13), wherein the catalyst compound used as the source of (a) palladium is a nitrile compound-coordination compound .

(15) The method for producing ketals and/or acetals as described in any one of (1) to (14), wherein as (b) at least one of Groups 8, 9, 10 and 14 of the Periodic Table of Elements A catalyst compound that is a source of a non-palladium metal is chloride.

(16) The method for producing ketal and/or acetal as described in any one of (1) to (15), wherein chlorine as (c) halogen is used as chloride of (a) or (b) .

(17) The method for producing ketal and/or acetal as described in any one of (1) to (16), wherein the olefin is a cycloalkene having 4 to 10 carbon atoms.

(18) The method for producing a ketal and/or acetal as described in (17), wherein the olefin is cyclohexene.

(19) The method for producing ketal and/or acetal as described in any one of (1) to (16), wherein the olefin is a terminal olefin having 2 to 25 carbon atoms.

(20) The method for producing ketal and/or acetal as described in any one of (1) to (16), wherein the olefin is an internal olefin having 4 to 25 carbon atoms.

(21) The method for producing ketal and/or acetal as described in any one of (1) to (20), wherein the polyhydric alcohol is an aliphatic or alicyclic diol.

(22) The method for producing ketal and/or acetal as described in any one of (1) to (21), wherein the polyhydric alcohol is used in an amount of 1 to 100 times that of the olefin, on a molar basis.

(23) A method for producing ketones and/or aldehydes by hydrolyzing the ketals and/or acetals produced by the method according to any one of claims (1) to (22) in the presence of an acid catalyst. Best Embodiment of the Invention (Catalyst)

The catalyst of the present invention consists of a component comprising (a) palladium, (b) at least one non-palladium metal belonging to Groups 8, 9, 10 and 14 of the Periodic Table of the Elements, and (c) a halogen. In this case, the components of (a) to (c) may exist in any form such as dissociated ions, salts or molecules in the reaction system.

(a) Palladium may be in divalent to tetravalent forms, and may optionally be selected from known and commercially available compounds. Examples thereof include palladium halides such as palladium chloride and palladium bromide, palladium salts of inorganic or organic acids such as palladium nitrate, palladium sulfate, palladium acetate, palladium trifluoroacetate and palladium acetylacetonate, and inorganic palladium such as palladium oxide and hydroxide palladium. Also useful are base coordination compounds derived from these metal salts, such as [Pd(en) ₂ ]Cl ₂ , [Pd(phen) ₂ ]Cl ₂ , [Pd(CH ₃ CN) 2 ]Cl 2 , [Pd(en) ₂ ]Cl ₂ , [Pd (C ₆ H ₅ CN) ₂ ]Cl ₂ , [Pd(C ₂ O ₄ ) ₂ ] ₂ , [PdCl ₂ (NH ₃ ) ₂ ] and [Pd(NO ₂ ) ₂ (NH ₃ ) ₂ ] (where en represents ethylenediamine; phen represents 1,10-phenanthroline), but not limited to these. Among these palladium sources, divalent palladium sources, especially chloride or nitrile compound-coordination compounds are preferably used.

The role of palladium in the catalyst system can be represented by its interaction with iron ions and polyols, although the conditions of action are not fully understood. In view of the fact that palladium expresses its activity by forming active species with other catalyst components, it is sufficient as long as there is a palladium source sufficient to induce this essence in the system.

As (b) at least one non-palladium metal belonging to Groups 8, 9, 10 and 14 of the periodic table of elements, iron, cobalt, nickel, ruthenium and tin are exemplified, among which iron is preferable.

Catalyst compounds used as sources of iron may exist in divalent or trivalent form. For example, it can be used in this reaction in the form of various salts, including chlorides such as ferrous chloride and ferric chloride, bromides such as ferrous bromide and ferric bromide, inorganic acid salts such as ferrous sulfate and Ferric sulfate, ferrous nitrate and ferric nitrate and salts such as ferrous acetate, ferric acetate, ferrous oxalate, ferric oxalate, ferric formate and ferric acetylacetonate, or in the form of complexes thereof. Similar to the case of palladium, the essence is that iron expresses its activity by constituting active species with other catalyst components, so as long as there is enough iron source in the system to induce this essence.

The catalyst compounds used as sources of cobalt, nickel, ruthenium or tin may take divalent, trivalent or tetravalent forms. By way of example, a wide variety of salts can be used, including their halides such as chloride and bromide, inorganic acid salts such as sulfate and nitrate, and salts such as acetate, oxalate, formate and acetylacetonate, etc. salt, or its coordination compound. When component (b) is cobalt, nickel or tin, it is preferred that it is further used in combination with copper.

The main effect of the present invention is that the precipitation of palladium is significantly suppressed due to the addition of component (b), and further adding copper compounds such as CuCl or _CuCl will bring into play other beneficial effects as an industrial process, That is, improvement in reaction rate and reduction in by-products such as halides.

Halogen (c) is chlorine (Cl) and/or bromine (Br), but chlorine (Cl) is particularly preferred. Halogen can be used as the counter anion of Pd and/or Fe in the reaction system. It can also be supplied to the reaction system as a chloride of other catalyst components or in a certain form such as HCl and HBr, provided that in any case this compound is present in the reaction system in the form of ions.

