JPS6035174B2 - Catalyst for producing alkylene glycol ethers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to catalysts for the production of alkylene glycol ethers.

To explain in detail, alcohol with 1 to 4 carbon atoms has 2 carbon atoms.
This invention relates to a catalyst for producing a corresponding alkylene glycol ether by reacting alkylene oxides of -4 in a liquid phase. More specifically, the present invention provides methanol,
Ethanol, propanols, butanols and ethylene oxide. The present invention relates to a catalyst capable of efficiently producing a corresponding alkylene glycol monoether by reacting pyrene oxide and butylene oxide in a liquid phase, and a method for producing the same. In general, alkylene glycol W
Tels are high boiling point water port solvents with excellent solvent power and moderate volatility, so they are suitable for many synthetic resins, fats,
Used as a solvent for dyes, etc. For example, they have a wide range of uses, including paint solvents, pesticide solvents, brake oils, automobile detergents, dry cleaning agents, printing ink solvents, dye solvents, plasticizers, penetrants, and softeners. Conventionally, it is well known that the corresponding alkylene glycol ethers can be obtained by reacting alkylene oxide with alcohol in the presence of an alkali or acid catalyst.
COLS” (Rei skin old P rib ljshing C
organization, New York, LI. S
．． A. According to Chap. 6) in 1953, ethylene glycol monoethylene was obtained by reacting ethanol and ethylene oxide using an alkali catalyst such as sodium hydroxide and trimethylamine, and German Patent No. 580075 (1933) ), it has been reported that ethylene glycol mona methyl ether is obtained by reacting methanol and ethylene oxide using an acid catalyst such as sulfuric acid, phosphoric acid, or 8-naphthalene sulfonic acid.

However, these alkylene glycol ethers are produced through sequential reactions, and are formed by reacting alkylene glycol monoether (hereinafter referred to as mono-GE) with alkylene oxide (hereinafter referred to as G-GE). ) and alkylene glycol trethers (hereinafter referred to as TREE GE) are inevitable.

Moreover, G-GE and Tory-OE have limited uses due to their volatility compared to Mono-GE, and are only used in paint solvents, brake oil, and automobile detergents. Therefore, when producing alkylene glycol ethers from alcohol and alkylene oxide, it is desired to produce mono-GE with good selectivity, and it is necessary to develop a useful catalyst for this purpose. When alcohol and alkylene oxide are reacted using the above-mentioned alkali catalyst, mono
Because the selectivity of E is low, it is necessary to use a large excess of alcohol, such as a molar ratio of alcohol and alkylene oxide of 7:1 to 15:1, and distillation is required to separate and recover unreacted alcohol from the reaction product liquid. There is a drawback that costs such as high costs are high.

When an acid is used as a catalyst, mono-
Although the selectivity of GE is at a nearly satisfactory level, ethers, aldehydes, and acetals are formed, making it difficult to separate and purify mono-GE from the reaction product solution.

On the other hand, according to the specification of JP-A-52-51307,
It has been found that solid acid catalysts such as y-alumina, titania or phosphotungstic acid may be advantageously used as catalysts for the above-mentioned reactions.

This solid acid catalyst is considered to have the following advantages in carrying out the reaction. That is, since it is used in a solid form, it is easy to separate it from the reactive liquid, the catalyst does not corrode the reaction vessel, and there are relatively few side reaction products, which improves the yield. However, even with these solid acid catalysts, the reaction conditions (generally 100 to 2000
isomerization of alkylene oxides to aldehydes at temperatures of 0 and pressures of 2 to 50 k9/mass G),
It has various drawbacks such as decreased activity and selectivity due to side reactions such as alkylene oxide polymerization reaction and the heat resistance of the catalyst itself, and it is still unable to sufficiently withstand industrial loads.

In view of the current situation, the present inventors focused on the excellent properties of solid acid catalysts as a catalyst that compensates for these drawbacks, and as a result of intensive research, we have succeeded in overcoming the drawbacks of known methods and maintaining stable activity over a long period of time. He discovered a catalyst and completed the present invention.

