JPH0449532B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing 9,10-phenanthrenequinone. Specifically, a tertiary alcohol is oxidized with hydrogen peroxide in the presence of an organic solvent that forms an azeotrope with water and an acid catalyst to convert it into a tertiary alkyl hydroperoxide. phenanthrene is converted into 9,10-phenanthrenequinone by liquid phase oxidation in the presence of an organic solvent that forms an azeotrope with water and a molybdenum-containing compound catalyst, and during the oxidation reaction, the tertiary alkyl hydro The tertiary alcohol, which is a peroxide separation product, and the water generated from the reaction are distilled out of the system as an azeotrope with an organic solvent, and the tertiary alcohol is continuously distilled together with the organic solvent from which the water is separated. The present invention relates to a production process for obtaining high-yield, high-purity 9,10-phenanthrenequinone, which is recovered and recycled to the tertiary alkyl hydroperoxide production process. Regarding the production method of 9,10-phenanthrenequinone, a liquid phase oxidation method using a chromic acid compound has been known industrially. However, this method has the following problems. In other words, discharging chromium compounds outside the system is strictly restricted due to pollution and environmental hygiene reasons, and solutions to these problems, such as using them in closed systems and improving working environment standards, require enormous costs, and as a result, there are serious consequences. The product purity of 9,10-phenanthrenequinone is at most 70%.
It has been pointed out that the disadvantages are that it is relatively low and that chromium compounds are unavoidable. In addition to chromic acid compounds, numerous synthetic methods for producing 9,10-phenanthrenequinone are described in literature and patent specifications. For example, gas-phase catalytic oxidation of phenanthrene using a vanadium-based solid catalyst, potassium permanganate, periodic acid or potassium iodate and acetic acid, hypochlorite, ammonium cerium sulfate, hydrogen peroxide and acetic acid,
Liquid phase oxidation methods using organic peroxides and the like have been proposed. However, these methods have low yields and oxidizing agents are expensive. Both methods have disadvantages such as unavoidable corrosion of the equipment and unavoidable contamination of impurities into the product, and neither has yet become an effective industrial manufacturing method. In producing 9,10-phenanthrene quinone from phenanthrene, product manufacturers have carefully studied methods that can produce it with high purity, high yield, and economically. The present invention was completed by discovering a method for obtaining 9,10-phenanthrenequinone with high quality and extremely high yield. That is, the present invention can be specified as follows. (1) When producing 9,10-phenanthrene quinone by liquid-phase oxidation of phenanthrene using an organic peroxide, (a) an acid catalyst is used as a catalyst, and the water produced by the reaction is The tertiary alcohol is converted into a tertiary alkyl hydroperoxide with hydrogen peroxide in the presence of an organic solvent which is distilled out of the system as a boiling mixture; (b) then,
Using the obtained tertiary alkyl hydroperoxide, using a molybdenum-containing compound as a catalyst, and supplying phenanthrene in the coexistence of an organic solvent that can distill water produced by the reaction out of the system as an azeotrope. The tertiary alkyl hydroperoxide is used in the range of 0.5 to 4 moles per mole, and the conversion rate of phenanthrene is kept in the range of 30 to 80%, and the tertiary alkyl hydroperoxide is produced as a by-product. A method for producing 9,10-phenanthrenequinone, which comprises recovering a tertiary alcohol and an organic solvent, which are decomposition products of 9,10-phenanthrenequinone, and recycling them in a process for producing tertiary alkyl hydroperoxide. (2) The production method described in (1) above, characterized in that tert-butyl alcohol or tert-amyl alcohol is used as the tertiary alcohol. (3) The above (1) or which is characterized in that a sulfonic acid-based strongly acidic cation exchange resin is used as the acid catalyst.