According to the invention, ketals and/or acetals are produced by reacting olefins with oxygen and polyols in a liquid phase in which the abovementioned catalysts are dissolved. (Olefin)

The olefin used in the present invention is an aliphatic or cycloaliphatic organic compound containing at least one olefinic double bond. As chain olefins, there may be mentioned olefins generally containing 2 or more, preferably 2 to 25, more preferably 3 to 10 carbon atoms, such as ethylene, propylene, butene, pentene, hexene and octene. In this case, the position of the double bond can be either terminal or internal, but mainly acetals or ketals of the methyl ketone type are formed in the case of terminal olefins, and mainly obtained in the case of internal olefins. corresponding ketal.

Examples of cycloalkenes include compounds having 4 to 10, preferably 5 to 8 carbon atoms, and containing at least one olefinic double bond, such as cyclopentene, cyclohexene, cyclohexadiene, cycloheptene and cyclooctene, Among them, cyclopentene and cyclohexene are especially industrially useful compounds. When cyclohexene is used as the olefin, 1,4-dioxaspiro[4,5]decane (hereinafter referred to as cyclohexanone ketal) is produced as a product.

At least one substituent, such as an alkyl group, an alkoxy group, an aryl group, a phenyl group, a carboxyl group, a halogen atom or a nitro group, may be present at any position of these olefin backbones. For example, olefins having a functional group in the 2-position, such as acrylonitrile, acrolein, acrylic acid or vinyl chloride, or styrene or methylstyrene are suitable for this reaction. In addition, a compound having fused rings, such as 3,4-dihydronaphthalene, can also be used if it has an olefinic double bond. (Polyol)

Polyols are generally divalent to tetravalent, and diols are particularly suitable. In the case of a diol, it generally has 2 or more carbon atoms, but when considering factors such as cost, stability, or ease of acetal or ketal formation, it is preferably 2 to 10, more preferably 3 to 8 carbon atoms atoms, and preferred illustrative examples of these diols include ethylene glycol, 1,3-propanediol, 1,2-dihydroxybutane, 1,2-dihydroxypropane, 1,4-butanediol, 1,4-cyclo Hexanedimethanol, 1,2-cyclohexanedimethanol, diethylene glycol, 1,2-trans-cyclopentanediol, 2,4-pentanediol, phenylethylene glycol, 1,5-dimethanol Hydroxycyclooctane, 1,4-dihydroxycyclooctane, 2,5-dihydroxynorbornane, 2,6-dihydroxynorbornane, 1,4-dihydroxy-2,3-dimethylbutane Alkane, 1,5-dihydroxy-2,4-dimethylpentane, cyclobutane-1,2-dimethanol, cyclohexane-1,3-dimethanol, 1,4-dihydroxy-2, 3-Dichlorobutane and 2,5-dihydroxyhexane, of which ethylene glycol, 1,3-propanediol, 1,2-dihydroxybutane, 1,2-dihydroxypropane, 1,4-butane Diol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, diethylene glycol, 1,2-trans cyclopentanediol, 2,4-pentanediol, phenylethylene glycol Alcohols are more preferred. Two or more of them may be used in combination.

Although the reason for the necessity of the use of polyols in the present invention is not fully understood, it is believed that palladium initially exists in a divalent form such as chloride, which subsequently forms a divalent peroxo complex as a new active component, Alcohol is also believed to be effective in inducing such active species. In addition to this action, it also reacts with the formed aldehyde or ketone to form the corresponding acetal or ketal, with the result that a much higher stability against oxidation by oxygen is achieved than free aldehydes and ketones. In this way, it is possible to maintain a remarkably high selectivity for the target product.

When monohydric alcohols such as methanol, ethanol or propanol are used in place of polyols, the products are mainly aldehyde or ketone compounds with very little formation of the corresponding acetals or ketals. Since these free aldehydes or ketones are unstable in the presence of oxygen, they will be subsequently oxidized, so that the yield of the target aldehyde or ketone cannot be guaranteed to be high. In contrast to this, when polyhydric alcohols including dihydric alcohols such as ethylene glycol, propylene glycol, and butanediol are used, corresponding acetals or ketals are obtained as main products. In view of the fact that the acetal or ketal produced in this way hardly undergoes subsequent oxidation under oxidation reaction conditions, the yield of aldehyde or ketone produced by the hydrolysis of the former is obviously high. (Reaction conditions)

According to the present invention, the use of oxygen-containing gas is a necessary condition, but in view of the possibility of forming explosive mixtures between oxygen and organic compounds at certain temperatures, certain pressure ranges and within certain composition ranges, this danger must be avoided. If the oxygen partial pressure is 0.001 MPa or higher, the reaction can proceed, but the reaction rate will be too slow, and the catalyst tends to passivate when the oxygen partial pressure is too low. In the present invention, the partial pressure of oxygen is preferably 0.01-10 MPa, more preferably 0.05-5 MPa, but the most preferred pressure should be selected in terms of safety and economy.

The reaction can proceed when the reaction temperature is 0°C or higher, but higher temperatures are desirable in view of the large temperature dependence of the reaction on the present invention. Although the choice of reactants should take into account the formation conditions of explosive mixtures and the increase of by-products caused by free radical autoxidation, economically beneficial reaction rates can be obtained at a temperature range of generally 20-200°C, preferably 40-180°C. The total pressure of the reaction may be equal to or greater than the pressure to maintain the liquid phase, but is generally 0.1 MPa to 20 MPa, preferably 0.1 MPa to 15 MPa. Also, the reaction time (residence time) is generally 5s to 20h, preferably 10s to 10h.

