JP2003128616A - Method for producing dimer and/or trimer of acetone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for keeping the activity of a basic solid catalyst as high as possible for a long period in dimerizing or trimerizing acetone using the basic catalyst. SOLUTION: A raw material acetone containing 50 wt.ppm or less of esters is used for producing a dimer and/or a trimer of the acetone by bringing the raw material acetone into contact with the basic solid catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an acetone dimer and / or trimer such as diacetone alcohol, triacetone dialcohol, and semiphorone by bringing acetone into contact with a basic solid catalyst. . For more information,
The present invention relates to a method for suppressing a decrease in the activity of a basic solid catalyst when an industrially produced acetone is contacted with a basic solid catalyst to produce an acetone dimer and / or trimer.

[0002]

2. Description of the Related Art Acetone dimer or trimer, such as diacetone alcohol, is a highly useful substance as a raw material for producing mesityl oxide, methyl isobutyl ketone, methyl isocarbinol, hexyl glycol and the like. . These acetone dimers or trimers can be produced by bringing acetone into contact with a basic solid catalyst.

Acetone, which is a raw material, is usually industrially produced based on the Wacker method and the cumene oxidation method, and in recent years, most of it has been by-produced acetone when phenol is produced by the cumene oxidation method. Further, as a method for producing an acetone dimer or trimer such as diacetone alcohol from acetone, acetone is contacted with a solid catalyst containing a hydroxide selected from an alkali metal or an alkaline earth metal. A method for producing acetone alcohol (JP-B-47-18731) or a method for producing diacetone alcohol from acetone using an anion exchange resin as a catalyst in the presence of a lower alcohol (JP-A-58-58).
No. 59935) has been reported.

The reaction for obtaining an acetone dimer or trimer such as diacetone alcohol from this acetone is an equilibrium reaction, and the production rate of diacetone alcohol varies greatly depending on the activity of the basic solid catalyst. However, the activity of this basic solid catalyst decreases significantly with time. Therefore, when deactivation of the catalyst occurs during continuous production, it is usually necessary to replace or regenerate the catalyst. However, there are problems that it is necessary to interrupt the operation of the reactor while the catalyst is exchanged or regenerated, and the catalyst exchange or regeneration operation is very complicated.

As a method for preventing the activity of the basic solid catalyst from decreasing, a method of removing an acidic component in acetone has been reported (Japanese Patent Publication No. 1-175952). In this publication, an acetone stream and an alkaline solution are brought into contact with each other to neutralize an acidic component contained in the acetone stream, and then acetone is brought into contact with a basic solid catalyst to form a dimer of acetone and / or
Or a method for producing a trimer is described.

[0006]

However, as a result of the investigations by the present inventors, even when the acid content in acetone is low (for example, 0.2 mg / l or less), the activity of the catalyst is evaluated by the catalyst evaluation. It has been found that it is difficult to carry out continuous operation for a long period of time due to large activity deterioration. In view of such circumstances, the inventors of the present invention have earnestly searched for a catalyst deactivating substance in a method of producing a dimer and / or trimer of acetone by bringing acetone into contact with a basic solid catalyst, and as a result, The esters contained in the product are the main cause of catalyst activity deterioration, and by controlling the concentration of the esters below a specified value, it is possible to maintain the activity of the basic solid catalyst in a higher state for a long period of time. The inventors have found out what can be done and have reached the present invention.

[0007]

The summary of the present invention is as follows.
In the method for producing an acetone dimer and / or trimer by contacting raw material acetone with a basic solid catalyst, the raw material acetone having an ester concentration of 50 ppm by weight or less is used. It exists in a method for producing a dimer and / or a trimer.

[0008]

The present invention will be described in more detail below. In the present invention, the starting material acetone is brought into contact with a basic solid catalyst to form an acetone dimer such as diacetone alcohol, triacetone dialcohol, and semiphorone, and / or
Alternatively, a trimer is produced.

The present invention is characterized in that the starting material acetone has a concentration of esters of usually 50 ppm by weight or less, preferably 10 ppm by weight or less, more preferably 2 ppm by weight or less. The concentration of esters contained in the raw material acetone is 50 weight pp
If it is larger than m, the effect of suppressing the activity decrease of the basic solid catalyst is not sufficient, which is not preferable. Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate,
Mention may be made of any one of methyl butyrate, ethyl butyrate, propyl butyrate and butyl butyrate or a mixture thereof.

