JPS6352533B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel catalyst for use in the production of morpholine from diethylene glycol and ammonia. Specifically, the present invention relates to a catalyst for producing morpholine, which is used in producing morpholine and 2-(2-aminoethoxy)ethanol by reacting diethylene glycol and ammonia in the presence of hydrogen. Conventionally, a method for producing morpholine by reacting diethylene glycol and ammonia in the liquid phase in the coexistence of hydrogen in the presence of a hydrogenation catalyst is already known. ) and (2). Therefore, the reaction product liquid contains not only the final product morpholine but also the intermediate product 2-2-aminoethoxy)ethanol. Each can be separated and purified to produce a product, but if the purpose is to produce only morpholine, 2-(2-aminoethoxy)ethanol can be recovered and used as a feedstock to the reactor. Therefore, an excellent catalyst used in the production of morpholine must exhibit high activity and selectivity for reactions (1) and (2), and must maintain this activity for a sufficiently long period of time. Catalysts for producing morpholine include, for example, copper, nickel, chromium, cobalt, magnesium, molybdenum, palladium, platinum, rhodium, oxides of these metals, or mixtures thereof, as disclosed in U.S. Pat. No. 3,151,112; is a catalyst containing about 60 to 85 mole percent nickel, about 14 to 37 mole percent copper, and about 1 to 5 mole percent chromium, U.S. Pat.
No. 3155657 contains approximately 0.2 to 5% by weight of metallic ruthenium.
JP-B No. 46-32188 uses a Raney nickel alloy or a nickel-based Raney alloy, and JP-B No. 1987-32189 uses a Raney nickel alloy or a nickel-based Raney alloy that has been brought into contact with water or steam in advance. The resulting alumina-supported catalyst, Japanese Patent Publication No. 47-41908, contains 50 to 90% nickel, 9 to 45% copper, 1 to 5% molybdenum oxide, and 20 to 70% as nickel.
(Weight) Containing catalyst, Japanese Patent Publication No. 49-32699
From 40-65 mol% nickel as NiO, 15-40 mol% copper as CuO, 1-10 mol% chromium as Cr ₂ O ₃ and 3-20 mol % aluminum as Al ₂ O ₃ A nickel-copper-chromium-titanium catalyst has been proposed in JP-A-54-100383. However, these conventionally known catalysts still have many points to be improved in terms of life, activity, selectivity, etc., and cannot be said to be sufficient. As a result of intensive studies aimed at developing an industrially practical catalyst, the present inventors found that a catalyst in which nickel, chromium, and rhenium are supported on an α-alumina support has not only high activity and selectivity, but also a sustained high activity. It has been found that this catalyst has excellent durability including mechanical strength, and is a useful catalyst for producing morpholine that is superior to conventionally known catalysts. Therefore, an object of the present invention is to provide a novel highly active and durable catalyst for producing morpholine in high yield by reacting diethylene glycol and ammonia. The present invention is a morpholine production catalyst used when diethylene glycol and ammonia are reacted in the presence of hydrogen to produce morpholine, and is characterized in that nickel, chromium, and rhenium are supported on an α-alumina carrier. This invention relates to catalysts for production. In general, many catalyst carriers other than α-alumina are known, but in the catalyst of the present invention, it is essential to use an α-alumina carrier, and when using other carriers, However, only catalysts with defects in any or all of the following, such as activity, selectivity, and life span, can be obtained. for example,
As shown in the comparative examples described below, the nickel catalyst using γ-alumina as a carrier shows a relatively high initial activity, but its activity decreases rapidly over time, making it difficult to put it into practical use industrially. However, not all nickel catalysts using alpha-alumina supports are useful. While the α-alumina support has excellent mechanical strength, it has a relatively small specific surface area, and therefore, catalysts in which nickel alone, nickel-chromium, or nickel-rhenium is supported on it have low activity as shown in the comparative examples below. However, when nickel, chromium, and rhenium were supported together on an α-alumina carrier, not only did they mutually enhance the activity, but also a catalyst with excellent performance in terms of selectivity and durability was obtained. Therefore, the catalyst of the present invention requires all three elements, nickel, chromium and rhenium, to be supported on the α-alumina carrier. The α-alumina carrier used in the present invention has a packing density of 0.6 to 1.5 g/ml, a water absorption rate of 15 to 60%, and a BET specific surface area of 0.01 to 10 m ² /g.
The α-alumina carrier can be in a wide range of shapes, including pellets, spheres, granules, cylinders, extrudates, and similar shapes.
Spherical pellets or diameters within ~6 mm
Cylindrical pellets with a length of 0.8 to 6.0 mm and a length of 0.8 to 12.7 mm are preferably used. The amount of each metal supported on the α-alumina support of the present invention is 2 for nickel for α-alumina.
~20% by weight, nickel to chromium atomic ratio of 1:
When the atomic ratio of nickel to rhenium is within the range of 0.5 to 1:0.05 and 1:0.3 to 1:0.01, a catalyst with excellent activity, selectivity, and service life that can withstand industrial use can be obtained. Nitrate,
It is used in the form of inorganic salts such as sulfates, carbonates, oxides, and hydroxides, organic salts such as acetates, oxalates, citrates, and lactates, or in the form of simple metals.
In particular, highly water-soluble salts are preferred. Raw materials for rhenium include ammonium perrhenate,
Used in forms such as rhenium peroxide. The catalyst for producing morpholine of the present invention is produced as follows. An α-alumina support is immersed in an aqueous medium in which nickel, chromium, and rhenium compounds are dissolved, and the required amount is supported.