(a) The concentration of palladium as a catalyst is 0.001-10% by weight, preferably 0.01-5% by weight, calculated as [Pd ²⁺ ] and based on the total weight of the reaction solution. Under the condition of high concentration, the reaction rate exhibits different concentration dependence than that under the condition of low concentration, and the catalytic efficiency tends to deteriorate, so the concentration with high efficiency should be selected according to the economic principle.

(b) The concentration of at least one non-palladium metal M belonging to Groups 8, 9, 10 and 14 of the Periodic Table can be described in terms of its relative concentration to (a) palladium. That is, it can be selected in the range of, generally, 0.1<[M]/[Pd]<100 (molar ratio), preferably 0.1<[M]/[Pd]<10 (molar ratio). A concentration below this range tends to lower the reaction rate and the precipitation-inhibiting effect of Pd, which is the main effect of the metal (b), tends to decrease. On the other hand, if the added amount thereof is too large, the reaction itself may not be inhibited, but it tends to limit the amount dissolved in the reaction system.

The relative concentration of halogen (c) relative to palladium is generally 1<[Cl and/or Br]/[Pd]<100 (molar ratio), preferably 0.3<[Cl and/or Br]/[Pd]<50 ( molar ratio). In view of the fact that the water in the reactor may cause corrosion of the reactor material under the condition of high halogen concentration, it is preferable to select the halogen concentration as low as possible to ensure the normal functioning of the catalyst system. Also, in some cases, a catalyst-derived halogen-containing component may be formed as part of by-products, and in this case, it is preferable to continuously or periodically replenish the consumed halogen in the form of, for example, a metal salt thereof.

The amount of polyhydric alcohol present in the reaction system may be a theoretical amount (1 mol) based on olefin, but according to the present invention, it is desirable to also use it as a reaction solvent at the same time. It is generally present in an amount of 1 to 99% by volume, preferably 5 to 99% by volume, based on the total reaction volume. In addition, the amount of the polyol is generally 1 to 100 mol, preferably 2 to 50 mol, based on olefin. The amount of olefin in the reaction system can be selected, generally in the range of 1-99% (volume), preferably 1-50% (volume).

When the concentration of polyol is relatively low, that is, when the relative concentration of olefin is too high, there is a tendency to easily cause palladium precipitation due to partitioning of part of the catalyst components into the olefin phase. On the other hand, if the polyol concentration is too large, the supplied olefin concentration will decrease accordingly, thus tending to bring about low productivity and difficulty in performing phase separation after the reaction. In such cases, the relative concentration of polyols and olefins can be adjusted and the phase separation characteristics can be further improved by adding an "oxidation-inert" third component in the reaction system.

According to the invention, activity and reactivity can be increased by adding another component. For example, an additive having an oxidation-promoting effect, such as a copper compound or an alkali metal, alkaline earth metal or rare earth metal, may be added. Furthermore, it is also possible to add a free radical scavenger to suppress side reactions.

In a large-scale production process, especially in the method for producing cyclohexanone by cyclohexene among the reactions of the present invention, when considering the material balance of the whole process, it is required to effectively separate out impurities, even trace amounts . For example, the formation of impurities such as cyclohexenone, cyclohexenol, chlorocyclohexanone, cyclohexanone ketal, which are particularly difficult to separate and may have an adverse effect on the product, should be kept as low as possible.

The reaction of the present invention can be carried out as a general oxidation reaction. When each catalyst component is present in solution, the oxidation reaction can be carried out using a batch reactor and contacting the olefin with the oxygen-containing gas for a defined period of time, or using a continuous phase reactor with a continuous supply of the oxygen-containing gas and the olefin . On the other hand, when the catalyst components of the present invention are fixed, a liquid phase reaction may be employed, or a so-called spray bed system in which a catalyst is packed in a fixed bed and corresponding olefins and oxygen are supplied in a liquid phase may be employed.

Regarding the supply of oxygen, the technique of dissolving oxygen in the reaction solution system can be adopted, for example, the technique of breaking up the oxygen-containing gas into fine bubbles by using stirring blades, and breaking up the oxygen-containing gas by using the baffle arranged in the reactor The technology of fine bubbles, or the technology of injecting gas from the nozzle into the system by using high linear velocity. (treatment after oxidation reaction)

The reaction product solution after the oxidation reaction contains the raw material olefin, the ketal and/or acetal as the product, the catalyst component, and the polyol. When the reaction product solution is under pressure, the pressure can be reduced by some degree of release. When the boiling point of olefins and ketals and/or acetals in the reaction product solution is much lower than the polyol solvent, these low boiling point components (olefins and ketals and/or acetals) can be directly separated from the reaction product solution by distillation come out. As the bottom product of the distillation, a polyol solution comprising the catalyst component is obtained, which can be recycled back to the oxidation reaction step.

Also, when the boiling point of olefins and ketals and/or acetals is higher than that of the polyol solvent, an organic solvent such as an organic solvent that forms two phases with the polyol is added as an extraction solvent, and then the two phases are separated by extraction, thereby separating the olefin-containing and the extraction solvent phase of the ketal and/or acetal and the polyol phase containing the catalyst component. Olefins and ketals and/or acetals are then recovered from the extraction solvent phase, which in turn can be separated by distillation. The polyol phase containing the catalyst components can be recycled back to the oxidation reaction step. In two-phase separation, when the side of the extraction solvent containing olefins and ketals and/or acetals is contaminated with trace amounts of catalyst components, the catalyst components in the extraction phase can be recovered by subjecting the extraction solvent phase to a polyol solvent. Two or more extractions reduce their carryover to negligible levels. It is also possible to use a technique in which, after the first two-phase separation, the olefins and ketals and/or acetals are separated from the extraction solvent phase by distillation, thereby increasing the residual catalyst concentration in the extraction solvent phase to a certain extent, and then carry out the extraction again.