That is, the present invention provides a compound of at least one metal selected from iron group metals and alkali metals on a porous silica alumina support in a range of 0.5 to 25% by weight in terms of the element of the metal. 600-1100℃
The present invention discloses a catalyst for producing alkylene glycol ethers from alkylene oxide and alcohol, which is characterized in that the compound is formed into a metal and/or oxide by firing at a temperature range of preferably has a water absorption rate of 30 as a porous silica alumina carrier.
Concerning catalysts using porous silica-alumina carriers with an alumina (AI203) content in the range of 10 to 4% by weight, with a specific surface area of 200 to 800 w/w. The invention relates to a catalyst made of The shape of this porous silica alumina support can be freely changed depending on the process used.
Monolithic ones or pellet-shaped ones (cylindrical, spherical, or irregular shapes) are used, but pellets with a size of 1 to 1 rib are usually used for catalyst preparation. It is convenient for use as a catalyst.

In addition, the supported catalyst components include iron group metals consisting of nickel, iron, and cobalt, as well as magnesium, calcium,
Strike.

One or more kinds of alkaline earth metals such as aluminum and barium are used, and it is particularly preferable to use one or more kinds of nickel, cobalt, magnesium, and calcium. These catalyst components are supported in the form of metallic elements or oxides, and are present in an amount of 0.5 to 25% by weight, preferably 1 to 1% by weight in terms of elements per finished catalyst.
It is supported in a range of 0% by weight. If the supported amount is less than 0.5% by weight, although the catalyst activity is good, the selectivity of mono-GE is insufficient, and the polymerization ability of alkylene oxide cannot be sufficiently lowered, so that during long-term use, polymerization may occur. Catalyst poisoning occurs, and a rapid decrease in activity is observed.

On the other hand, increasing the amount supported to exceed 25% by weight,
This results in a decrease in the catalyst activity itself, and furthermore, such a large amount of support is uneconomical in the preparation of the catalyst and cannot be used. ．． A preferred method for preparing the catalyst according to the present invention
For example, the silica alumina support is immersed in an aqueous solution in which the iron group metal and/or alkali metal compound (especially water-soluble salts) is dissolved, and the required amount is loaded, and then
50-20000, preferably dried at 100-150°C, 600-110000, preferably 800-10
The finished catalyst is obtained by calcination with a reducing gas, an inert gas or an oxidizing gas, preferably hydrogen, nitrogen or air, at a temperature in the range of 0,000°C.

In this case, the above-mentioned calcination temperature is 600 to 1,100°C, preferably 800 to 100,000°C, but if the temperature is lower than 60,000°C, not only will the selectivity to mono-GE not be sufficiently improved, but the polymerization ability of alkylene oxide may be suppressed. As a result, the life of the catalyst is insufficient, and its mechanical strength inevitably decreases with long-term use.

Further, a temperature exceeding 110,000 is not preferable because it significantly reduces the activity, although the life of the catalyst becomes longer. As the iron group metal or alkali metal compound, it is preferable to use water-soluble inorganic or organic salts, such as nitrates, sulfates, acetates, and formates, with nitrates having high water solubility being particularly advantageous. It is not limited to this.

For example, complex salts of the above-mentioned metals such as ammonia or organic amines such as ethylenediamine and ethanolamine can also be supported and calcined and can be advantageously employed without any disadvantage in terms of catalyst performance. Further, the solution used for impregnation is not limited to the above-mentioned aqueous solution, and the purpose of the present invention can be fully achieved using solutions of known organic solvents such as acetone, ethers, and alcohols. If a reducing gas such as hydrogen is used for firing, the impregnated and supported metal compound will be reduced to the form of a metal element, but if an inert gas such as nitrogen or an oxidizing gas such as air is used, Supported in oxide form.

In the present invention, any combination is effective, and therefore combinations such as hydrogen and nitrogen, hydrogen and inert gas such as methane, or air and flammable gas such as natural gas can be used. In order to achieve the above-mentioned amount of metal supported, it is usually sufficient to carry out the above-mentioned dipping, impregnating, drying and firing operations once or twice, but in some cases they may be repeated several times.

