JP2534310B2 - Ketone manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a ketone, more specifically, a compound selected from the group consisting of an aliphatic carboxylic acid and its ester, an aliphatic carboxylic acid ester and an aromatic carboxylic acid. In the case of producing a ketone by reacting a mixture with a compound selected from the group consisting of acid esters in the presence of a catalyst under heating, as a catalyst, the II
IA, VIA, VIIA, VIII, IB, I
The present invention relates to a method for producing a ketone, which comprises using a catalyst in which a simple substance and / or a compound of a metal element of Group IB or Group IIIB is supported on activated carbon.

The ketones such as acetone and acetonephenone provided by the production method of the present invention are useful as solvents, raw materials for fragrance synthesis, and the like.

[Prior Art] Conventionally, an ester such as an aliphatic carboxylic acid and / or a methyl ester, or a metallic element such as calcium, barium, manganese, zinc, or zirconium which is not loaded with an aliphatic carboxylic acid and benzoic acid on a carrier is used. Carbonate,
It is known that a corresponding ketone such as an aliphatic ketone or acetophenone can be obtained by reacting at a temperature of 370 to 600 ° C. in the presence of a solid catalyst such as an oxide. Further, instead of the solid catalyst not supported on the above carrier,
It has been shown that by using a catalyst in which a compound of a metal element such as manganese is supported on an oxide such as asbestos or silica gel, stability of catalytic activity is improved and handling of the catalyst is facilitated.

[Problems to be Solved by the Invention] In the method for producing a ketone using the solid catalyst not supported on the carrier or the catalyst supported on the oxide, the reaction rate at a reaction temperature near 400 ° C. Since it is low, industrially unfavorable manufacturing conditions such as a remarkably low space velocity in order to carry out the reaction at a sufficiently high conversion rate, or a remarkably high reaction temperature exceeding 400 ° C. are adopted. There is a need.

Therefore, the object of the present invention is to obtain a good yield of a ketone from a mixture of a compound selected from the group consisting of an aliphatic carboxylic acid and its ester and a compound selected from a group consisting of an aliphatic carboxylic acid ester and an aromatic carboxylic acid ester. The object is to provide an industrially advantageous method for producing a high rate and high selectivity.

[Means for Solving the Problems] According to the present invention, the above object is from a group consisting of a compound selected from the group consisting of an aliphatic carboxylic acid and an ester thereof and an aliphatic carboxylic acid ester and an aromatic carboxylic acid ester. When a ketone is produced by reacting a mixture with a selected compound with heating in the presence of a catalyst, the ketone is used as a group IIIA group VIA group in the periodic table.
Group, Group VII A, Group VIII, Group IB, Group II B or Group
It is achieved by providing a method for producing a ketone, which comprises using a catalyst in which a simple substance and / or a compound of a group IIIB metal element is supported on activated carbon.