When the raw material acetone contains a high concentration of esters, the concentration of the ester contained in the raw material acetone is adjusted to 50 by performing a pretreatment operation such as distillation or adsorption.
The weight can be reduced to ppm or less. As the basic solid catalyst, a solid catalyst containing a hydroxide selected from alkali metals or alkaline earth metals can be used. Examples of the alkali metal or alkaline earth metal include sodium hydroxide, magnesium hydroxide,
Examples thereof include calcium hydroxide, strontium hydroxide, barium hydroxide and the like. These basic solid catalysts are
They may be used alone or in combination of two or more.
Further, these can be used alone as a catalyst, but can also be used by supporting them on a carrier. As the carrier, a carrier having low solubility in water, for example, talc, diatomaceous earth, kaolin, titanium oxide or the like can be used.
Also, these can be used by bonding with alumina cement,
You may use what baked at low temperature with the silicon compound, such as sodium metasilicate.

An anion exchange resin can also be used as the basic solid catalyst. The anion exchange resin can be produced by a known method, for example, by introducing various anion exchange resins into a polymer substrate obtained by copolymerizing styrene and divinylbenzene. Such anion exchange resin includes a strongly basic ion exchange resin and a weakly basic ion exchange resin, each of which is a so-called gel type,
There are a porous type and a high porous type, and any of them can be used in the present invention. When an anion exchange resin is used as the solid catalyst, it is preferable that a lower alcohol is present during the reaction. As the lower alcohol, for example, an alcohol having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol, propanol, butanol and isobutanol can be used.

The basic solid catalyst can be packed in the reactor in the form of a fixed bed, fluidized bed, moving bed or the like and brought into contact with acetone. In the present invention, the basic solid catalyst is fixed bed. It is preferable to contact with acetone. The temperature at which acetone and the basic solid catalyst are brought into contact is usually -40 ° C to 50 ° C, preferably -5 ° C to 25 ° C.
Is. The other reaction conditions may be the same as those in the conventionally known method.

[0013]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following examples, "%" is "% by weight" and "ppm" is "weight pp."
m ”and“ mg / l ”are“ mg / liter ”and“ ml /
“H” means “milliliter / hour” and “Hr” means “hour”.

Example 1 The acidic components and esters in acetone used as a raw material were measured by the method shown in the analytical methods shown in Tables 1 and 2. The acidic components were 0.2 mg / l or less, and the esters were acetic acid. Methyl was present at 1 ppm. Methyl acetate was measured by an absolute calibration curve method from mass chromatography of an EI fragment (m / z = 74) characteristic of methyl acetate. The calibration curve was prepared by the standard addition method. Water was added to this acetone so that the water concentration was 1.4%, and used as a raw material. As the catalyst, a basic solid catalyst obtained by aging a mixture of barium hydroxide, cement and talc in a closed container at 50 ° C. was used. Acetone having a water concentration of 1.4% as a raw material was passed through a reactor having a catalyst filling amount of 15 g at 150 ml / H, and the compositions of acetone, diacetone alcohol, and triacetone dialcohol in the outlet reaction liquid were measured. The reaction temperature was constant at 10 ° C. and the reaction pressure was atmospheric pressure. Table 3 shows the yields of diacetone alcohol 8 hours and 176 hours after the start of the reaction.

Example 2 A reaction was carried out in the same manner as in Example 1 except that 20 ppm of methyl acetate was added to the starting acetone of Example 1 as the starting acetone. 5 from the start of the reaction in Table 3
The diacetone alcohol yields after hours and 197 hours are shown.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that 100 ppm of methyl acetate was added to the starting acetone of Example 1 as the starting acetone. Table 3 shows the yields of diacetone alcohol after 5 hours and 63 hours from the start of the reaction.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

EFFECTS OF THE INVENTION According to the present invention, in a method for producing a dimer and / or a trimer of acetone by contacting acetone with a basic solid, the basic solid catalyst has a higher activity. Since it can be maintained in the state for a long time, the dimer and / or trimer of acetone can be continuously produced in high yield for a long time.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shunji Katsuki             10-10 Shiodotsu, Kurashiki City, Okayama Prefecture Mitsubishi Chemical             Within the corporation F-term (reference) 4H006 AA02 AC25 AC41 BA02 BA06                       BA29 BA72                 4H039 CA60 CL11 CL19

Claims (4)

[Claims] 1. A method for producing an acetone dimer and / or trimer by bringing raw material acetone into contact with a basic solid catalyst, the raw material acetone having an ester concentration of 50 ppm by weight or less is used. Acetone 2 characterized by
A method for producing a monomer and / or a trimer. 2. The acetone dimer and / or 3 according to claim 1, wherein the basic solid catalyst contains at least one hydroxide selected from alkali metals and alkaline earth metals.
Method for producing a polymer. 3. The method for producing an acetone dimer and / or trimer according to claim 1, wherein the basic solid catalyst is an anion exchange resin. 4. The ester is methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate,
Ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate,
Acetone 2 according to any one of claims 1 to 3, which is any one of butyl butyrate or a mixture thereof.
A method for producing a monomer and / or a trimer.