The catalyst produced by the above-mentioned method of the present invention has excellent etherification activity and mechanical strength, and can be used as a catalyst for general liquid phase etherification reactions.It is especially suitable for converting alcohol into glycol ether and converting it into alkylene glycol monomer. It exhibits particularly stable and excellent activity and selectivity in reactions with ethers, and enables long-term continuous production on an industrial scale, which was previously impossible. The glycol etherification reaction of alcohol using the catalyst of the present invention can be carried out in either gas phase or liquid phase, but in particular, inert gas (e.g. nitrogen,
It is desirable to react by applying pressure using methane, hydrogen, etc.), and the reaction temperature is 50 to 25,000, preferably 100 to 25,000.
The temperature is 200°C, and either fixed bed or suspended bed is used.

Since this reaction is an exothermic reaction, it is preferable to use a solvent as a raw material diluent, and there are many types of solvents, but there are no particular restrictions as long as they do not participate in the reaction, such as dioxane, tetrahydrofuran, benzene, cyclohexane, etc. The solvent is appropriately selected from various solvents, taking into account the ease of recovery and separation of the product from the product. The following examples further illustrate the excellent properties of the catalyst according to the invention and describe the method for its preparation as well as the method for producing alkylene glycol ethers, but the invention is not limited to these examples.

Example 1 Commercially available silica alumina carrier (AI203 content 13% by weight, trade name: N631-L, manufactured by JGC Chemical Co., Ltd.) 5
After drying by heating at a ratio c of 15,000, the mixture was allowed to stand in a desiccant oven until room temperature.

Nickel nitrate Ni (N03)2 fine 203 at room temperature
2.9 was soaked in a solution prepared by adding and dissolving 67.1 cc of water for 30 minutes, then taken out, kept at 100° C., and stirred for 30 minutes to perform impregnation and drying. The catalyst was calcined for 800 oo for 3 hours by flowing 2 NI/hr of nitrogen per catalyst.

The nickel content of this catalyst is 4. It was mother weight %. 48 hours of ethanol, 12 hours of ethylene oxide,
20 days of dioxane and the above catalyst pillow c (5.2 days) were charged, and after adjusting to 5k9/c fin G with nitrogen,
Time reacted. Analysis of the reaction product liquid showed that the conversion rate of ethylene oxide was 98%, the selectivity of monoethylene glycol ethyl ether was 72%, the selectivity of diethylene glycol ethyl ether was 19%, and the selectivity of triethylene glycol ethyl ether was 7%. Ta.

Here, the conversion rate and selectivity are defined as follows.

Conversion rate (%) = Number of moles of alkylene oxide before reaction - Number of moles of alkylene oxide after reaction Satte harm soft rhombus number X/selectivity of dialkylene glycol ether (
%) Number of moles of dialkylene glycol ether produced x 2 x 100 Number of moles of reacted alkylene oxide Selectivity of trialkylene glycol ether (%) 20 Monograph of trialkylene glycol ether produced x
3×.

〇 Number of moles of reacted alkylene oxide Examples 2 to 4 Commercially available silica alumina carrier (AI203 content 28% by weight, trade name: N631-HN, manufactured by JGC Chemical Co., Ltd.)
A solution obtained by adding and melting 73.7 cc of water in place of the nickel nitrate aqueous solution with magnesium nitrate M (N03) 2 and bait 2026.3, and calcium nitrate Ca N03) 2nd and 4th 2015
．． 2 saws 84. The solution was dissolved by adding water of ring c, and the barium nitrate ball (N03.27.0 Noko93. Ratio C
The solution was prepared by adding and melting water, and the solution was soaked, impregnated, and dried.

These catalysts were fired under the same conditions as in Example 1 to obtain catalysts with a metal content of 2.0% by weight.

A reaction was carried out using these catalysts under the same reaction conditions as in Example 1, and the results shown in Table 1 below were obtained.

Table 1 Examples 5 to 8 The same carrier used in Example 1 was used in the same manner as in Example 1, Ni(N03)2, group 204.0, Yumoko water 96. To the solution to which ratio C was added, 5 ratio c, , Ni(N03)2・Misaki2
07.9 To the solution to which 92.1 cc of water was added, 5 ratio c,
and M (N03) 21 groups were immersed in a solution of 20 to 62 ml of water at 5 ratios, and then impregnated and dried.