The aliphatic carboxylic acid used in the present invention is a linear or branched alkanoic acid having a basicity of 1 or more,
A hydrocarbon group such as an aryl group such as a phenyl group and a tolyl group, a cycloalkyl group such as a cyclohexyl group; a group having a hetero atom such as an oxygen atom and a nitrogen atom; It may have a substituent. The number of carbon atoms contained in the aliphatic carboxylic acid is not particularly limited, but it is usually preferably in the range of 2 to 30, and more preferably in the range of 2 to 18. Examples of the aliphatic carboxylic acid include acetic acid, propionic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, isohexanoic acid, neohexanoic acid, heptanoic acid, octane. Acids, isooctanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, icosanoic acid, etc. having a basicity of 1; ethane-1,2-dicarboxylic acid, propane-1,3-dicarboxylic acid Acids, butane-1,4-dicarboxylic acid, pentane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid and other basic alkanoic acids; and ethane-1,2-dicarboxylic acid monomethyl, propane- 1,3-Dicarboxylate monoethyl, butane-1,4-dicarboxylate monomethyl, pentane-1,5-dicarboxylate monoethyl, hexane-1,6 Such as monoalkyl esters of alkanoic acids basicity 2 such as dicarboxylic acid monomethyl can be exemplified. Examples of the aliphatic carboxylic acid ester include alkyl esters such as methyl ester and ethyl ester of the above aliphatic carboxylic acids; aryl esters such as phenyl ester and tolyl ester; aralkyl esters such as benzyl ester; cycloalkyl esters such as cyclohexyl ester. Among them, it is preferable to use the methyl ester of the aliphatic carboxylic acid. The ester of an aliphatic polycarboxylic acid having a basicity of 2 or more is a neutral ester in which all of the two or more carboxyl groups of the aliphatic polycarboxylic acid are esterified. As typical examples of the aliphatic carboxylic acid ester, methyl acetate, ethyl acetate,
Propyl acetate, isopropyl acetate, butyl acetate, phenyl acetate, methyl propionate, methyl butanoate, methyl 2-methylpropanoate, methyl pentanoate, methyl 2-methylbutanoate, methyl hexanoate, methanoic acid octanoate, methyl decanoate, Esters of alkanoic acid having a basicity of 1 such as methyl undecanoate, methyl dodecanoate, methyl pentadecanoate, methyl hexadecanoate, methyl octadecanoate, methyl icosanoate; butane-1,4-dicarboxylate dimethyl, pentane-1,5- Examples thereof include diesters of alkanoic acids having a basicity of 2 such as dimethyl dicarboxylate and dimethyl octane-1,8-dicarboxylate. As the above-mentioned aliphatic carboxylic acid or its ester, one kind may be used alone, or two or more kinds may be used in combination.

Examples of the aromatic carboxylic acid ester used in the present invention include alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of aromatic carboxylic acid; aralkyl esters such as benzyl ester; aryl esters such as phenyl ester. Can be mentioned. The aromatic carboxylic acid is an aromatic carboxylic acid in which one or more carboxyl groups are bonded to the aromatic ring, and examples of the aromatic ring include a benzene ring, a naphthalene ring, a pyridine ring and the like, and a benzene ring is particularly preferable. . In addition, the aromatic ring may be a hydrocarbon group such as an alkyl group, an alkenyl group or a cycloalkyl group; a group having a hetero atom such as an oxygen atom or a nitrogen atom; You may have. The ester of an aromatic polycarboxylic acid having a basicity of 2 or more is a neutral ester in which all of the two or more carboxyl groups of the aromatic polycarboxylic acid are esterified. As the aromatic carboxylic acid ester, it is preferable to use a methyl ester of an aromatic carboxylic acid. As typical examples of aromatic carboxylic acid esters, methyl benzoate, ethyl benzoate, phenyl benzoate, 4-
Methyl methylbenzoate, methyl 3-methylbenzoate, 2
-Methyl methyl benzoate, methyl 2,4-dimethyl benzoate, methyl naphthalene-1-carboxylate, naphthalene-
Esters of aromatic monocarboxylic acids such as methyl 2-carboxylate, methyl biphenyl-4-carboxylate, methyl 4-chlorobenzoate, methyl 4-acetoxybenzoate, methyl 4-hydroxybenzoate and methyl 4-methoxybenzoate. Dimethyl terephthalate, dimethyl isophthalate,
Examples thereof include esters of aromatic dicarboxylic acids such as dimethyl phthalate, dimethyl biphenyl-4,4'-carboxylate, and dimethyl naphthalene-2,6-dicarboxylate. Among these aromatic carboxylic acid esters,
Particular preference is given to using methyl benzoate. As said aromatic carboxylic ester, 1 type may be used individually and 2 or more types may be used together.

The reaction according to the present invention is formally shown by a chemical reaction formula as follows.

