JP2000015094A - Catalyst for addition of alkylene oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce by-products in a reaction product and to eliminate an operation for separating a catalyst from the product after a reaction by forming the catalyst for the addition of alkylene oxides by mixing/molding magnesium oxide with a specified quantity of alumina. SOLUTION: In the preparation of a catalyst for addition of alkylene oxides which are used as an intermediate of solvents, surfactants, and other chemical products, magnesium oxide is mixed with alumina in an amount of 5-80 wt.% of magnesium oxide, and the mixture is molded. The molded product is dried at 80-120 deg.C and baked at 400-1000 deg.C, preferably at 500-800 deg.C, in an inert gas current, air, or in vacuum. An active hydrogen-containing organic compound is reacted with an alkylene oxide in the presence of the catalyst to produce an alkylene oxide adduct. Alcohols, phenols, and others are named as the organic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an alkylene oxide addition catalyst and a method for producing an alkylene oxide adduct using the catalyst.

[0002]

BACKGROUND OF THE INVENTION Alkylene oxide adducts of active hydrogen-containing organic compounds such as alcohols and phenols are useful as solvents, surfactants, and intermediates for various chemicals. It is a substance that has been conventionally obtained by reacting an alkylene oxide such as ethylene oxide or propylene oxide with an active hydrogen-containing organic compound such as an aliphatic alcohol, ethylene glycol, or propylene glycol.

Conventionally, as a catalyst used for such a reaction, there is a magnesium oxide catalyst disclosed in, for example, Japanese Patent Publication No. 6-15038 and Japanese Patent Application Laid-Open No. 5-85979.
However, in any of the examples in which such a magnesium oxide-based catalyst is used for producing an alkylene oxide adduct, the catalyst is mixed with an active hydrogen-containing organic compound in powder form, and the alkylene oxide is subjected to addition polymerization. Therefore, after the reaction, a complicated operation of separating and recovering the catalyst by filtration, centrifugation or the like is indispensable, and there is a disadvantage that the production equipment becomes very energy-consuming.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to an alkylene oxide addition catalyst obtained by mixing and molding magnesium oxide and 5-80% by weight of alumina with respect to magnesium oxide, and an activity of the catalyst in the presence of the catalyst. This is a method for producing an alkylene oxide adduct in which a hydrogen-containing organic compound is reacted with an alkylene oxide. ADVANTAGE OF THE INVENTION According to this invention, the by-products, such as a polyethylene glycol, are few, and the addition mole number distribution can narrowly produce an alkylene oxide adduct.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The magnesium oxide used in the present invention preferably has a BET surface area of 100 m ² / g or more. The catalyst of the present invention is, for example, a magnesium oxide powder catalyst in an amount of 5 to 80% by weight based on magnesium oxide,
Preferably 10-80% by weight, more preferably 30-50% by weight
Is obtained by adding and kneading the alumina as an alumina sol, kneading, molding, and then firing. For kneading, for example, a known kneader or the like can be used. The molding can be performed by, for example, a known extrusion molding method. After being formed, it is dried at 80 to 120 ° C, and dried at 400 to 1000 ° C, preferably in an inert gas stream, air or under vacuum.
Bake at 500-800 ° C. The calcined catalyst is preferably cooled in an inert gas or vacuum to prevent adsorption of water or carbon dioxide, and after cooling, it is preferable to immerse the active hydrogen-containing organic compound used in the reaction or store it in a vacuum desiccator. . If the amount of alumina relative to magnesium oxide is less than 5% by weight, a molded catalyst having sufficient strength cannot be obtained.

The active hydrogen-containing organic compound used in the present invention may be any compound as long as it is alkoxylated, but includes alcohols, phenols, polyols, carboxylic acids, thiols, amines and amides. And the like. Among them, alcohols are preferable, and the alcohols have 1 to 1 carbon atoms.
Preferred are 30 linear or side chain primary or secondary alcohols, and more preferred are primary alcohols having 6 to 24 carbon atoms.

The alkylene oxide used in the present invention may be any alkylene oxide capable of reacting with an active hydrogen-containing organic compound to form an adduct. Epoxidized ones are preferred, and ethylene oxide, propylene oxide or mixtures thereof are particularly preferred.

The reactor used for the reaction between the active hydrogen-containing organic compound and the alkylene oxide may be any of a stirred tank batch type, a stirred tank flow type, a fixed bed flow type and the like. When used in a batch reactor, the amount of the catalyst used in the present invention is usually 0.1% based on the active hydrogen-containing organic compound.
-20% by weight is preferred, and 0.5-8% by weight is more preferred. The reaction temperature is preferably from 80 to 230 ° C, more preferably from 120 to 180 ° C, most preferably from 120 to 180 ° C.
~ 160 ° C. The reaction pressure depends on the reaction temperature, but is preferably 2 MPa absolute pressure or less, more preferably 0.3 to 0.9 M
Pa absolute pressure.

For the production of the alkylene oxide adduct, the shaped catalyst of the present invention is put into a stirring blade having a basket made of, for example, a stainless steel wire, and this and an active hydrogen-containing organic compound are charged into a reactor, and a nitrogen atmosphere is added. The reaction can be carried out by introducing an alkylene oxide under a predetermined temperature and pressure condition and then reacting, cooling, and extracting only the generated alkylene oxide adduct.