The catalyst is dried at a temperature of 80 to 120°C, preferably 80 to 120°C, and then subjected to reduction treatment with hydrogen or a hydrogen-containing gas at a temperature of 200 to 450°C, preferably 250 to 350°C to obtain a finished catalyst. The reduction treatment with hydrogen gas is preferably performed with 100% hydrogen gas, but may be performed with a hydrogen-containing gas diluted with an inert gas such as nitrogen or methane. The catalyst produced by the above method of the present invention can be used in the reaction of producing morpholine by reacting diethylene glycol and ammonia in the presence of hydrogen,
With its excellent activity, selectivity, and lifespan, it is capable of producing morpholine in high yield by conducting the reaction at relatively low temperatures and low pressures, making long-term continuous production possible on an industrial scale. As for the reaction method, either fixed bed or suspended bed can be used. In particular, a continuous process using a fixed bed of catalyst is preferred since it makes the features of the present invention effective. For continuous reactions, the reaction temperature
The reaction can be carried out at a temperature of 150 to 300°C and a reaction pressure of 15 to 300 Kg/cm ² . The following examples will explain in more detail the catalyst having excellent characteristics according to the present invention, and will specifically explain the method for producing the catalyst and the method for producing morpholine, but the present invention is not limited to these examples. . Here, conversion rate of diethylene glycol, selectivity of morpholine and 2-(2-aminoethoxy)
The selectivity of ethanol is derived from the following equation. Conversion rate of diethylene glycol (%) = Number of moles of diethylene glycol reacted/Number of moles of diethylene glycol subjected to reaction x 100 Selectivity of morpholine (%) = Number of moles of morpholine produced/Number of moles of diethylene glycol reacted x
100 Selectivity of 2-(2-aminoethoxy)ethanol (%) = Number of moles of 2-(2-aminoethoxy)ethanol produced/Number of moles of reacted diethylene glycol x 100 Example 1 Specific surface area 1 m ² /g, 16.15 g of nickel nitrate [Ni(NO ₃ ) _{2.6H 2} O] and chromium nitrate [Cr
17 ml of an aqueous solution containing 6.67 g of (NO ₃ ) _{3.9H 2} O] and 0.74 g of ammonium perrhenate [NH ₄ ReO ₄ ]
and dried at 100°C for 1 hour. This catalyst was subsequently subjected to hydrogen reduction treatment at 300° C. for 2 hours in a hydrogen gas atmosphere. The content of each metal in this catalyst was 6.5% by weight of nickel with respect to the carrier, chromium with an atomic ratio of 0.30 with respect to nickel, and rhenium with an atomic ratio of 0.05 with respect to nickel. Put 15 ml of the above catalyst and 150 g of diethylene glycol into a stainless steel autoclave with an internal volume of 0.5 and equipped with an electromagnetic rotary stirrer, and after replacing with hydrogen, add 120 g of ammonia.
After adding hydrogen and then injecting hydrogen equivalent to 27 atmospheres,
The reaction was carried out at 240°C for 2 hours. Analysis of the reaction product liquid showed a conversion rate of diethylene glycol of 74%, selectivity to morpholine of 43%, and 2-(2-aminoethoxy).
The selectivity to ethanol was 42%. Display the results -
Shown in 1. Examples 2 to 6 In Example 1, the catalysts were prepared in the same manner as in Example 1 except that the supported metals shown in Table 1 were used as catalysts, and the reaction was carried out in the same manner as in Example 1 to obtain the results shown in Table 1. . Example 7 Using the catalyst used in Example 1, the reaction was repeated under the same reaction conditions as in Example 1, using new raw materials each time. The results of analyzing the reaction product liquid after the fifth use of the catalyst were as shown in Table 1. Example 8 Repeat the reaction of Example 7 and use the catalyst 10 times.
The results of the analysis of the reaction product liquid for the second time were as shown in Table 1. Comparative Examples 1 to 3 In Example 1, the catalysts were prepared in the same manner as in Example 1 except that the supported metals shown in Table 1 were used as catalysts, and the reaction was carried out in the same manner as in Example 1 to obtain the results shown in Table 1. . Comparative example 4 Specific surface area 150m ² /g, 3φ x 3mm pellet-shaped γ
-Nickel nitrate [Ni] on 50 ml of alumina carrier
It was impregnated with 20 ml of an aqueous solution containing 26.42 g of (NO ₃ ) ₂ ·6H ₂ O and dried. The obtained catalyst was subsequently subjected to hydrogen reduction treatment at 300° C. for 2 hours in a hydrogen gas atmosphere.
The nickel content of this catalyst is
It was 10.0% by weight. A reaction was carried out under the same reaction conditions as in Example 1 using 15 ml of the obtained catalyst.
The results were as shown in Table-1. Comparative Example 5 Using the catalyst used in Comparative Example 4, the reaction was repeated under the same reaction conditions as in Example 1, using new raw materials each time. The results of analyzing the reaction product liquid after the fifth use of the catalyst were as shown in Table 1. Comparative Example 6 Continue the repeated reaction of Comparative Example 5 and use the catalyst 10 times.
The results of analyzing the reaction product liquid for the second time were as shown in Table 1. 【table】

Claims (1)

[Scope of Claims] 1. As a catalyst for producing morpholine used in producing morpholine by reacting diethylene glycol and ammonia in the presence of hydrogen, α
- A catalyst for producing morpholine, characterized in that nickel, chromium, and rhenium are supported on an alumina carrier. 2 Nickel is 2 to 20% by weight relative to α-alumina, and the atomic ratio of nickel to chromium is 1:0.5 to 1:
0.05 and the atomic ratio of nickel to rhenium is 1:
The catalyst according to claim 1, which is supported in a ratio of 0.3 to 1:0.01.