(In the formula, R ¹ represents an alkyl group which may have a substituent, R ² represents an alkyl group which may have a substituent or an aryl group which may have a substituent, X ¹ represents a hydrogen atom or a hydrocarbon group, and X ² represents a hydrocarbon group.) As can be understood from the above chemical reaction formula, in the present invention, the starting compound carboxylic acid and / or its ester is appropriately used. The desired ketone can be obtained by selective use. For example, an acyclic aliphatic ketone can be obtained by using a compound selected from the group consisting of an aliphatic monocarboxylic acid and its ester and an aliphatic monocarboxylic acid ester as a raw material compound. A cyclic ketone can be obtained by using an aliphatic dicarboxylic acid ester as a raw material compound. Further, a mixture of a compound selected from the group consisting of an aliphatic monocarboxylic acid and its ester (hereinafter referred to as compound A) and an aromatic monocarboxylic acid ester (hereinafter referred to as compound B) is used. An alkyl aryl ketone can be obtained by using it as a raw material compound. In this case, the use ratios of the compound A and the compound B are not particularly limited, but if the use ratio of the compound B is increased, the selectivity to the alkyl aryl ketone tends to increase, and therefore the alkyl aryl ketone When production is desired, it is preferable to use the compound A and the compound B in a ratio such that the molar ratio (the number of compounds A / the number of compounds B) is 1/2 or less, and 1/4 to It is more preferable to use it at a ratio within the range of 1/15. Generally, when a carboxylic acid ester is used as the raw material compound, the operation of supplying the raw material to the reaction system is easy.

The catalyst used in the present invention is a group III A in the periodic table.
Clan, VIA, VIIA, VIII, IB, IIB
A catalyst in which a simple substance and / or a compound of a group III or group IIIB metal element is supported on activated carbon. Lanthanoid elements such as lanthanum and cerium as metal elements of Group IIIA in the periodic table; chromium, molybdenum, tungsten, etc. as metal elements of Group VIA;
Group III metal elements such as manganese; Group VIII metal elements such as iron, cobalt and nickel; Group IB metal elements such as copper; Group IIB metal elements such as zinc; and Group III Examples of the metal element of Group B include aluminum and the like. Among these metal elements, lanthanum, chromium, manganese, cobalt, copper, zinc, aluminum and the like are particularly preferable. Compounds of metal elements include oxides; hydroxides; hydrated oxides; mineral salts such as nitrates, carbonates, bicarbonates, sulfates, halides, oxyhalides, basic carbonates; carboxylic acids. Organic acid salts such as salts; organometallic compounds such as alkylated compounds; complex compounds such as ammine complexes, acetylacetonato complexes, carbonyl complexes; complex metal compounds or compositions such as alloys; or mixtures or complex compounds thereof. To be By supporting the simple substance and / or compound of these metal elements on activated carbon, the catalytic activity thereof can be effectively exhibited. Among these, metal salt carboxylates, nitrates, sulfates, chlorides and the like are preferable from the viewpoint that they can be easily supported on activated carbon by a wet supporting method such as an impregnation method as an aqueous solution, and among them, acetates and propionates are preferable. More preferred are aliphatic carboxylic acid salts such as; carboxylic acid salts such as aromatic carboxylic acid salts such as benzoate. Typical examples of carboxylates of metal elements are manganese (II) acetate, lanthanum acetate, cobalt (II) acetate, cobalt (III) acetate, copper (II) acetate, zinc acetate, cerium (III) acetate, aluminum acetate, Chromium (III) acetate
Among these, manganese (II) acetate, zinc acetate, lanthanum acetate, aluminum acetate, cerium (III) acetate and the like are preferable, and manganese (II) acetate and the like are particularly preferable. Compared to other compounds, acetate of metal element can be easily supported on activated carbon, is easily available, and exhibits high activity even with a catalyst prepared at a relatively low temperature. It is advantageous. The form of the simple substance and alloy of the metal element to be supported on the activated carbon is not particularly limited, but the metal particles in a highly dispersed state on the activated carbon during the preparation of the catalyst, the pretreatment, or the reaction for producing the ketone. Alternatively, ultrafine particles, vapor-deposited metals, colloidal metals and the like are preferable because they can be easily converted into metal compounds. The loading rate of the metal element in the catalyst cannot always be specified uniformly depending on the type and form of the metal element used,
The ratio of the weight of the metal element to the total weight of the weight of the metal element and the weight of the activated carbon is preferably in the range of 1 to 40%, more preferably 6 to 25%. If the loading rate is too low, the activity of the obtained catalyst tends to be insufficient. Conversely, if it is too high, the activity per unit amount of the metal element in the obtained catalyst decreases, resulting in a low reaction. The high activity at temperature tends to be insufficient. As the activated carbon used as a catalyst carrier,
Examples include plant-based activated carbon such as coconut shell charcoal and charcoal-based activated carbon; animal-based activated carbon such as animal charcoal; petroleum-based activated carbon such as petroleum pitch-based activated carbon and synthetic resin-based activated carbon; and coal-based activated carbon or a mixture thereof. Among these activated carbons, it is preferable to use activated carbon which can be generally used as a catalyst, a catalyst carrier or an adsorbent. The shape of the activated carbon used as the carrier is not particularly limited, and it may be powdery, granular,
Any shape such as a pellet shape, a spherical shape, a cloth shape, a plate shape, or a fiber shape can be appropriately selected and used.

