JPS58225078A - Catalyst for preparation of morpholine - Google Patents

Abstract

PURPOSE:To provide a novel catalyst for the synthesis of morpholine, having high activity and selectivity, and excellent durability, by supporting nickel, copper, chromium and rhenium at specific atomic ratios on an alpha-alumina carrier. CONSTITUTION:A novel catalyst for the synthesis of morpholine of formula IIby the reaction of diethylene glycol of formula I with ammonia in the presence of hydrogen, is composed of nickel, copper, chromium, and rhenium supported on an alpha-alumina carrier. The amount of Ni is 2-20wt% based on alpha- alumina, and the atomic ratios of Ni:Cu, Ni:Cr and Ni:Re are 1:(0.4-0.02), 1:(0.5-0.05) and 1:(0.3-0.01), respectively. The catalyst can be prepared by dissolving the compounds of the above metals in an aqueous medium, immersing an alpha-alumina carrier in said solution, drying at 50-150 deg.C, and reducing with hydrogen at 200-450 deg.C. It has high activity and selectivity for the morpholine preparation reaction 1 and 2, and the activity, etc. can be maintained for a long period.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel catalyst for use in the production of morpholine. Specifically, diethylene glycol and ammonia 7 are reacted in the presence of hydrogen to form morpholine and 2-(2-
Concerning the catalyst for producing morpholine used in producing (aminoethoxy) ethanol〇 Conventionally, there is already a known 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. The production reaction proceeds according to the following sequential reaction equations (1) 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 for morpholino production must exhibit high activity and selectivity for reactions (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.
No. 151112 contains copper, nickel, chromium, cobalt,
Magnenium, molybdenum, palladium, platinum, rhodium, oxides of these metals, or mixtures thereof; U.S. Pat. U.S. Pat. No. 3,155,657 discloses an alumina catalyst containing about 0.2 to 5 moles of metallic ruthenium;
No. 6-32188 discloses a Raney nickel alloy or a nickel-based Raney alloy, and Japanese Patent Publication No. 46-32189 discloses a Raney nickel alloy or a nickel-based Raney alloy prepared by using alumina as a carrier, which is obtained by contacting a Raney nickel alloy or a nickel-based Raney alloy with water or steam in advance. Catalyst, Special Publication No. 47-41908
No. contains 50-90% nickel, 9-45% copper, 1-5% molybdenum oxide, and has a content of 20-70% as nickel.
% (by weight) of nickel, 40 to 65 moles of nickel as NiO, and CuO
15 to 40 mol of copper as 'Cr203, 1 to 10 mol of chromium as 'Cr203, and 3 to 2 mol of Al2O3.
Catalyst consisting of 0 mole of aluminum, JP-A-1987-
No. 100383 proposes nickel-copper-chromium-titanium catalysts. 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 with the aim of developing a catalyst that can be used industrially, and have found that a catalyst in which nickel, copper, chromium, and rhenium are supported on an α-alumina support has not only high activity and selectivity but also high selectivity. It has been found that the catalyst has excellent durability including sustained activity 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 provides a catalyst for producing morpholine, which is used when producing morpholine by reacting diethylene glycol and ammonia in the presence of hydrogen, in which nickel, copper, chromium, and reniuno are supported on an α-alumina carrier. The present invention relates to a catalyst for producing morpholine characterized by:

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, as shown in the comparative example below, a nickel catalyst using r-alumina as a carrier exhibits a relatively high initial activity, but its heating temperature decreases rapidly, making it impractical for industrial use. sea bream. However, not all nickel catalysts using alpha-alumina supports are useful.

While the α-alumina support has excellent mechanical strength, its specific surface area is relatively small, so catalysts with nickel-gaku, nickel-copper-chromium, or nickel-rhenium supported on it have low activity as shown in the comparative examples below. It is. However, when nickel, copper, chromium, and rhenium were supported together on an α-alumina support, they not only increased the activity but also produced a catalyst with excellent performance in terms of selectivity and durability. . Therefore, the catalyst of the present invention is supported on an α-alumina carrier, and all of the four elements of nickel, copper, chromium, and rhenium are essential.

The α-alumina carrier in the present invention has a packing density of 0
．． 6-1.5 f/mi, water absorption rate 15-60%, B
Those having an ET specific surface area of 0.01 to 10 m/f are used. The α-alumina carrier can be in a wide variety of shapes, including pellets, spheres, granules, cylindrical extrudates, and similar shapes, especially those with a diameter of 3 to 6 mm.
Spherical pellets within the range of dragon or diameter 0.8-6.
O, m, length 0.8-12.7. .

