JPS6155417B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to catalysts for producing alkylene glycol ethers. To explain in detail, the number of carbon atoms is 1~
The present invention relates to a catalyst for producing a corresponding alkylene glycol ether by reacting an alkylene oxide having 2 to 4 carbon atoms with a C4 alcohol in a liquid phase. More specifically, the present invention provides methanol,
A catalyst capable of reacting ethanol, propanols, and butanols with ethylene oxide, propylene oxide, and butylene oxide in a liquid phase to efficiently produce the corresponding alkylene glycol monoether while suppressing by-product impurities as much as possible. and its manufacturing method. In general, alkylene glycol ethers are high-boiling water-soluble solvents with excellent dissolving power and moderate volatility, so they are used in many synthetic resins, fats,
Used as a solvent for dyes, etc. For example, it has a wide range of uses, including paint solvents, pesticide solvents, brake oils, automobile detergents, dry cleaning agents, printing ink solvents, paint solvents, plasticizers, penetrants, and softeners. It is well known that the corresponding alkylene glycol ethers can be obtained by reacting alcohol with alkylene oxide in the presence of an alkali or acid catalyst, such as "GLYCOLS".
(Reinhold Publishing Corporation, New
York, USA 1953, Chapter 6), ethylene glycol monoethyl ether was obtained by reacting ethanol and ethylene oxide using an alkali catalyst such as sodium hydroxide and trimethylamine, and German Patent Specification No. 580075 (1933)
reported that ethylene glycol monomethyl ether was obtained by reacting methanol with ethylene oxide using an acid catalyst such as sulfuric acid, phosphoric acid, or β-naphthalene sulfonic acid.
However, these alkylene glycol ethers are produced through sequential reactions, and are produced by reacting alkylene glycol monoether (hereinafter referred to as mono-GE) with alkylene oxide (hereinafter referred to as G-GE). The by-products of tri-GE) and alkylene glycol triethers (hereinafter referred to as tri-GE) are unavoidable. Furthermore, G-GE and Tory-GE are less volatile than Mono-GE, so their uses are limited to paint solvents, brake oil, and automobile detergents. Therefore, when producing alkylene glycol ethers from alcohol and alkylene oxide, monoge
It is desired to produce these with good selectivity, and it is necessary to develop useful catalysts for this purpose. When alcohol and alkylene oxide are reacted using the above-mentioned alkali catalyst, the selectivity of mono-GE is low even if the alcohol is used by about 5 times the mole (relative to alkylene oxide), so the molar ratio of alcohol and alkylene oxide must be adjusted. 7:1～
A large excess of alcohol, such as 15:1, must be used, and there is a drawback that costs such as distillation costs are high because unreacted alcohol is separated and recovered from the reaction product liquid. When an acid is used as a catalyst, even when alcohol and alkylene oxide are reacted at a molar ratio of 3:1 to 7:1, the selectivity of mono-GE is almost at a satisfactory level, but ether, aldehyde and Acetals are produced as by-products, making it difficult to separate mono-GE from the reaction product solution. On the other hand, according to the specification of JP-A-52-51307, it has been revealed that solid acid catalysts such as γ-alumina, titania, or phosphotungstic acid can be advantageously used as catalysts for the above-mentioned reaction. 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 reaction product liquid, the catalyst does not corrode the reaction container, and the yield is improved because there are relatively few side reaction products. However, even with these solid acid catalysts, under the relevant reaction conditions (generally a temperature of 100 to 200°C and a pressure of 2 to 50 kg/cm ² G are used), the isomerization of alkylene oxide to aldehyde and the polymerization of alkylene oxide are possible. However, it has various drawbacks such as a decrease in activity and selectivity due to the formation of by-products of impurities such as ethers and acetals, and the heat resistance of the catalyst itself, and it is still not able to sufficiently withstand the load at an industrial level. 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. The present invention was completed by discovering a catalyst that does the following. That is, the present invention provides at least one metal compound selected from iron group metals and alkaline earth metals on a porous inorganic support, particularly a porous silica alumina support, in an amount of 0.5 to 25% by weight in terms of the metal element. 600 ~
After firing in a temperature range of 1100°C, nickel or a composite compound combining nickel, copper, and chromium is supported so that the total elemental equivalent of the metal is in the range of 0.5 to 15% by weight, and then 250 to 450℃
The present invention discloses a catalyst for producing alkylene glycol ethers from alkylene oxide and alcohol, which is characterized in that the compound is reduced to a metal form by reduction at a temperature range of As a carrier, water absorption rate is 30-100% by weight and specific surface area is 200-800m ² /g.