The method for preparing the catalyst to be used in the present invention is not particularly limited, and an adsorption supporting method and an impregnation method from a solution such as an aqueous solution, a wet kneading method using a suspension, a wet deposition method and a wet colloid adsorption method, etc. Wet-supporting method; dry-supporting method such as solid dry mixing method; vapor-phase adsorption method, vapor-phase deposition method (CV
A known supporting method such as a vapor phase supporting method such as a method D) or a vapor deposition method can be adopted. Among these supporting methods,
In particular, an impregnation method from a solution such as an aqueous solution can be preferably adopted. The catalyst obtained by the loading operation may be subjected to a drying treatment, if necessary. In particular, the catalyst obtained by the wet loading method is preferably subjected to a drying treatment. The conditions of this drying treatment are not particularly limited, but the drying treatment is generally performed under reduced pressure or normal pressure at room temperature to 20 ° C.
It is preferable to carry out at a temperature in the range of about 0 ° C. for a time in the range of about 0.5 to 30 hours. The activated carbon-supported catalyst obtained as described above is used in the reaction according to the present invention as it is or after appropriately subjected to pretreatment such as activation treatment. The conditions of this pretreatment include the type of the simple substance and / or the compound of the metal element used, the loading rate of the metal element on the carrier, the type of the raw material compound used for the ketonization reaction,
Although it cannot always be uniformly specified depending on reaction conditions, the pretreatment is generally performed in a stream of an inert gas such as nitrogen gas or helium gas or under reduced pressure exhaust when a compound of a metal element is used in catalyst preparation. Under an inert atmosphere, usually at a temperature in the range of 100 to 550 ° C, preferably 150 to 430
It is preferable to carry out the treatment at a temperature in the range of 0 ° C. for usually 0.5 to 10 hours. Further, when a metal element simple substance or alloy is used in the catalyst preparation, the activity of the catalyst can be improved by treating with a reducing gas such as hydrogen gas or carbon monoxide gas at the above temperature. .

The reaction temperature in the reaction according to the present invention is not necessarily uniformly defined depending on the catalyst used and the starting compound, but is usually in the range of 200 to 450 ° C, preferably in the range of 250 to 420 ° C. Is the temperature of. If the reaction temperature is too low, sufficient reaction results may not be obtained, and on the contrary, if it is too high, the occurrence of undesirable side reactions and the decrease in catalyst activity may not be negligible. The reaction pressure is not particularly limited and may be any of reduced pressure, normal pressure and increased pressure, but it is preferable to adopt a pressure within the range of normal pressure to 10 kg / cm ² (gauge pressure). Is.