(2) The manufacturing method described. (4) The production method described in (1), (2) or (3) above, characterized in that acetylacetonate of a molybdenum compound is used as the molybdenum-containing compound. According to the method of the present invention specified above, 9,10-
Not only can phenanthrenequinone be produced and obtained with high selectivity, but only a small amount of diphenic acid (biphenyl-2,2'-dicarboxylic acid), which is a sequential oxide of 9,10-phenanthrenequinone, is produced as a by-product. generate. On the other hand, tertiary alcohol, which is a decomposition product of tertiary alkyl hydroperoxide, which is extracted with a high recovery rate along with the organic solvent during the oxidation reaction, is converted to tertiary alkyl hydroperoxide by hydrogen peroxide, and then reused. It is recycled and used by supplying it to the liquid phase oxidation reaction of phenanthrene. The product thus obtained, 9,10-phenanthrenequinone, can be obtained with a purity of 90% or more simply by separating the reaction solution by cooling and crystallization operations. Organic peroxides that can be used in the product include common organic peroxides, especially tertiary alkyl hydroperoxides.
tert-butyl hydroperoxide and tert-
Amyl hydroperoxide is advantageous;
Examples of starting materials for the tertiary alkyl hydroperoxide include tert-butyl alcohol and tert-amyl alcohol. The amount of tertiary alcohol used is sufficient if it is present in a stoichiometric amount relative to hydrogen peroxide, but usually 1 to 1 tertiary alcohol is used per mole of hydrogen peroxide.
It is used in an amount of 3 mol, preferably 1 to 1.5 mol. The hydrogen peroxide used in the conversion of tertiary alcohol to tertiary alkyl hydroperoxide can be used at any concentration, but usually a 10-80% aqueous solution is used. Any organic solvent that can be used as a reaction solvent can be used as long as it is stable under the conditions of use, forms an azeotropic mixture with water, does not dissolve in each other, and can be easily separated. The conversion of tertiary alcohol to tertiary alkyl hydroperoxide is promoted by removing the water of hydrogen peroxide and the water generated in the reaction out of the reaction system, but in actual operation, the reaction The purpose can be achieved by using an organic solvent that forms an azeotrope with water in the boiling state of the liquid as a reaction solvent, condensing and separating the evaporated water and organic solvent, and then circulating and replenishing only the organic solvent into the reaction system. can be achieved. Examples include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, n-hexane, n-heptane,
Examples include aliphatic and alicyclic hydrocarbons such as n-octane and cyclohexane, with benzene, ethylbenzene and n-hexane being particularly preferred.
Further, these organic solvents can be used alone or as a mixed solvent. The amount of organic solvent to be used can be arbitrarily changed as long as it forms an azeotrope with water, and is usually used in an amount 1 to 10 times the amount (parts by weight) of the tertiary alcohol. Examples of the acid catalyst used in the present invention include mineral acids such as sulfuric acid and phosphoric acid, organic sulfonic acids, and strongly acidic cation exchange resins having sulfonic acid groups. When using acids that dissolve in the resulting tertiary alkyl hydroperoxide solution, it is necessary to use a sulfonic acid-based strong acid that does not remain in the solution and can be easily separated. Preferably, a cation exchange resin is used. The amount of catalyst used is in the range of 0.0001 to 0.1 times (part by weight), preferably 0.001 to 0.05 times (part by weight), based on the charging liquid. The reaction temperature varies widely depending on the reactivity of the reactants and the properties of the solvent, but is usually carried out within the range of 40 to 80 °C, and the pressure can be elevated, normal pressure, or subatmospheric pressure. It is. The reaction time is usually 1 to 20 hours, preferably 3 to 10 hours. The reaction mode can be either batchwise or continuous, and may be appropriately selected depending on the production scale. When tertiary alcohol is converted to tertiary alkyl hydroperoxide under the above reaction conditions, the conversion rate of hydrogen peroxide is over 90% and the selectivity of tertiary alkyl hydroperoxide is over 90%. The single flow yield of tertiary alkyl hydroperoxide is based on the hydrogen peroxide used.
It becomes 80-90 mol%. The resulting tertiary alkyl hydroperoxide is obtained as a solution containing a small amount of hydrogen peroxide, a tertiary alcohol, a by-product dialkyl hydroperoxide, and an organic solvent as a reaction solvent. It is desirable that the phenanthrene used in the present invention be of high purity, but in view of economic efficiency, it can be used as long as it has a purity of 80% or more, especially 90% or more. In the actual oxidation reaction, after removing the 9,10-phenanthrenequinone produced in the reaction,
It is also possible to wash and purify the by-product diphenic acid and small amounts of impurities contained in the reaction solution with water, alkaline water, etc., and then reuse them as they are.