The present invention relates to a catalyst using a porous silica-alumina carrier having an alumina (Al ₂ O ₃ ) content of 10 to 40% by weight. The shape of this porous silica alumina support can be freely changed depending on the process used, and it can be integrally molded into a monolith shape or formed into a pellet shape (cylindrical, spherical, or irregular shape). However, pellets having a size of 1 to 10 mm are usually convenient for catalyst preparation and catalyst use. One or more of iron group metals consisting of nickel, iron, and cobalt and alkaline earth metals consisting of magnesium, calcium, strontium, and barium are used as components to be supported on the supported composition until calcination. It is preferable to use one or more of the following: , cobalt, magnesium, and calcium. These components are supported in the form of metallic elements or oxides, and are supported in an amount of 0.5 to 25% by weight, preferably 1 to 10% by weight in terms of elements per finished catalyst. If the supported amount is less than 0.5% by weight, the catalytic activity is good, but some impurity by-products are observed, and if the supported amount exceeds 25% by weight, the catalytic activity itself decreases. Supporting a large amount is not economical in catalyst preparation. The above supporting composition is heated to 600 to 1100°C, preferably 800°C.
Calcination is carried out in a reducing gas, inert gas or oxidizing gas, preferably hydrogen, nitrogen or air, at a temperature range of ~1000°C, but in this case, if the above firing temperature is lower than 600°C, the polymerization ability of the alkylene oxide is suppressed. Therefore, the life of the catalyst is insufficient and its mechanical strength inevitably decreases after long-term use.On the other hand, temperatures exceeding 1100°C are undesirable because although the life of the catalyst is extended, the activity is significantly reduced. 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 gases such as methane, or air and flammable gases such as natural gas can be used. After the above firing, nickel or nickel,
A metal compound containing a combination of copper and chromium, that is, nickel alone, nickel and copper, nickel and chromium, and nickel, copper and chromium, preferably nickel alone or a combination of nickel, copper and chromium, in which the total elemental equivalent of the metal is It is supported in a range of 0.5 to 15% by weight, preferably 2 to 1.0% by weight, but in this case, the supported metal is essential to be nickel, which is important for stability of catalyst activity and suppression of impurity by-products such as ether and acetal. In consideration of the above, copper and/or chromium are supported in an appropriate combination. These components are supported in the form of metal elements in an amount ranging from 0.5 to 15% by weight in terms of element per finished catalyst. If the supported amount is less than 0.5% by weight, the catalyst activity is good, but the effect of suppressing impurity by-products such as ether and acetal is insufficient.On the other hand, if the supported amount exceeds 15% by weight, the catalytic activity itself may be affected. This has resulted in a decline in performance, making it unsuitable for adoption. Also, reduction is 250-450℃, preferably 270-370℃
The process is carried out using hydrogen or a hydrogen-containing gas within a temperature range of . In this case, if the above reduction temperature is lower than 250℃, the reduction effect will not be sufficient and on the contrary,
If the temperature exceeds 450°C, the catalyst activity will decrease, which is not preferable. As for the reducing gas, it is preferable to use 100% hydrogen gas, but hydrogen-containing gas diluted with an inert gas such as nitrogen or methane may also be used. Furthermore, prior to reduction, decomposition may be performed using an inert gas that does not contain hydrogen gas, such as nitrogen or methane, and then the above hydrogen-containing gas may be used. In any case, reduction using hydrogen gas is essential for the production of this catalyst. Iron group metals, alkaline earth metals used in the present invention,
Copper or chromium compounds include water-soluble inorganic or organic salts such as nitrates, sulfates,
It is preferable to use acetates and formates, and nitrates, which have high water solubility, are particularly advantageous, but are not limited thereto. 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 reduced 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 objects of the present invention can be sufficiently achieved using solutions of known organic solvents such as acetone, ethers, and alcohols. In order to achieve the above metal loading, the above-mentioned dipping, impregnation, drying, calcination, and reduction operations are usually carried out 1 to 2 times.
It is sufficient to repeat the process several times, but depending on the situation, it may be repeated several times. The catalyst produced by the above method in the present invention is
It has excellent etherification activity and mechanical strength, and can be used as a catalyst for general liquid phase etherification reactions. Above all, it is particularly stable and has excellent activity and selectivity in the reaction of glycol etherification of alcohol to alkylene glycol monoether. , which exhibits the effect of suppressing impurity by-products and enables long-term continuous production on an industrial scale, which was previously unachievable. The glycol etherification reaction of alcohol using the catalyst of the present invention can be carried out in either the gas phase or the liquid phase. In particular, inert gas (e.g. nitrogen, methane, , hydrogen, etc.), and the reaction temperature is 50-250℃, preferably 100-250℃.