Additionally, due to subsequent oxidation, albeit slightly, water will be formed in the reactor during ketal formation. It is preferable to remove as much water thus produced as possible from the reaction system, but even so, when a halogen component such as chlorine remains in the system, there is a high possibility that it participates in the corrosion of the reactor. Therefore, the necessary parts must use materials with high corrosion resistance to corrosive acids such as hydrochloric acid.

Materials such as glass, ceramics and Teflon can be used in areas where reaction pressures are not too high, but in the case of high reaction pressures it is preferable to use vessels normally used as corrosion resistant reactors, i.e. made of materials such as stainless steel alloys especially Containers made of stainless steel alloys, titanium-containing alloys or zirconium-containing alloys, commonly known as Hastelloy, or containers obtained by coating or pressing these alloys on the surface. Although the reactor has a particularly high corrosion potential, if a resting vessel and a separation vessel are additionally arranged, these parts also have a high risk of corrosion. In addition, in the case of distillation of the product-containing oil phase, when catalyst components remain, there is a possibility of concentration of halogen components and thus a high risk of corrosion. Ideally, corrosion-resistant materials should be used throughout these primary vessels and piping connected to them, as determined by the extent of corrosion that is economically practicable.

The polyol present as an essential component in the reaction system is not completely inert to the oxidation reaction. Furthermore, some compounds formed by the subsequent oxidation of alkenes have a polarity close to that of polyols, albeit in very small amounts. Thus, when the batch reaction is repeated over a long period of time or in the case of a continuous reaction, certain components derived from polyols and olefins but not necessarily desired for the reaction will accumulate in the alcohol phase containing the catalyst component. In order to achieve stable operation of the process, the total material balance must be controlled in time. Therefore, it is necessary to replenish a fresh solution of catalyst material by withdrawing a portion of the catalyst-containing polyol phase from the system at a rate corresponding to the rate of formation of these impurities and the subsequent rate of formation of oxidized components. In this case, the removal ratio of the catalyst components taken out of the system is large and thus causes a large economic burden, and it is therefore necessary to recover these catalyst components. The method is not limited, but techniques including removal of organic matter, washing, and recovery of metal components are effective.

Accumulation of impurities also occurs when extraction solvents such as organic solvents are recovered by distillation from an extraction solvent phase containing two-phase separation products (ketals and/or acetals), so in this case It is also possible to remove a portion of the old extraction solvent to add new extraction solvent.

The ketals and/or acetals prepared according to the invention are converted into the corresponding ketones and/or aldehydes by hydrolysis in the presence of water and acid. Acids usable in this case include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, polyacids such as heteropolyacids, and solid acids such as ion exchange resins, zeolites and clays. Interesting aldehydes and ketones can be efficiently produced by recovering water and polyols from the aldehyde- and/or ketone-rich reaction product solution thus obtained, followed by isolation and purification of the aldehydes and ketones as expected compounds.

Also, the ketals and/or acetals produced according to the present invention can be efficiently converted to the corresponding alcohols by hydrogenation in the presence of water, a hydrogen source and a hydrogenation catalyst. Examples of hydrogen sources include hydrogen gas, formalin, and disodium borohydride (NaBH ₄ ), and examples of hydrogenation catalysts include Raney nickel, Raney cobalt; oxides containing Cu—Cr, made of Group 8 metals such as Catalysts composed of Pd, Pt or Ru loaded on the carrier, and complex catalysts using Group 8 metals such as Ru, Pt or Pd as the central metal. Alcohols of interest can be efficiently produced by recovering water and alcohols generated from acetals and/or ketals from the alcohol-rich reaction product solution obtained by hydrogenation, followed by isolation and purification of the alcohols as expected compounds.

Hereinafter, the present invention will be described more specifically by way of examples, however, the present invention is not limited to these examples.

Example 1

Add 0.1mmol Pd(CH ₃ CN) ₂ Cl ₂ , 0.1mmol CuCl ₂ , 0.1mmol FeCl in a drum-shaped borosilicate heat-resistant glass reactor with an inner diameter of 40mm and a height of 12mm equipped with a magnetic stirrer and a gas introduction tube. _3. 10mL of ethylene glycol and 20mmol of cyclohexene, replace the air with pure oxygen, and then react under stirring at 40°C for 5h. An internal standard compound was added to the reaction solution, and the product was analyzed by gas chromatography. As a result, the conversion rate of cyclohexene was 2.5%, and cyclohexanone ketal was obtained in a yield of 2.5%. TOF is 1.0/h. TOF refers to the rate of formation of cyclohexanone and cyclohexanone ketal per 1 mole of palladium per hour. In this case, only cyclohexanone ketal was formed. After the reaction, no precipitation of palladium was found in the solution. Chlorocyclohexane was also not formed. Example 2

The reaction was carried out according to the procedure of Example 1, except that CuCl ₂ was not added. As a result, the conversion rate of cyclohexene was 2.5%, and cyclohexanone ketal was obtained in a yield of 2.5%. TOF is 1.0/h. Chlorocyclohexane, a by-product, was found at 1.0 mol% based on cyclohexanone ketal. After the reaction, no precipitation of palladium was found in the solution. Comparative example 1

The reaction was carried out according to the procedure of Example 1, except that FeCl ₃ was not added. As a result, the conversion rate of cyclohexene was 2.3%, and cyclohexanone ketal was obtained in a yield of 2.3%. TOF is 0.92/h. After the reaction, the reaction solution was turbid due to the fine black powder containing palladium black, and palladium precipitation was found on the bottom and inner wall of the reactor.