Furthermore, phenanthrene can be recovered and reused from the reaction solution containing unreacted phenanthrene by a conventional distillation operation. The organic peroxide that can be used as an oxidizing agent for phenanthrene is the tertiary alkyl hydroperoxide obtained by converting the tertiary alcohol mentioned above with hydrogen peroxide. It is a solution containing hydrogen, tertiary alcohol, by-product dialkyl peroxide, and an organic solvent, and can be used as it is or after being appropriately concentrated and purified by conventional methods. It is preferable that the amount of tertiary alkyl hydroperoxide used is within the range of 0.5 to 4 moles per mole of phenanthrene, and the conversion rate of phenanthrene is kept within the range of 30 to 80%. In other words, the smaller the phenanthrene conversion rate, the more
-Phenanthrenequinone selectivity tends to be high, and when the phenanthrene conversion rate is increased to nearly 100%, the selectivity for 9,10-phenanthrenequinone is 80%.
It will drop below. Therefore, by setting the phenanthrene conversion rate to 90% or less, preferably 80% or less, the 9,10-phenanthrenequinone selectivity can be maintained at 80% or more, and even 90% or more.
By simply cooling this reaction solution and crystallizing the reaction product, the 9,10-phenanthrenequinone purity of the product is over 90%, and even higher than 98%. easily obtained. During the oxidation reaction of phenanthrene, the tertiary alkyl hydroperoxide decomposes almost 100% and is converted into tertiary alcohol, but the tertiary alcohol produced is separated from the organic solvent in the tertiary alkyl hydroperoxide or by the reaction. It can be continuously taken out of the reaction system together with a part of the organic solvent, or most of the produced 9,10-phenanthrenequinone can be removed from the reaction solution by a conventional distillation operation. It can be recovered. The recovered tertiary alcohol containing the organic solvent may be used as it is or after the organic solvent is separated and purified by a conventional distillation process, it is converted to tertiary alkyl hydroperoxide using hydrogen peroxide, and then liquid-phase oxidation of phenanthrene is carried out again. It is recycled by supplying it to the reaction. The organic solvent used in the phenanthrene oxidation reaction that can be used in the present invention is stable against tertiary alkyl hydroperoxides under the conditions used, forms an azeotrope with water, and is easily separated without dissolving them. Any organic solvent can be used. In the present invention, the operation of distilling and removing the reaction product water generated in the oxidation reaction of phenanthrene to 9,10-phenanthrenequinone as an azeotrope together with the organic solvent that is the reaction solvent is important in the present invention. Unless the produced water generated during the reaction is removed from the reaction system, the oxidation reaction of phenanthrene will not proceed at all, and of course the desired 9,10-
No phenanthrenequinone is produced. Therefore, in order to remove the product water generated in the reaction, an organic solvent that forms an azeotrope with water in a boiling state is used, the evaporated water and the organic solvent are condensed and separated, and only this organic solvent is released into the reaction system. By circulating and replenishing it, you can achieve that purpose. Examples include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene; aliphatic and alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane; ethyl acetate, propyl acetate, and acetic acid. Examples include organic carboxylic acid esters such as butyl, and particularly preferred are benzene, ethylbenzene, and n-hexane. Further, these organic solvents can be used alone or as a mixed solvent. Furthermore, it is recommended to use the same organic solvent used in the conversion of tertiary alcohol to tertiary alkyl hydroperoxide with hydrogen peroxide. The amount of organic solvent used can vary within wide limits. The reaction can be carried out in a uniform layer or in a heterogeneous layer, but in order to obtain high purity 9,10-phenanthrenequinone, the amount (parts by weight) of phenanthrene is usually 1 to 50 times, preferably 3 to 30 times the amount of phenanthrene. Amount (parts by weight)
used within the range of As molybdenum-containing compounds that can be used as catalysts in the present invention, both inorganic and organic molybdenum compounds are effective, but those that are soluble in organic solvents are particularly desirable; examples include enols such as acetylacetonate. salts, naphthenic acids,
Examples include organic carboxylic acid salts such as stearic acid, carbonyl, etc., and acetylacetonate is particularly preferred. The amount of catalyst used can vary within a wide range, but is usually
It is used within the range of 0.001 mol to 0.2 mol, preferably 0.003 to 0.1 mol. The reaction temperature in the phenanthrene oxidation reaction varies widely depending on the reactivity of the reactants and the properties of the solvent, but is usually 40 to 120°C, preferably 60 to 100°C.