The temperature is 200°C, and both fixed bed and suspended bed systems are used. In particular, when the reaction is carried out under a hydrogen atmosphere, the by-product of acetals is further suppressed. Since this reaction is an exothermic reaction, there are no particular restrictions on the solvent used as the raw material diluent as long as it does not participate in the reaction.
The solvent is appropriately selected from various solvents such as dioxane, tetrahydrofuran, benzene, and cyclohexane, taking into consideration the difficulty of recovering and separating 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 50 ml of a commercially available silica-alumina carrier (Al ₂ O ₃ content 28% by weight, trade name: N631H-N, manufactured by JGC Chemical Co., Ltd.) was heated and dried at 150° C., and then allowed to stand in a desiccator until the temperature reached room temperature. Add this to nickel nitrate at room temperature.
After immersing in a solution of 9.2 g of Ni (NO ₃ ) ₂ 6H ₂ O and 70.8 ml of water dissolved in it for 30 minutes, take it out and remove it.
Impregnation and drying were performed by keeping at ℃ and stirring for 30 minutes. This supported treatment composition was calcined at 1000° C. for 3 hours under air flow of 2 N/hour per gram of catalyst. The nickel content of this supported treatment composition was 5% by weight. After that, let it stand in a desiccator until it reaches room temperature, and then dissolve it in a solution of 54.2 g of nickel nitrate and 45.8 ml of water at room temperature.
After soaking for 30 minutes, the sample was taken out, kept at 100°C, and stirred for 30 minutes to perform impregnation and drying.
The catalyst was reduced at 300° C. for 4 hours with a flow of 1.2 N/h of hydrogen per gram of catalyst. This ring element further increases the nickel content in the form of metallic elements by 5
increased by % by weight. 48 g of ethanol, 12 g of ethylene oxide, 20 g of dioxane, and 8 ml of the above catalyst in a 200 ml stainless steel autoclave equipped with an electromagnetic rotary stirrer.
(8.4g) and adjusted to 5Kg/cm ² G with nitrogen.
The reaction was carried out at 120°C for 2 hours. Analysis of the reaction product liquid revealed a conversion rate of ethylene oxide of 92%, a selectivity of monoethylene glycol ethyl ether of 72%, a selectivity of diethylene glycol ethyl ether of 18%, a selectivity of triethylene glycol ethyl ether of 7%, and acetaldehyde as a by-product as an impurity. Selectivity of diethyl acetal
0.6% was obtained. Note that the conversion rate and selectivity are defined as follows (the same applies hereinafter). Conversion rate [%] (hereinafter referred to as C _EO ) = Number of moles of alkylene oxide before reaction - Number of moles of alkylene oxide after reaction / Number of moles of alkylene oxide before reaction × 100 Selectivity of monoalkylene glycol ether [%] (hereinafter S _MGE ) = Number of moles of monoalkylene glycol ether produced/Number of moles of reacted alkylene oxide x 100 Selectivity of dialkylene glycol ether [%] (hereinafter referred to as S _DGE ) = Number of moles of produced dialkylene glycol ether Number of moles x 2/Number of moles of reacted alkylene oxide x 100 Selectivity of trialkylene glycol ether [%] (hereinafter referred to as S _TGE ) = Number of moles of trialkylene glycol ether produced x 3/Mole of reacted alkylene oxide number × 100 Selectivity of acetal [%] (hereinafter referred to as _{S ETR} ) is defined as follows. S _ETR [%] = Number of moles of ether produced/Number of moles of alkylene oxide reacted x 100 Examples 2 to 4 50 ml each of the same carrier used in Example 1
In the same manner as in Example 1, 87.1 ml of cobalt nitrate CO (NO ₃ ) _{2.6H 2} O was added to 12.9 g instead of nickel nitrate.
A solution of magnesium nitrate dissolved in water
Mg(NO ₃ ) ₂・6H ₂ O26.3g was dissolved in 73.7ml of water, and calcium nitrate Ca
Each sample was immersed in a solution prepared by adding 84.8 ml of water to 15.2 g of (NO ₃ ) _{2.4H 2} O, and was then impregnated and dried. These supported treatment compositions were fired under the same conditions as in Example 1 to obtain metal contents of 2% by weight. Thereafter, nickel was further soaked, impregnated, dried and reduced in the same manner as in Example 1 to obtain a catalyst with a newly increased nickel content of 5% 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] Examples 5 to 8 Commercially available silica alumina carrier (Al ₂ O ₃ content 13
%, product name: N631-L, manufactured by JGC Chemical Co., Ltd.)