Table 1 palladium compound Iron compounds copper compound CHE conversion rate ^★ Ketal Yield ^★★ TOF ^★★★ Remark Example 1 0.1mmol 0.1mmol 0.1mmol 2.5% 2.5% 1.0/hour No palladium precipitation, no formation of chlorocyclohexane Example 2 0.1mmol 0.1mmol Unused 2.5% 2.5% 1.0/hour No palladium precipitation, resulting in chlorocyclohexane Comparative example 1 0.1mmol Unused 0.1mmol 2.3% 2.3% 0.92/hour palladium precipitation

^★ : Cyclohexene conversion rate ^★★ : Cyclohexanone ketal yield ^★★★ : Generation rate of cyclohexanone and cyclohexanone ketal per 1 mole of palladium per hour

Comparing Examples 1 and 2 with Comparative Example 1, it can be seen that the precipitation of palladium is suppressed by the addition of Fe. It can also be seen that the formation of chlorocyclohexane is suppressed by the additional addition of copper compound. Example 3

A cylindrical Teflon beaker equipped with a magnetic stirring bar, an internal diameter of 40mm, and a height of 15mm is inserted into a SUS-316 autoclave with a pressure resistance of 100kG and a size that matches the beaker, and the reaction adopts the same feed composition as that of Example 1. conditions, at a reaction temperature of 80° C. and an oxygen pressure of 7 kG for 1 h. As a result, the reaction product rate of cyclohexanone ketal/cyclohexanone = 24.8, and that of cyclohexanone ketal/cyclohexenone = 26.1, wherein the cyclohexene conversion rate was 30%, and TOF was 60/h were obtained. After the reaction was completed, no precipitation of palladium was found. Example 4

The reaction was carried out in the same manner as in Example 3, except that CuCl was not used. As a result, the conversion rate of cyclohexene was 34%, and the TOF was 67/h. The amount of chlorocyclohexane produced was 1 mol% based on the ketal. After the reaction was completed, no precipitation of palladium was found. Comparative example 2

The reaction was carried out in the same manner as in Example 4, except that FeCl ₃ was not used, and CuCl ₂ or CuCl was used in the prescribed amount. The results are shown in Table 2. Precipitation of palladium was found in all cases.

Table 2 copper compound Cyclohexene conversion TOF*(/hour) CuCl(0.1mmol) _CuCl2 (0.1mmol) _CuCl2 (0.2mmol) 13.5% 21.0% 45.0% 274290 *: Formation rate of cyclohexanone and cyclohexanone ketal per 1 mole of palladium per hour

From the above results, it can be seen that when iron is present in the system, palladium does not precipitate and the catalyst works efficiently, even when the oxygen concentration is increased and the conversion of cyclohexene reaches a high value. Example 5

The reaction was carried out in the same manner as described in Example 1, except that ethylene glycol was replaced with a mixed solution of 5 mL of ethanol+2.5 g of ethylene glycol. As a result, the conversion rate of cyclohexene is 22%; (cyclohexanone+cyclohexanone ketal) yield is 21.0%; (cyclohexanone ketal+cyclohexanone) selectivity is 95%; TOF is 8.4/h . After the reaction, no precipitation of palladium was found in the solution. Example 6

The reaction was carried out in the same manner as described in Example 1, except that ethylene glycol was replaced with a mixed solution of 5 mL of methanol+2.5 g of ethylene glycol. As a result, the ratio of cyclohexanone ketal to cyclohexanone was 17.6, the conversion rate of cyclohexene was 10.0%, the yield (cyclohexanone+cyclohexanone ketal) was 10.0%, and the TOF was 4.0/h. After the reaction, no precipitation of palladium was found in the solution. Example 7

The reaction was carried out in the same manner as described in Example 1, except that ethylene glycol was replaced with a mixed solution of 7.5 g of 1,4-butanediol+2.5 g of ethylene glycol. As a result, the cyclohexene conversion rate was 22%; TOF was 8.0/h. After the reaction, no precipitation of palladium was found in the solution. Example 8

The reaction was carried out in the same manner as described in Example 1, except that 1,3-propanediol was used instead of ethylene glycol. As a result, reaction products cyclohexanone ketal/cyclohexanone=2.87, cyclohexanone ketal/cyclohexenone=16.1 were obtained, and the conversion rate of cyclohexene was 16%. As for the formation rate of (cyclohexanone + ketal), TOF was 6.4/h. After the reaction, no precipitation of palladium was found in the solution. Example 9

The reaction was carried out in the same manner as described in Example 1, except that 1,4-butanediol was used instead of ethylene glycol. As a result, reaction products cyclohexanone ketal/cyclohexanone=0.41, cyclohexanone ketal/cyclohexenone=4.93 were obtained, and the conversion rate of cyclohexene was 27%. (Cyclohexanone+ketal) selectivity is 79%, TOF is 8.5/h. After the reaction, no precipitation of palladium was found in the solution. Example 10