Implemented within the scope of. The reaction is carried out under pressure conditions sufficient to maintain a liquid reaction phase, although elevated or subatmospheric pressures are also possible and are usually carried out at atmospheric pressure. The reaction time in the present invention varies depending on the desired phenanthrene conversion rate and 9,10-phenanthrenequinone selectivity, but is usually 1 to 14 hours, preferably 2 to 8 hours. The reaction mode can be either batchwise or continuous, and may be appropriately selected depending on the production scale. 9, produced by liquid phase oxidation reaction of phenanthrene
To remove 10-phenanthrenequinone from the reaction solution, the reaction solution containing 9,10-phenanthrenequinone is cooled to room temperature or below to precipitate 9,10-phenanthrenequinone, and then the reaction solution is separated using a centrifuge and a filter. If solid-liquid separation is performed using a press or the like, a product of 9,10-phenanthrenequinone with a purity of 90% or more, excluding the organic solvent, can be obtained. The main small amounts of impurities are the by-product diphenic acid and unreacted phenanthrene, and other than that, there are only impurities present in the raw material phenanthrene and a small amount of oxidation products for the impurities. . If necessary, a new 9,10-phenanthrenequinone product with a purity of 98% or higher can be easily obtained by washing with an organic solvent, hot water, alkaline aqueous solution, etc. After the 9,10-phenanthrene quinone is extracted, unreacted phenanthrene exists along with a small amount of phenanthrene quinone and diphenoic acid, but when this liquid is reused as part of the raw material phenanthrene, It is necessary to wash the liquid with warm water or an alkaline aqueous solution to remove diphenoic acid. That is, when a phenanthrene-containing liquid containing diphenic acid is used as a phenanthrene raw material and subjected to an oxidation reaction again, the selectivity of 9,10-phenanthrenequinone is extremely reduced, and the production of diphenic acid as a by-product increases. Not only is the yield of 9,10-phenanthrenequinone significantly reduced, but the purity of 9,10-phenanthrenequinone in the resulting product is reduced to below 80%. Further, by recovering unreacted phenanthrene contained in the liquid by a conventional distillation operation, it can be supplied again as a phenanthrene raw material to the oxidation reaction. Therefore, 9,10-phenanthrene can be obtained in high yield without loss of phenanthrene. The device of the present invention will be specifically explained below with reference to Examples, but it goes without saying that the present invention is not limited to these examples. Example 1 (a) Preparation of tert-butyl hydroperoxide solution In a 500 ml glass round bottom three-necked flask equipped with a stirrer, thermometer and condenser with water separator, 20.0 g of 60.2% hydrogen peroxide solution and tert-butyl hydroperoxide solution were added. Alcohol 30.0
g, 270 g of benzene and 0.7 g of strong acidic cation exchange resin “Diaion SKIBH” manufactured by Mitsubishi Kasei Industries, Ltd.
The pressure inside the reaction system was controlled at 270 to 3300 Torr so that the liquid temperature of the contents remained at 50° C. and in a boiling state. The evaporated azeotropic mixture of water and benzene was condensed and separated into water and benzene, and the benzene was directly refluxed into the flask and maintained for 8 hours. Gas chromatography and chemical analysis of various components of the reaction solution, tert-butyl hydroperoxide solution, and the distilled water separated outside the system were performed using conventional methods, and the results shown in Table 1 were obtained. (b) Oxidation reaction of phenanthrene and recovery of tert-butyl alcohol Purity was measured in a 500 ml glass round bottom four-necked flask equipped with a stirrer, thermometer and condenser with water separator.
19.3g of 92.5% raw material phenanthrene is 100 mmol as phenanthrene, 300g of benzene, and 0.6g of bis(acetylacetonato)oxomolybdenum.