The reaction according to the present invention can be carried out by any of gas phase contact reaction, liquid phase contact reaction and gas liquid phase contact reaction, and a diluent gas, a solvent and the like can be present in the reaction system as necessary. . An inert gas such as nitrogen, argon, or helium; carbon dioxide; steam or the like is used as the diluent gas. Examples of the solvent include alkanes such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone and acetophenone; ethers; alcohols such as methanol. Used as a mixture.

As the reaction method, a continuous flow method, a semi-continuous method, a batch method or the like can be adopted, but it is generally preferable to carry out the reaction by a continuous flow method using a fixed bed catalytic reactor.

The contact time and the reaction time in the reaction according to the present invention cannot be necessarily defined uniformly depending on the catalyst and the starting compound used, the reaction temperature adopted, etc., but when the reaction is carried out by a continuous flow method, for example, the contact time 0.1 to 2
It is preferably in the range of 00 hours · g-catalyst / mol-feedstock compound, more preferably in the range of 5 to 100 hours · g-catalyst / mol-feedstock compound. When the reaction is carried out by the batch method, it is preferable to set the reaction time within the range of the reaction time converted based on the above-mentioned preferable contact time.

Separation and purification of the ketone from the reaction mixture obtained by the reaction according to the present invention can be carried out by a known method such as distillation. When an unreacted starting compound remains in the reaction mixture, the starting compound can be recovered from the reaction mixture and reused.

[Examples] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

Example of catalyst preparation Using activated carbon shown in Table 1 or silica gel shown in Table 2 as a carrier, immersing it in an aqueous solution of a predetermined metal compound (concentration: 10 to 50 g / l), and then heating it in a hot water bath Impregnated to dryness. The obtained dried product is placed in a drier for 12
A catalyst having a predetermined supporting rate was obtained by drying at 0 ° C. for 24 hours. However, the catalyst represented by C-14 in Table 1 and the catalyst represented by CB-14 in Table 2 were obtained after mixing the powdery carrier and MnCO ₃ in a mortar (dry mixing). The resulting mixture was prepared by subjecting it to the dry drying process described above.

Example 1 As a catalyst, 2.5 g of C-3 described in Table 1 was used and charged into a Pyrex reaction tube having an inner diameter of 12 mm,
Layers of quartz wool and Raschig rings were provided on the upper and lower sides to form a fixed layer. Helium was passed through the reaction tube at 100 ml / min, the temperature was raised from room temperature to 200 ° C., and pretreatment was performed at the same temperature for 2 hours. Then, the flow rate of helium was set to 30 ml / min, and methyl acetate was fed at a constant feed rate (10 ml
Liquid / h) to the reaction tube and the temperature of the catalyst layer is 200 ℃, 250
The reaction was carried out by holding at each temperature of ℃, 300 ℃ and 350 ℃ for 1.5 hours each stepwise rising. As a product one hour after setting each reaction temperature, a liquid product of the product was collected for 30 minutes around the product in a water-cooled trap provided at the outlet of the reaction tube. The collected product was injected into a gas chromatograph using a microsyringe, and its components were quantitatively analyzed. The yields of acetone after 1 hour at each temperature were 2.0% and 9%, respectively.
%, 85% and 98%, and the selectivity to acetone was almost 100% at any temperature.

Comparative Example 1 The same operation as in Example 1 was performed except that CR-3 was used instead of C-3 as the catalyst. As a result, the reaction temperature is 200
Acetone yields after 1 hour at ℃, 250 ℃, 300 ℃ and 350 ℃ were 0.5%, 8%, 38% and 82%, respectively.

Example 2 Methyl propionate was used as the reaction raw material in place of methyl acetate, and the reaction temperatures were 240 ° C, 280 ° C, 320 ° C and 3 ° C.
The same operation as in Example 1 was performed except that the temperature was 60 ° C. The yields of diethyl ketone after 1 hour at each temperature were 8.0%, 32%, 40% and 47%, respectively, and the selectivity to diethyl ketone was almost 100% at any temperature.