The reaction was carried out in the same manner as described in Example 1 except that 2,3-butanediol was used instead of ethylene glycol. As a result, the cyclohexene conversion rate was 7%. (Cyclohexanone ketal+cyclohexanone) selectivity is 91.5%, TOF is 2.6/h. After the reaction, no precipitation of palladium was found in the solution. Example 11

The reaction was carried out in the same manner as described in Example 1, except that 1,2-cyclohexanediol was used instead of ethylene glycol. As a result, the cyclohexene conversion rate was 12%. Cyclohexanone ketal/cyclohexanone is 3.7, (cyclohexanone ketal+cyclohexanone) selectivity is 90%, TOF is 4.3/h. After the reaction, no precipitation of palladium was found in the solution. Comparative example 3

The reaction was carried out in the same manner as described in Example 1 except that ethanol was used instead of ethylene glycol. As a result, the conversion of cyclohexene was 35%. Cyclohexanone yield was 17%. The selectivity of cyclohexanone was 51%. No precipitation of palladium was found on the inner wall of the reactor. No cyclohexanone acetal was formed.

The results of Examples 5-11 and Comparative Example 3 are shown in Table 3 below together with the results of Example 1.

table 3 alcohol CHN ketal/CHN* TOF** Remark Example 1 Ethylene glycol (EG) 10mL 100 1.0/h No palladium precipitation, no chlorine cyclohexane Example 5 Ethanol 5mL+EG 2.5g >10 8.4/h No palladium precipitation Example 6 Methanol 5mL+EG 2.5g 17.6 4.0/h No palladium precipitation Example 7 1,4-Butanediol (BG) 7.5g+EG 2.5g >10 8.0/h No palladium precipitation Example 8 1,3-Propanediol 10mL 2.87 6.4/h No palladium precipitation Example 9 1,4-Butanediol (BG) 10mL 0.41 8.5/h No palladium precipitation Example 10 2,3-Butanediol 10mL 5-10 2.6/h No palladium precipitation Example 11 1,2-cyclohexanediol 10mL 3.7 4.3/h No palladium precipitation Comparative example 3 Ethanol 10mL 0 6.8/h No palladium precipitation, no ketal formation *: cyclohexanone ketal/cyclohexanone **: formation rate of cyclohexanone and cyclohexanone ketal per 1 mole of palladium per hour

Through the comparison of Examples 1 and 5-11 with Comparative Example 3, it can be seen that CHN ketal is generated when polyhydric alcohol is present. Given that little subsequent oxidation occurs in CHN ketals compared to CHN in the reaction system, it is desirable for (CHN+CHN ketal) selectivities to obtain products with high CHN ketal/CHN ratios. Example 12

The reaction was carried out in the same manner as described in Example 7, except that Pd(CH ₃ CN) ₂ Cl ₂ was replaced by Pd(BzCN) ₂ Cl ₂ . As a result, the conversion rate of cyclohexene was 5%; TOF was 2/h. After the reaction, no precipitation of palladium was found in the solution. Example 13

The reaction was carried out in the same manner as described in Example 7, except that Pd(CH ₃ CN) ₂ Cl ₂ was replaced by PdCl ₂ . As a result, the conversion rate of cyclohexene was 4%; TOF was 1.6/h. After the reaction, no precipitation of palladium was found in the solution. Example 14

A cylindrical Teflon beaker equipped with a magnetic stirring bar, an internal diameter of 40mm, and a height of 15mm is inserted into a SUS-316 autoclave with a pressure resistance of 100kG and a size that matches the beaker, and the reaction adopts the same feed composition conditions as in Example 1 , at a reaction temperature of 70, 80, 90 or 100 °C and an oxygen pressure of 7 kG for 1 h. After the reaction was completed, no precipitation of palladium was found in the solution. The results are shown in Table 4. It can be seen that the reaction rate is highly dependent on the reaction temperature or oxygen pressure.

Table 4 Reaction temperature (°C) Cyclohexene conversion TOF* Ketal/Cyclohexanone Ketal/Cyclohexenone 708090100 21% 30% 50% 58% 425893110 >4024.828.518.3 >100026.112.315.7 *: Formation rate of cyclohexanone and cyclohexanone ketal per 1 mole of palladium per hour Example 15

The reaction was carried out in the same manner as described in Example 14, except that a mixture of 2.5 g ethylene glycol + 7.5 g 1,4-butanediol was used as the reaction solvent and the reaction temperature was 40, 60, 80 or 90°C. After the reaction, no precipitation of palladium was found in the solution. The results are shown in Table 5.

table 5 temperature reflex Cyclohexene conversion TOF* Ketal/Cyclohexanone Ketal/Cyclohexenone 40608090 4% 13% 46% 87% 82484154 5.32.62.31.1 12.58.07.23.7 *: Formation rate of cyclohexanone and cyclohexanone ketal per 1 mole of palladium per hour

It can be seen that the reaction rate increases rapidly with the increase of reaction temperature. Example 16

The reaction of Example 14 was carried out, except that the reaction temperature was fixed at 80° C. and the amount of cyclohexene added was changed. After the reaction, no precipitation of palladium was found in the solution. The results are shown in Table 6.

