JPS594444A - Catalyst for manufacture of morpholine - Google Patents

Abstract

PURPOSE:To enhance activity and durability, by depositing nickel, chromium, and rhenium on an alpha-alumina carrier. CONSTITUTION:Metals consisting of 2-20wt% nickel based on alpha-alumina, chromium and rhenium in 1:(0.5-0.05) Ni/Cr atomic ratio and 1:(0.3-0.01) Ni/Re atomic ratio are added to an alpha-alumina carrier having 0.6-1.5g/ml filling density, 15-60% water absorptivity, and 0.01-10m<2>/g BET specific area. The treatment method is as follows: The alpha-alumina is dipped into an aq. soln. dissolving each compd. of Ni, Cr, and Re, and the necessary amt. of them are deposited thereon, then they are dried at 50-150 deg.C, preferably, 80-120 deg.C, and reduced with hydrogen at 200-450 deg.C.

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-amine ethoxy)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 presence of a hydrogenation catalyst in a liquid phase in the coexistence of hydrogen has already been known. ) and (2).

Therefore, in addition to the final product morpholine, the intermediate product 2-(2-amine ethoxy) is present in the reaction product solution.
Also includes 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 is a reaction (
It must exhibit high activity and selectivity for 1) and (2), and must maintain this activity for a sufficiently long period of time.

As a catalyst for producing morpholine, for example, U.S. Pat.
1 '51112 contains copper, nickel, chromium, cobalt, red sea bream, molybdenum, halusium, platinum,
rhodium, oxides of these metals or mixtures thereof, nickel in U.S. Pat.
U.S. Pat. No. 3,155,657 discloses an alumina catalyst containing about 0.2 to 5 moles of metallic ruthenium, and Japanese Patent Publication No. 32,188/1975 discloses Raney nickel alloy or nickel-based rye alloy, Special Publication 1976-32
No. 189 Niharai - Catalyst using alumina as a carrier obtained by contacting a nickel alloy or a nickel-based Ufuichi alloy with water or steam as a carrier, Special Publication No. 1977-
No. 41908 describes a catalyst containing 50 to 90% nickel, 9 to 45% copper, 1 to 5% molybdenum oxide, and 20 to 70% (by weight) of nickel.
No. 2699 contains 40-65 mol% nickel as NiO, 15-40 mol% copper as CuO, and Cr2O.
A catalyst consisting of 1 to 10 moles of chromium as 3 and 3 to 20 moles of aluminum as Al2O3, and a nickel-copper-chromium-titanium catalyst have 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.

The inventors of the present invention have conducted intensive studies on the development of industrially practical catalysts, and have 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 high activity. It has been found that the catalyst has excellent durability including long-term retention and 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 characterized in that nickel, 1,000 chromium, and rhenium are supported on an α-alumina carrier as a catalyst for producing morpholine, which is used when producing morpholine by reacting diethylene glycol and ammonia in the presence of hydrogen. This invention relates to a catalyst for producing morpholine.

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 shortcomings in all aspects, such as activity, selectivity, and life span, can be obtained. For example, a nickel catalyst using γ-alumina as a carrier shows a relatively high initial activity, as shown in the comparative example below, but its activity deteriorates rapidly over time, making it difficult to put 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 in the present invention has a packing density of 0
．． 6-1.5 p/ml, water absorption rate 15-60%, BET
A specific surface area o, o having a range of 1 to 1 om'/El is used. The α-alumina carrier can be in a wide variety of shapes, including pellets, spheres, granules, cylinders, extrudates, and similar shapes. In particular, spherical pellets or Diameter is 0.8~6.0
mm, and cylindrical pellets with a length within the range 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 to 20% by weight of nickel relative to α-alumina,
The atomic ratio of nickel to chromium is 1=05 to 1:0.05 and the atomic ratio of nickel to rhenium is 3 to 1:0.0.
When the ratio is within the range of 1, a catalyst with excellent activity, selectivity, and service life that can withstand industrial use can be obtained.