Ni(NO ₃ ) _{2.6H 2} O 4.0 g in the same manner as in Example 1.
Add 96.0 ml of water to the solution, add 50 ml of Ni(NO ₃ ) ₂ .
Add 50 ml to a solution of 34.1 g of 6H ₂ O and 65.9 ml of water.
and Ni(NO ₃ ) ₂ ·6H ₂ O (58.0 g) and 42.0 ml of water (50 ml each) for impregnation and drying. These supported treatment compositions were added at a concentration of 2Nl/g/g.
It was fired at 600°C for 3 hours by passing nitrogen through it. The nickel content of these supported treatment compositions is 0.5% by weight, 5% by weight, and 5% by weight, respectively.
It was 10% by weight. Also, nickel content is 10% by weight.
Regarding the composition, half of it was taken and the above-mentioned dipping, impregnation, drying and firing were repeated one more time to obtain a composition with a nickel content of 18% by weight. Thereafter, these catalyst compositions were added to Ni in the same manner as in Example 1.
It was immersed in a solution prepared by dissolving 29.9 g of (NO ₃ ) _{2.6H 2} O in 70.1 ml of water, and after impregnating and drying, it was reduced at 350° C. for 4 hours while flowing hydrogen. The nickel content of these catalysts increased by an additional 2% by weight in the form of metallic elements due to the reduction described above. A reaction was carried out using these catalysts under the same reaction conditions as in Example 1, and the results shown in Table 2 below were obtained.

[Table] Example 9 50ml of the same carrier used in Example 1 was
(NO ₃ ) ₂・6H ₂ O12.8g and Mg (NO ₃ ) ₂・6H ₂ O26.3g
and was simultaneously dissolved in 60.9 ml of water, and after impregnating and drying, this supported treatment composition was added per 1 g.
The product was calcined at 600°C for 3 hours while flowing hydrogen at 1.2 Nl/hr to obtain a product with a nickel content of 2% by weight and a magnesium content of 2% by weight. After firing, nickel was soaked, impregnated and dried in the same manner as in Example 1, and heated at 400°C for 3
A catalyst with an additional 5% by weight increase in nickel content was prepared by time reduction. A reaction was carried out using this catalyst under the same reaction conditions as in Example 1, and the results shown below were obtained. C _EO 97% S _MGE 67% S _DGE 19% S _TGE 6% S _ACL 0.8% Examples 10 to 12 The same carrier 1 used in Example 1 was dried in the same manner as in Example 1, and then cooled with ice. 127g of nickel acetate (CH ₃ COO) 2.4H ₂ O was gradually added to 310g of aqueous ammonia (ammonia content 28 _% ), and the mixture was immersed in the solution for 2 hours, then kept at 100℃ and stirred for 1 hour. Impregnation and drying were performed by this method. This supported treatment composition was calcined at 1000° C. for 6 hours while circulating air at 1 Nl/hour per gram. The nickel content of this composition was 5% by weight. Then, take 50 ml of this composition and apply Example 1
Similarly, add 67.5 g of Ni(NO ₃ ) ₂・6H ₂ O to 32.5 ml of water.
In addition, the solution heated and dissolved, Ni(NO ₃ ) ₂ .
A solution of 67.5 g of 6H ₂ O and 7.6 _g of copper nitrate Cu(NO ₃ ) 2.3H ₂ O added to 24.9 ml of water and dissolved by heating, and Ni
(NO ₃ ) ₂・6H ₂ O67.5g and Cu (NO ₃ ) ₂・3H ₂ O3.7g
and chromium nitrate Cr (NO ₃ ) ₃・9H ₂ O7.5g and water 21.3
ml of the solution was added and heated to dissolve, and the samples were immersed, impregnated, and dried. These supporting treatment compositions were reduced under the same conditions as in Example 1, and 5% by weight of nickel, 5% by weight of nickel and 0.5% by weight of copper, and 5% by weight of nickel, 0.25% by weight of copper, and 0.25% by weight of chromium were respectively added. A catalyst with a weight % increase was obtained. 180 g of ethanol, 45 g of ethylene oxide, 75 g of dioxane, and 30 ml of the above catalyst were placed in a stainless steel autoclave with an internal capacity of 50 ml and equipped with an electromagnetic rotary stirrer, and after adjusting to 5 Kg/cm ² G with nitrogen, they were reacted at 120°C for 2 hours. The results shown are obtained. Further, as Comparative Example 1, an experiment was also conducted on a product which had a nickel content of 5% by weight and was simply calcined at 1000° C. for 6 hours without carrying out the latter supported reduction described above, and the results were shown.