Table 6 Cyclohexene/Palladium Reaction time Cyclohexene conversion TOF*(/h) Ketal/Cyclohexanone Ketal/Cyclohexenone 200400 1.03.01.03.0 26% 70.5% 37% 60% 50434737 24.811.727.617.2 26.110.419.011.9 *: Formation rate of cyclohexanone and cyclohexanone ketal per 1 mole of palladium per hour Example 17

The reaction of Example 15 was carried out, except that the reaction temperature was fixed at 90° C., and the addition amount of each of palladium, copper and iron was fixed at 0.025 mmol. As a result, the cyclohexene conversion rate was 58%; the TOF value was 425/h; the cyclohexanone ketal/cyclohexanone ratio was 4.4; and the cyclohexanone ketal/cyclohexenone ratio was 8.5. After the reaction, no precipitation of palladium was found in the solution. Example 18

Carry out the oxidation reaction identical with example 3, difference is, _FeCl Change the cocatalyst shown in table 7 into. As a result, the product was mostly cyclohexanone ketal. The TOF values are shown in Table 7.

Table 7 Co-catalyst TOF/h palladium black precipitate Example 3 _FeCl3 60 none Example 18 _FeCl3 70 slight _CoCl3 57 slight Sn(acac) ₂ Br ₂ 27 none Ni(acac) ₂ 4 none acac: acetylacetonate Example 19

A cylindrical Teflon beaker equipped with a magnetic stirrer, an inner diameter of 40mm, and a height of 15mm is inserted into a SUS-316 autoclave with a pressure resistance of 100kG and a size that just matches the beaker, and the reaction is performed at a reaction temperature of 80°C and an oxygen pressure of 7kG Adopt the same feed composition as example 1 and carry out under the condition of adding 20mmol styrene. After reacting for 1 h, the material was taken out and analyzed by gas chromatography. As a result, the TOF value is 154/h; the EG acetal compound selectivity of phenylacetaldehyde is 54%; the EG ketal compound selectivity of acetophenone is 11%; (phenylacetaldehyde+acetophenone) selectivity is 25 %. After the reaction, no precipitation of palladium was found in the solution. Example 20

The reaction was carried out in the same manner as in Example 19, except that α-methylstyrene was used instead of styrene. As a result, the TOF value was 54/h; only 2-phenylpropanal and its EG acetal compound were produced. The acetal/aldehyde ratio was 2.5. After the reaction, no precipitation of palladium was found in the solution. Example 21

The reaction was carried out in the same manner as in Example 19, except that 3,4-dihydronaphthalene was used instead of styrene. As a result, the TOF value was 90/h. After the reaction, no precipitation of palladium was found in the solution. Example 22

The reaction was carried out in the same manner as in Example 19, except that 1-octene was used instead of styrene. As a result, the TOF value was 46/h; the (ketal compound + acetal compound) selectivity was 70%; and the main product obtained was the ketal compound of the corresponding ketone compound of octene in which the double bond in octene was transferred. After the reaction, no precipitation of palladium was found in the solution. Example 23

The reaction was carried out in the same manner as in Example 22, except that 2-octene was used instead of 1-octene. As a result, the TOF value was 40/h; (ketal compound+acetal compound) selectivity was 84%. The distribution of the resulting products was the same as in Example 22. After the reaction, no precipitation of palladium was found in the solution. (The embodiment that uses the mixed material of cyclooctene and benzene) Example 24

A cylindrical Teflon beaker equipped with a magnetic stirrer, an inner diameter of 40 mm, and a height of 15 mm is inserted into a SUS-316 autoclave with a pressure resistance of 100 kg and a size that matches the beaker. Under the condition that benzene coexists, add 2.2 g of benzene , 2 g cyclohexene, 0.3 mmol Pd(CH ₃ CN) ₂ Cl ₂ , 0.3 mmol CuCl ₂ , 0.3 mmol FeCl ₃ and 6.2 g 1,4-butanediol. The reaction was carried out at a reaction temperature of 70°C and various oxygen pressures as indicated in the table below. The major product besides cyclohexanone and cyclohexanone ketal is cyclohexenone. The results are shown in Table 8.

Table 8 Oxygen pressure (kG) Response time (minutes) Cyclohexene conversion (%) selectivity (%) 456789 24202224911 636768627285 717277847074 Selectivity = cyclohexanone + cyclohexanone ketal Example 25

Using the same reaction equipment as Example 24, take the working condition of coexistence with benzene, add 2.2g benzene, 2g cyclohexene, 0.6mmol Pd(CH ₃ CN) ₂ Cl ₂ , 0.6mmol CuCl ₂ , 0.6mmol FeCl ₃ and 6.2g1 , 4-butanediol. The reactions were carried out at an oxygen pressure of 7 kG and at various reaction temperatures as shown in the table below. The major product besides cyclohexanone and cyclohexanone ketal is cyclohexenone. The results are shown in Table 9.

Table 9 Reaction temperature (°C) Response time (minutes) Cyclohexene conversion (%) selectivity (%) 706560 81128 807572 707679 Selectivity = cyclohexanone + cyclohexanone ketal Example 26

Use the same reaction equipment as Example 24, take the working condition of coexistence with benzene, add 1.1g benzene, 1g cyclohexene, 0.3mmol Pd(CH ₃ CN) ₂ Cl ₂ , 0.3mmol CuCl ₂ , 0.3mmol FeCl ₃ and 6.2g1 , 4-butanediol. The reaction was carried out for 3.5 min at an oxygen pressure of 7 kG and a reaction temperature of 80°C. As a result, the conversion rate of cyclohexene was 92%; the selectivity of cyclohexanone and cyclohexanone ketal was 70%. The major product besides cyclohexanone and cyclohexanone ketal is cyclohexenone. Example 27