Comparative Example 2 The same operation as in Example 2 was performed except that CR-3 was used instead of C-3 as the catalyst. As a result, 240 ℃, 280 ℃, 32
The yields of diethyl ketone after 1 hour at temperatures of 0 ° C and 360 ° C were 0%, 19%, 28% and 33% respectively, and the selectivity to diethyl ketone was actually 280 ° C at which diethyl ketone was produced at 280 ° C. It was almost 100% at all temperatures of 320 ℃ and 360 ℃.

Example 3 The same operation as in Example 1 was carried out except that an equimolar mixture of acetic acid and methyl acetate was used as the reaction raw material instead of methyl acetate. As a result, the yields of acetone after 1 hour at the respective temperatures of 200 ° C., 250 ° C., 300 ° C. and 350 ° C. were 3%, 15%, 93% and 100%, respectively, and the selectivity to acetone was It was almost 100% at any temperature.

Comparative Example 3 The same operation as in Example 3 was performed except that CR-3 was used instead of C-3 as the catalyst. As a result, 200 ℃, 250 ℃, 30
The yields of acetone after 1 hour at temperatures of 0 ° C. and 350 ° C. were 0.5%, 8%, 10% and 55% respectively,
At the reaction temperatures of 200 ° C and 250 ° C, the selectivity to acetone was almost 100%, but at the reaction temperatures of 300 ° C and 350 ° C, methane was by-produced and the selectivity to acetone was 95% respectively. And stayed at 90%.

Example 4 Instead of acetic acid, a mixture of acetic acid and methyl benzoate (molar ratio: 1: 5) was used as a reaction raw material, and the reaction temperature was 300.
The same operation as in Example 1 was performed except that the temperature was changed to ° C. As a result, the yield of acetophenone (based on methyl benzoate) and the yield of acetone (based on acetic acid) at 1 hour after the reaction temperature was set to 300 ° C. were 24% and 46%, respectively. The molar percentages of acetophenone and acetone in the product were 72% and 28%, respectively, indicating that acetophenone was selectively obtained. On the other hand, the yield of benzophenone (based on methyl benzoate) was less than 0.5%.

Comparative Example 4 The same operation as in Example 4 was performed except that CR-3 was used instead of C-3 as the catalyst. As a result, reaction temperature 300 ℃
Yield of acetophenone (based on methyl benzoate) and yield of acetone (based on acetic acid) 1 hour after setting to
Were 8% and 21%, respectively. The molar percentages of acetophenone and acetone in the product were 66
% And 34%.

Example 5 The same operation as in Example 4 was carried out, except that a mixture of acetic acid and methyl benzoate (molar ratio: 1: 8) was used instead of acetic acid as a reaction raw material. As a result, the yield of acetophenone (based on benzoic acid) and the yield of acetone (based on acetic acid) after 1 hour at the reaction temperature of 300 ° C were 52%, respectively.
% And 8%. The molar percentages of acetophenone and acetone in the product were 98% and 2%, respectively.
And acetophenone was obtained with high selectivity. On the other hand, the yield of benzophenone was less than 0.5%.

[Effects of the Invention] According to the present invention, as is clear from the above examples, a compound selected from the group consisting of aliphatic carboxylic acids and their esters and a group consisting of aliphatic carboxylic acid esters and aromatic carboxylic acid esters are selected. The corresponding ketone can be produced from a mixture with the compound described above in good yield, high selectivity and without deterioration in reaction results over time. Further, according to the present invention, a ketone can be produced with good reaction results even at a relatively low reaction temperature.

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Claims (1)

(57) [Claims] 1. A mixture of a compound selected from the group consisting of an aliphatic carboxylic acid and an ester thereof and a compound selected from a group consisting of an aliphatic carboxylic acid ester and an aromatic carboxylic acid ester under heating in the presence of a catalyst. In producing a ketone by reacting, the catalyst is used as a catalyst of Group IIIA, Group VIA, Group VIIA, Group VIA in the periodic table.
A method for producing a ketone, which comprises using a catalyst in which a simple substance and / or a compound of a metal element of group II, group IB, group IIB or group IIIB is supported on activated carbon.