These catalysts were calcined for 600 oo for 3 hours by passing 2 NI/hr of air per catalyst 19. The nickel content of these catalysts is 0.5% by weight and 1% by weight, respectively.
．． and 11.0% by weight. Also, the nickel content is 11. For a catalyst with a weight percent of 21.5% by weight, take half of it and repeat the above soaking, soaking, drying, and calcination once more to obtain a nickel content of 21. % by weight of the catalyst was also obtained. A reaction was carried out using these catalysts under the same reaction conditions as in Example 1, and the results shown in Table 2 were obtained. In addition, as comparative examples, experiments were conducted with 0 nickel content, that is, with only the carrier fired under the same conditions as above, and with the carrier simply dried at 150°C for 3 hours in an air atmosphere, and the results are reported. did. Table 2 [Note] In Comparative Example 1, only the carrier was fired at 600°C for 3 hours.

In Comparative Example 2, only the carrier was dried at 15,000°C for 3 hours.

Examples 9 to 13 The same carrier used in Example 2 was immersed in an aqueous solution of 2024.1% by weight of Ni(N03)2, followed by impregnation and drying.

The obtained nickel bath immersion catalyst was passed through air under the same conditions as in Example 1 to give 400 ri, 6000 ○, and 80 ri.
000 and 100,000 for 3 hours, respectively.
However, for No. 30,000, hydrogen was passed for 3 hours and reduction firing was performed. The nickel content of these catalysts is all 4.0.
It was in weight%. A reaction was carried out using these catalysts under the same conditions as in Example 1, and the results shown in Table 3 were obtained.

Table 3 Examples 14-15 The same carrier used in Example 2 was dried in the same manner as in Example 1, and then ammonia water (ammonia content 28%) was cooled with ice. Nickel acetate
(CH3COO) On days 2 and 4, 20 was gradually added and immersed in a solution for 2 hours, and then impregnated and dried by keeping the temperature at 10,000 and stirring for 1 hour.

The catalyst was calcined for 6 hours each at 800 q○ and 100,000 by flowing INI/hour of air per night of catalyst.

The nickel content of these catalysts was 4.8% by weight.

180 ml of ethanol and 4 ml of ethylene alkoxide in a stainless steel autoclave with an electromagnetic rotary attenuator with a content of 50%.
5 evenings, dioxane 759 and the above catalyst 3 ratio c (26.
1 night), and after adjusting the fin G to 5k9/c with nitrogen,
2000 for 2 hours and the results shown in Table 4 were obtained.

Table 4 Examples 16 to 20 The same carrier used in Example 2 was used in the same manner as in Example 2, and the magnesium content was 2. After obtaining a catalyst of about 6% by weight, this catalyst was further added to Ni (N03) for 2.6 days and 20 days.
6 weight 95 aqueous solution, i2. $wt% aqueous solution and. and 24
．． Each sample was immersed in a 1% by weight aqueous solution, impregnated, and dried.

These catalysts were calcined under the same conditions as in Example 2, and the magnesium content was 2.0% by weight and the nickel content was 1.0% by weight.
% by weight, magnesium content 2.0% by weight, nickel content 2.0% by weight, and magnesium content 2.0% by weight. Three types were obtained, with a nickel content of 4.0% by weight and a nickel content of 4.0% by weight. On the other hand, in addition to the catalysts for the two-time impregnation method, two types of catalysts for the one-time impregnation method shown below were also prepared.

That is, the same carrier as in Example 2 was used as Mg(N03)2.
26.3 evening and Ni (N03) 2 / Hoso 20 12.9 evening and Wednesday 60. Pillow c is soaked and impregnated in an aqueous solution that is simultaneously melted.
After drying, it was fired under the same firing conditions as Example 1 at 80,000 in nitrogen and air to obtain a magnesium content of 2.0% by weight.
Two types of catalysts with a nickel content of 2.0% by weight were prepared. Reactions were carried out using these five types of catalysts under the same conditions as in Example 1, and the results shown in Table 5 were obtained.