[Table] Example 13 Using 725 ml of the catalyst of Example 12 as a fixed bed catalyst, continuous experiments were conducted on the alkylene glycol ether production reaction between ethylene oxide and ethanol. A raw material with a composition of 75% by weight of ethanol, 10% by weight of ethylene oxide, and 15% by weight of dioxane is supplied at a feed rate (SV) of 2.0 g (raw material)/ml (catalyst)/hour, and hydrogen is cocurrent with this at a rate of 30 Nl/hour. supply 10
The reaction was carried out at 140° C. under a pressure of Kg/cm ² G. Analysis of the composition of the produced 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 shown in Table 4 below.

[Table] Even if this reaction is carried out continuously for about two months under the same conditions, there is almost no change in the activity or selectivity of the catalyst.
The appearance of the catalyst itself was not contaminated with polymer, and its strength was sufficiently maintained. As a comparative example, continuous experiments were conducted under the same reaction conditions for the catalyst in Comparative Example 1 (only calcination was performed at 1000° C. after supporting nickel, and the subsequent supporting reduction operation was not performed). The initial results and the results obtained under the same conditions for about two consecutive months are shown in Table 5 below.

[Table] Although the appearance of the catalyst itself was good and the strength was almost maintained, as shown in the results above, long-term continuous experiments showed that the conversion rate of ethylene oxide and the selectivity of glycol ethyl ether decreased, and the selectivity of impurities decreased. An increase was seen. Example 14 50 ml of a commercially available silica-alumina carrier (Al ₂ O ₃ content 28% by weight, trade name: N631H-N, manufactured by JGC Chemical Co., Ltd.) was heated and dried at 150° C., and then allowed to stand in a desiccator until the temperature reached room temperature. This is heated to iron nitrate (Fe) at room temperature.
(NO ₃ ) ₂・6H ₂ After immersing in a solution of 29.2 g of O2 and 70.8 ml of water for 30 minutes, take it out and
Impregnation by stirring for 30 minutes at ℃
I did drying. 1 g of catalyst is added to this supported treatment composition.
Calcining was performed at 1000°C for 3 hours under air flow of 2Nl/h. The iron content of this supported treatment composition is 5
It was in weight%. After that, let it stand in a desiccator until it reaches room temperature, and then add 54.2 g of iron nitrate at room temperature.
After immersing it in a solution prepared by adding 45.8 ml of water for 30 minutes, it was taken out, kept at 100° C., and stirred for 30 minutes to perform impregnation and drying. This catalyst was heated at 300 m
Reduced at ℃ for 4 hours. This reduction further increased the iron content by 5% by weight in the form of metallic elements. 48 g of ethanol, 12 g of ethylene oxide, 20 g of dioxane, and 8 ml of the above catalyst in a stainless steel electromagnetic rotary stirrer autoclave with a capacity of 200 ml.
(8.4g) and adjusted to 5Kg/cm ² G with nitrogen.
The reaction was carried out at 120°C for 2 hours. Analysis of the reaction product liquid revealed a conversion rate of ethylene oxide of 98%, a selectivity of monoethylene glycol ethyl ether of 70%, a selectivity of diethylene glycol ethyl ether of 19%, a selectivity of triethylene glycol ethyl ether of 7%, and acetaldehyde as a by-product as an impurity. Selectivity of diethyl acetal
0.8% was obtained.

Claims (1)

[Claims] 1 A compound of at least one metal selected from iron group metals and alkaline earth metals is placed on a porous silica alumina support in an amount of 0.5 to 25 in terms of the element of the metal.
After firing the supported composition in a temperature range of 600 to 1100°C, it is further added with 0.5 to 15% by weight of nickel and 0 to 15% of copper in terms of elements.
2% by weight of chromium and 0 to 2% by weight of chromium (however, the total is 0.5 to 15% by weight in elemental terms). A catalyst for producing alkylene glycol ethers from an alkylene oxide and an alcohol, characterized in that the alkylene oxide is formed into an elemental form.