When the contents are heated to a boiling state (liquid temperature of about 80°C), the 9.62% tert-
281 g (300 mmol) of butyl hydroperoxide solution was added dropwise over 3 hours, and the evaporated azeotropic mixture of water and benzene was condensed and separated into water and benzene, with most of the benzene refluxing directly into the flask. However, a portion equivalent to about 50 c.c./hr was continuously extracted from the system and recovered as a tert-butyl alcohol-benzene solution over 6 hours to complete the oxidation reaction. After the reaction is complete, the reaction solution is 20%
The resulting cake was cooled to 60°C and dried at 60°C for 6 hours under a pressure of 50 Torr or less to obtain a product. Various components of the recovered tert-butyl alcohol solution, product, and reaction solution were analyzed by gas chromatography and liquid chromatography using conventional methods, and the results shown in Table 2 were obtained. (c) Recovery of phenanthrene The reaction solution obtained in Example 1(b) was placed in a glass cylindrical oil-water separator equipped with a stirrer, a thermometer, and a condenser, and an extraction nozzle (Kotuku) at the bottom. and 100 g of a 5% caustic soda aqueous solution were charged, and the contents were vigorously stirred for 30 minutes while maintaining the liquid temperature at 50° C., and then left to stand and the separated lower layer (aqueous layer) was extracted. The same operation was repeated again using a 5% aqueous solution of caustic soda, and then washing was performed in the same manner with water until the alkaline content disappeared. Various components of the obtained cleaning solution were analyzed by gas chromatography and liquid chromatography using conventional methods, and the results shown in Table 3 were obtained. Examples 2 to 5 (a) Preparation of tert-butyl hydroperoxide solution Example 1(a) was prepared by adding tert-butyl alcohol and benzene to the recovered tert-butyl alcohol solution obtained in Example 1(b). A tert-butyl hydroperoxide solution was prepared in the same manner as (Example 2(a)). Below, the recoveries obtained in Examples 2(b), 3(b), and 4(b)
The same operation was performed for tert-butyl alcohol solution (Examples 3(a), 4(a), and 5(a)). The results are shown in Table-1. (b) Oxidation reaction of phenanthrene and recovery of tert-butyl alcohol This was carried out by adding 92.5% purity raw material phenanthrene, bis(acetylacetonato)oxomolybdenum, and benzene to the cleaning solution containing phenanthrene obtained in Example 1(c). Prepared in Example 2(a)
The oxidation reaction of phenanthrene and the recovery of tert-butyl alcohol were carried out using a tert-butyl hydroperoxide solution in the same manner as in Example 1(b) (Example 2(b)). Below, the cleaning solutions containing phenanthrene obtained in Examples 2(c), 3(c), and 4(c) and Examples 3(a), 4(a), and 5
The same procedure was carried out using the tert-butyl hydroperoxide solution prepared in (a) (Example 3).
(b), 4(b), 5(b)). The results are shown in Table-2. (c) Recovery of phenanthrene The reaction solution obtained in Example 2(b) was operated in the same manner as in Example 1(c) to obtain a cleaning solution containing phenanthrene (Example 2(c)). Hereinafter, the reaction solutions obtained in Examples 3(b), 4(b), and 5(b) were operated in the same manner (Examples 3(c), 4
(c), 5(c)). The results are shown in Table 3.

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Claims (1)

[Claims] 1. When producing 9,10-phenanthrene quinone by liquid-phase oxidation of phenanthrene using an organic peroxide, (a) using an acid catalyst as a catalyst and producing it by reaction; In the coexistence of an organic solvent capable of distilling water out of the system as an azeotrope, the tertiary alcohol is converted to a tertiary alkyl hydroperoxide with hydrogen peroxide, and (b) the resulting tertiary alcohol is Using an alkyl hydroperoxide and a molybdenum-containing compound as a catalyst, the water produced by the reaction is coexisted with an organic solvent that can be distilled out of the system as an azeotrope. tertiary alkyl hydroperoxide is used within the range of 0.5 to 4 mol, and
Production of tertiary alkyl hydroperoxide by keeping the conversion rate of phenanthrene in the range of 30 to 80% and recovering the tertiary alcohol and organic solvent, which are the decomposition products of the by-produced tertiary alkyl hydroperoxide. A method for producing 9,10-phenanthrenequinone, which is characterized in that it is recycled in the process. 2. The manufacturing method according to claim 1, characterized in that tert-butyl alcohol or tert-amyl alcohol is used as the tertiary alcohol. 3. The manufacturing method according to claim 1 or 2, characterized in that a sulfonic acid-based strongly acidic cation exchange resin is used as the acid catalyst. 4. The manufacturing method according to claim 1, 2 or 3, characterized in that acetylacetonate of a molybdenum compound is used as the molybdenum-containing compound.