When the production of the alkylene oxide adduct is carried out in a fixed bed flow system, the catalyst of the present invention is charged into a fixed bed flow reactor, and the alkylene oxide and the active hydrogen-containing organic compound are passed therethrough. The flow rate of the liquid component containing the alkylene oxide adduct is 0.1 to 10 in terms of liquid hourly space velocity.
0 hr ^-1, more preferably 0.2~70hr ^-1, 1~
50 hr ^-1 is particularly preferred. The pressure in the reaction tube is not particularly limited, and may be a known degree which is usually carried out. Specifically, an absolute pressure of 0.1 to 3 MPa is preferable, an absolute pressure of 0.2 to 2 MPa is more preferable, and an absolute pressure of 0.2 to 1.6 MPa is particularly preferable. The reaction temperature is preferably from 50 to 300 ° C, and from 80 to 300 ° C.
250 ° C is more preferable, and 100 to 230 ° C is particularly preferable.
When a lower alkylene oxide, particularly ethylene oxide, is used as the alkylene oxide, it is preferable to carry out the reaction in a nitrogen atmosphere in order to reduce the risk of explosion.

The alkylene oxide adduct obtained by using the catalyst of the present invention does not contain a component metal of the catalyst,
After the reaction as in the case of using a conventional catalyst, there is no need for a separation treatment such as filtration and centrifugation of the alkylene oxide adduct and the catalyst. Further, the product obtained by the method of the present invention is essentially neutral, and it is not necessary to neutralize the product by adding an acid or alkali as in the case of using a conventionally widely used alkali or acid catalyst. Absent.

[0012]

The percentages in the following examples are by weight unless otherwise specified.

Example 1 100 g of magnesium oxide powder (Kyomag 150, manufactured by Kyowa Chemical Co., Ltd.)
300 g of 10.2% alumina sol (manufactured by Nissan Chemical) was added to the mixture.
This mixed system is kneaded with a kneader for 15 to 30 minutes, and extruded to form a column having a diameter of 3 mm and a length of 5 mm.
It was dried at 110 ° C. for 24 hours. After drying, the molded catalyst was obtained by calcining at 600 ° C. for 2 hours in a nitrogen stream.

In an autoclave, lauryl alcohol
500 g and a basket made of stainless steel wire in which the above-mentioned molded catalyst was added at 6% with respect to lauryl alcohol were charged. After the system was replaced with nitrogen, the temperature was raised to 160 ° C. while stirring. At the same temperature, introduce 355 g of ethylene oxide while maintaining the pressure at 0.3 to 0.5 MPa absolute pressure,
The reaction was performed. When the obtained ethoxylate was analyzed by gas chromatography, the average addition mole number of ethylene oxide was 3.0. The content of by-products was 2.4%.

Comparative Example 1 Commercially available molded catalyst (KW2030 manufactured by Kyowa Chemical Co., Ltd., composition: _0.7 A)
l _0.3 O _1.15 ), and an alkylene oxide adduct was obtained in the same manner as in Example 1. The average number of moles of alkylene oxide added to the obtained ethoxylate was 3.0. The content of by-products was 1.4%.

Comparative Example 2 Commercially available powder catalyst (KW1000 manufactured by Kyowa Chemical: composition: Mg _4.5 Al
_{2 (OH) 13 CO 3 ·} mH 2 O, a 10.2% alumina sol m = 3-3.5) 100g was added 100g of water 40 g, were kneaded for 15-30 minutes with a kneader, 3mm diameter by extrusion, the length It was formed into a 5 mm column and dried at 110 ° C. for 24 hours. After drying, the mixture was calcined at 600 ° C. for 2 hours in a nitrogen stream to obtain a molded catalyst. An alkylene oxide adduct was obtained in the same manner as in Example 1 except that the obtained molded catalyst was used. The average number of moles of ethylene oxide added to the obtained ethoxylate was 3.0. Further, the content of the by-product was 11.6%.

Table 1 summarizes the catalyst strength and by-product content of each of the shaped catalysts used in Example 1 and Comparative Examples 1-2 before and after the reaction. The catalyst strength was measured by the following method.

<Measurement Method of Catalyst Strength> The crushing strength per molded catalyst was measured using a destruction tester (Kiya Seisakusho, Kiya type hardness tester). The crushing strength referred to here indicates a point at which cracks start to occur in the catalyst when a force is applied in the radial direction of the columnar catalyst.

[0019]

[Table 1]

As can be seen from Table 1, the catalyst of Example 1 had a sufficient strength, the amount of by-products was small and the selectivity of the reaction was good, whereas the strength of the catalyst of Comparative Example 1 was good. Was extremely low at 1.2 kgf / piece per catalyst pellet, collapse of the catalyst pellet was confirmed during the reaction, and a separation operation of the catalyst component and the generated ethoxylate was required. Although the catalyst of Comparative Example 2 had sufficient strength, it had many by-products and had a problem in the selectivity of the reaction.

[0021]

According to the present invention, an alkylene oxide adduct having few by-products in a reaction product can be produced. Also, by using the shaped catalyst of the present invention,
A simple process development in which the operation of separating the product and the catalyst after the reaction is omitted can be performed. Therefore, the present invention
Extremely valuable in industry.

Continued on the front page F term (reference) 4G069 AA02 AA08 BA01A BA01B BB06A BB06B BC10A BC10B CB25 CB38 CB70 DA06 EA02Y EB18Y FA01 FB06 FB30 FB31 FB65 FC08 4H006 AA02 AC43 BA06 BA09 BA30 BC32 GN61 GP01 CF01

Claims (2)

[Claims] 1. An alkylene oxide addition catalyst obtained by mixing and molding magnesium oxide and 5-80% by weight of alumina based on magnesium oxide. 2. A process for producing an alkylene oxide adduct, comprising reacting an active hydrogen-containing organic compound with an alkylene oxide in the presence of the catalyst according to claim 1.