Cylindrical pellets within the range of 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 with respect to α-alumina,
The thickness ratio of nickel to copper is 1:04 to 1:0.02, the atomic ratio of nickel to chromium is 1:0.5 to l:0.05, and the atomic ratio of nickel to rhenium is 1:03 to I:0. ．．
When the ratio is within the range of 0.01, a catalyst with excellent activity, selectivity, and service life that can withstand industrial use can be obtained.

The raw material compounds for nickel, copper 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, oxalates, and citric acids. It is used in the form of a salt, an organic salt such as a 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, copper, chromium, and rhenium compounds are dissolved, and the required amount is supported at 50 to 150°C, preferably 80°C.
Dry at ~120°C, then i-1,2oo~
The 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 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 invention17 can be used in the reaction of producing morpholine by reacting diethylene glycol and ammonia in the presence of hydrogen, and has excellent activity, selectivity, and life, and can be used at relatively low temperatures and low pressure F. It exhibits the effect of producing morpholin in high yield through reaction, 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 makes the features of the present invention effective.
``f suitable'' 6. Continuous E tv K i, ld L
Response □i +1150~300℃, reaction pressure 15~
It can be carried out at 300 kg/i.

The following examples will explain in more detail the catalyst with 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. Not.

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

Conversion rate of diethylene glycol @) Selectivity of morpholine) Selectivity of 2-(2-amine ethoxy)ethanol (4)
Example 1 Specific surface area 1 m2/'f, diameter 21 nm, length 47
1? Nickel nitrate [Ni("03')2.61120) 16,1
59, Copper nitrate (CLl (NO,)2.3l-120)
0.67? , nitrate oxide [Cr(No3)3.911
20) 17 m of an aqueous solution containing 4.459 and ammonium perrhenate (NII, Re04) 0.749
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 is 65% by weight of nickel with respect to the carrier, and 0.00% of copper with respect to nickel.
The atomic ratio of chromium to nickel was 0.5, the atomic ratio of chromium to nickel was 0.020, and the atomic ratio of rhenium to nickel was 0.005.

15 ml of the above catalyst and 1 ml of diethylene glycol were placed in a stainless steel autoclave with an internal volume of 0.51 and equipped with an electromagnetic stirrer.
After replacing with hydrogen, add 1209 ml of ammonia, then pressurize hydrogen equivalent to 27 atm, and heat at 240℃ for 2 hours.
Allowed time to react. Analysis of the reaction product liquid showed that the conversion rate of diethylene glycol was 60%, the selectivity to morpholine was 35%,
Selectivity to 2-, (2-aminoethoxy)ethanol 5
It was 1%. The results are shown in Table 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 reactions were carried out in the same manner as in Example 1 to obtain the results shown in Table 1.

Example 7 The reaction was repeated under the same reaction conditions as in Example 1, using the catalyst used in Example 1 and using a new raw material 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 The reaction of Example 7 was repeated, 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 conducted in the same manner as in Example 1 to obtain the results shown in Table 1.

Comparative Example 4 A pellet having a specific surface area of 150 m'/fI and a size of 3φ×3 mm was impregnated with 20me of an aqueous solution containing γ6)(,,0)26.429 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 100% relative to the carrier.
He was in charge of weight. A reaction was carried out under the same reaction conditions as in Example 1 using 15 mg of the obtained catalyst. The results were as shown in Table 1.

Comparative Example 5 Reactions were repeated using the same catalyst as in Comparative Example 4 under the same reaction conditions as in Example 1 to 1, using different 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 Repetition of Comparative Example 5 The reaction 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.

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Claims (2)

[Claims] (1) A catalyst for producing morpholine used when producing morpholine by reacting diethylene glycol and ammonia in the presence of hydrogen, characterized by supporting nickel, copper, chromium, and rhenium on an α-alumina carrier. Catalyst for morpholine production. (2) Nickel is 2 to 20 times heavier than α-alumina, and the atomic ratio of nickel to copper is 1:04 to 1:002.
The atomic ratio of nickel to chrome 11 is 1:0.5 to 1:0.0
5 and the atomic ratio of nickel to rhenium is 1:0.3~l
The catalyst according to claim 1, wherein the catalyst is supported within a range of: 0.01.