Table 5 Example 21 Using the 1000 oo calcined catalyst 72&c in Example 15 as a fixed bed catalyst, continuous experiments were conducted on alkylene glycol ether production reaction using ethylene oxide and ethanol.

The feed rate (S
V) Supply at 2.0 ni (raw material)/cc (catalyst)/hour, and supply hydrogen at 30 NI/hour in parallel with this to generate 10 k9/kg.
The reaction was carried out under a pressure of 140 qo. Analysis of the composition of the product liquid and gas at the reactor outlet revealed that the initial conversion rate of ethylene oxide was 92%, and the selectivity of each product was as follows. Monoethylene glycol ethyl ether 75%
Diethylene glycol ethyl ether 18% Triethylene glycol ethyl ether 6% Ethylene oxide polymer 1% Even if this reaction was carried out under the same conditions for about two months continuously, there was almost no change in the activity or selectivity of the catalyst, and the appearance of the catalyst itself It was also found that it was not contaminated with polymer and maintained sufficient strength. Further, as a comparative example, continuous experiments were conducted using the same catalyst as above but fired at 600 qo under the same reaction conditions.

Initial results showed that the conversion rate of ethylene oxide was 94%, and the selectivity of monoethylene glycol ethyl alcohol was 94%.
77% selectivity of diethylene glycol ethyl ether 17% selectivity of triethylene glycol ethyl ether
5% ethylene oxide polymer
However, when this reaction was continued under the same conditions for about a month, the conversion rate of ethylene oxide was
83% Selectivity of monoethylene glycol ethyl ether 77% Selectivity of diethylene glycol ethyl ether
A result of 15% selectivity of triethylene glycol ethyl ether and 4% ethylene oxide polymerization was obtained, and the appearance of the catalyst itself was slightly dirty with polymer, and the strength had begun to decrease.

Examples 22 to 24 Each alkylene oxide shown in Table 6 was reacted with ethanol under the conditions of Example 1, using as a catalyst the alkylene oxide calcined at 800°C of Example 12.

The reaction results are shown in Table 6. Table 6 Examples 25 to 29 Reactions were carried out under the conditions of Example 15 using the alcohols shown in Table 7 and ethylene oxide, which were calcined at 100,000 in Example 15, as catalysts.

The reaction results are shown in Table 7. Table 7 Examples 30 to 32 Ferric nitrate Fe (N03) 2 / Sail 20 using the same carrier as used in Example 2 and using the same 5 ratio C as in Example 2
18.6% by weight aqueous solution, cobalt nitrate C0 (N03)
2. Fine 20 12.9% by weight aqueous solution and C0 (N03
) 2, string 20 12.9 evening and Mg (N03) 2, thin 20
26.3 evening and Wednesday 60. Each of the aqueous solutions simultaneously dissolved in pillow c was soaked, impregnated, and dried.

These catalysts were each calcined under the same conditions as in Example 1 at 90,000 for 3 hours by circulating air.

The metal content of each of these catalysts is, in order, iron 2.0
Weight %, cobalt2. , cobalt 2.0 weight %, and magnesium 2.0 weight %. A reaction was carried out using these catalysts under the same reaction conditions as in Example 1, and the results shown in Table 8 were obtained. Table 8

Claims (1)

[Scope of Claims] 1. A compound of at least one metal selected from iron group metals and alkaline earth metals is added on a porous silica alumina carrier in an amount of 0.5 to 25% by weight in terms of the element of the metal. Alkylene glycol ethers are prepared from alkylene oxide and alcohol by supporting the compound in a metal and/or oxide form by supporting the compound in a temperature range of 600 to 1100°C. Catalyst for manufacturing. 2 As a porous silica alumina carrier, water absorption rate is 30-1
2. The catalyst according to claim 1, wherein the catalyst has a specific surface area of 200 to 800 m^2/g. 3. The catalyst according to claim 1 or 2, which uses a porous silica-alumina carrier having an alumina (Al_2O_3) content in the range of 10 to 40% by weight. 4. The catalyst according to claim 1, 2 or 3, which uses nickel as the iron group metal.