Materials and catalyst components were charged into the reaction equipment in the same manner as in Example 24, except that 1,2-cyclohexanedimethanol was used instead of 1,4-butanediol. The reaction was carried out for 32 min at a reaction temperature of 70 °C and an oxygen pressure of 7 kG. As a result, the conversion of cyclohexene was 52%; the selectivity of cyclohexanone and cyclohexanone ketal was 84%. The cyclohexanone ketal/cyclohexanone ratio is 3. Example 28

Materials and catalyst components were added to the reaction equipment in the same manner as in Example 27, except that 2.3g1, 2-cyclohexanedimethanol and 3.9g1, 4-cyclohexanedimethanol were used instead of 6.2g1, 2-Cyclohexanedimethanol. The reaction was carried out for 20 min at a reaction temperature of 70 °C and an oxygen pressure of 7 kG. As a result, the conversion of cyclohexene was 70%; the selectivity of cyclohexanone and cyclohexanone ketal was 63%. The cyclohexanone ketal/cyclohexanone ratio is 1. Industrial availability

According to the present invention, ketals and/or acetals can be produced from olefins with high conversion rate and high selectivity while the precipitation of palladium is suppressed, so it has high industrial practical value.

Although the present invention has been described above in conjunction with specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therefrom without departing from the spirit and scope of the present invention.

This application is based on Japanese Patent Application No. 2000-125535 filed on April 26, 2000, the entire contents of which are hereby incorporated by reference.

Claims (23)

1. A process for the production of ketals and/or acetals by reacting an olefin having at least one olefinic double bond with oxygen and a polyhydric alcohol in the presence of a catalyst, the process comprising (a) palladium, (b) the element The reaction is carried out in the presence of at least one non-palladium metal of groups 8, 9, 10 and 14 of the periodic table and (c) a halogen as catalyst. 2. The method for producing ketals and/or acetals according to claim 1, wherein the reaction is carried out in a liquid phase in which the catalyst is dissolved. 3. The process for producing ketals and/or acetals according to claim 1 or 2, wherein copper is also included as catalyst. 4. The method for producing ketals and/or acetals according to claim 3, wherein the catalyst compound used as the copper source is at least one of cuprous chloride and copper chloride. 5. The method for producing ketals and/or acetals according to claim 3 or 4, wherein the amount of copper is 0.1% of (b) at least one non-palladium metal belonging to Groups 8, 9, 10 and 14 of the Periodic Table of Elements ~100 times, in moles. 6. The method for producing ketals and/or acetals according to any one of claims 1 to 5, wherein (b) at least one non-palladium metal belonging to Groups 8, 9, 10 and 14 of the Periodic Table of the Elements selected from iron, cobalt, nickel and tin. 7. The method for producing ketals and/or acetals according to claim 6, wherein (b) at least one non-palladium metal belonging to groups 8, 9, 10 and 14 of the periodic table is iron. 8. A process for the production of ketals and/or acetals as described in any one of claims 1 to 7, wherein (c) halogen is chlorine. 9. The method for producing ketals and/or acetals according to any one of claims 1 to 8, wherein the concentration of palladium in the reaction solution is 0.001 to 10% by weight. 10. The method for producing ketals and/or acetals according to any one of claims 1 to 9, wherein in the reaction solution (b) belongs to at least one non-palladium group of 8, 9, 10 and 14 groups of the periodic table of elements The molar ratio of metal to palladium is 0.1-100. 11. The method for producing ketal and/or acetal according to any one of claims 1-10, wherein the molar ratio of (c) halogen to palladium in the reaction solution is 0.1-100. 12. The process for producing ketals and/or acetals according to any one of claims 1 to 11, wherein the catalyst compound used as a source of (a) palladium is palladium chloride. 13. The method for producing ketals and/or acetals according to any one of claims 1 to 12, wherein the catalyst compound used as a source of (a) palladium is a compound of divalent palladium. 14. The method for producing ketals and/or acetals according to any one of claims 1 to 13, wherein the catalyst compound used as a source of (a) palladium is a nitrile compound-coordination compound. 15. The method for producing ketals and/or acetals according to any one of claims 1 to 14, wherein as (b) at least one metal other than palladium belonging to Groups 8, 9, 10 and 14 of the Periodic Table of the Elements The source catalyst compound is chloride. 16. The method for producing ketals and/or acetals according to any one of claims 1 to 15, wherein chlorine as (c) halogen is used as the chloride of (a) or (b). 17. The process for producing ketals and/or acetals according to any one of claims 1 to 16, wherein the olefin is a cycloalkene having 4 to 10 carbon atoms. 18. The process for producing ketals and/or acetals according to claim 17, wherein the olefin is cyclohexene. 19. The process for producing ketals and/or acetals according to any one of claims 1 to 16, wherein the olefin is a terminal olefin having 2 to 25 carbon atoms. 20. The process for producing ketals and/or acetals according to any one of claims 1 to 16, wherein the olefin is an internal olefin having 4 to 25 carbon atoms. 21. The process for producing ketals and/or acetals according to any one of claims 1 to 20, wherein the polyol is an aliphatic or cycloaliphatic diol. 22. The method for producing ketals and/or acetals according to any one of claims 1 to 21, wherein the polyol is used in an amount of 1 to 100 times that of the olefin in terms of moles. 23. A method for producing ketones and/or aldehydes, which is to produce ketones and/or aldehydes by hydrolyzing ketals and/or acetals produced by the method according to any one of claims 1 to 22 in the presence of an acid catalyst By hydrolysis in the presence of a catalyst.