The raw material compounds for nickel and chromium supported on the α-alumina support of the present invention include inorganic salts such as nitrates, sulfates, carbonates, oxides, and hydroxides, and acetates, 7-alumates, and citrates. It is used in the form of an organic salt such as lactate or an elemental metal, but highly water-soluble salts are particularly preferred. The raw material compound for rhenium is used in the form of ammonium perrhenate, rhenium peroxide, or the like.

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 at a temperature of 50 to 150°C, preferably 80 to
Dry at 120°C and then dry at 200°C.
A finished catalyst is obtained by reduction treatment with hydrogen or hydrogen-containing gas at a temperature range of 450°C, preferably 250-350°C. The reduction treatment with hydrogen gas is preferably carried out with 100 g of hydrogen gas, but may be carried out 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 for the reaction of diethylene glycol and ammonia in the presence of hydrogen to produce morpholine, and has excellent activity, selectivity, and lifetime, and can be reacted at relatively low temperatures and low pressures. This method is effective in producing morpholine in high yield, and enables long-term continuous production 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. Continuous reaction has a reaction temperature of 150 to 300
C. and reaction pressure of 15 to 300 kg/d.

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, the conversion rate of diethylene glycol, the selectivity of morpholine, and the selectivity of 2-(2-amine ethoxy)ethanol are derived from the following equations.

Conversion rate of diethylene glycol@) Selectivity of morpholine) Selectivity of 2-(2-aminoethoxy)ethanol@) Example 1 5 oml of a pellet-shaped α-alumina carrier with a specific surface area of 1 m'/11 diameter of 2 mm and length of 4 mm Nickel nitrate (Ni
(NO3)2.6H20] 16.15 g, chromium nitrate [Cr(NO3)3.9H20)] 6.67 g and ammonium perrhenate (NH4ReO4) 0.
Impregnated with 1'7 ml of an aqueous solution containing 749 and heated at 100°C.
Dry for an 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 65% 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.

15+++ liters of the above catalyst and 150 g of diethylene glycol were placed in a stainless steel autoclave with an internal volume of 0.51 and equipped with an electromagnetic rotary stirrer, and after replacing with hydrogen, 120 g of ammonia was added, and then hydrogen was introduced under pressure for an amount equivalent to 27 atm, and the temperature was heated to 240°C.
The mixture was allowed to react for 2 hours. From the analysis of the reaction product liquid, the conversion rate of diethylene glycol was 74% and the selectivity to morpholine was 43%.
, selectivity to 2-(2-amine ethoxy)ethanol 4
It was 2%. The results are shown in Table-1.

Examples 2 to 6 In Example 1, the reaction of the supported metals shown in Table 1 was carried out.Example 7 Using the catalyst used in Example 1, the reaction was repeated under the same reaction conditions as in Example 1 using a new raw material each time. I did it. The results of analyzing the reaction product liquid after the fifth use of the catalyst were as shown in Table 1.

Example 8 The reaction of Example 7 was continued, and the reaction product liquid after the 10th use of the catalyst was analyzed, and the results 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 reactions were carried out in the same manner as in Example 1, and the results shown in Table 1 were obtained. .

Comparative Example 4 Nickel nitrate (Ni
(NO3)2.6l-120) 26.42.9 was impregnated with 20ml of an aqueous solution 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 was 10.0% by weight based on the carrier. 51 nl of the obtained catalyst
The reaction was carried out under the same reaction conditions as in Example 1. 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. As a result of analyzing the reaction product liquid after using the catalyst for the fifth time,
It was as shown in Table 1.

Comparative Example 6 The reaction of Comparative Example 5 was repeated, and the reaction product liquid after the 10th use of the catalyst was analyzed. The results are shown in Table 1.

Claims (2)

[Claims] (1) Production of morpholine characterized by supporting nickel, chromium, and rhenium on an α-alumina carrier as a catalyst for producing morpholine used when producing morpholine by reacting diethylene glycol and ammonia in the presence of hydrogen. Catalyst for use. (2) Nickel is 2 to 20% by weight based on 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 0.3 to
The catalyst according to claim 1, which is supported in a ratio of 1:0.01.