Preparation of amines

Details Preparation of amines Preparation of amines

1999-12-14

2001-02-13

Barts, Samuel (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C564S397000, C564S401000, C564S446000, C564S447000, C564S472000, C564S479000, C546S184000, C546S246000

Reexamination Certificate

active

06187957

ABSTRACT:

The present invention relates to a process for the preparation of primary, secondary or tertiary amines by reacting primary or secondary alcohols, aldehydes or ketones with nitrogen compounds selected from the group consisting of ammonia and primary and secondary amines at elevated temperatures and superatmospheric pressures in the presence of hydrogen and of a catalyst containing copper and oxygen-containing compounds of titanium.
The preparation of amines by the catalytic amination of alcohols, aldehydes or ketones in the presence of hydrogen plays an important role in the chemical industry. The reaction products are used mainly as process chemicals (for example, blowing agents for polyurethane production), catalysts (for the preparation of surfactants and polymers) and intermediates for relatively highly finished products, for example dyes and crop protection agents.
SU-A-644 526 (Derwent Abstract no. 76773B/42) describes the alkylation of aromatic amines by reaction with alcohols in the gas phase at elevated temperatures in the presence of hydrogen and a catalyst consisting of 45% by weight of CuO, 19% by weight of Cr
2
O
3
, 25% by weight of TiO
2
, 6% by weight of BaO and 5% by weight of graphite.
SU-A-464 178 (Derwent Abstract no. 49191C/28) discloses a synthesis for morpholine by reacting diethylene glycol with ammonia in the presence of hydrogen and a nickel-copper-chromium-titanium catalyst at from 200 to 250° C.
SU-A-968 029 (Derwent Abstract no. 83-746162/34) and SU-A-1 113 375 (Derwent Abstract no. 85-085786/14) describe the simultaneous preparation of 2-amino-2′-hydroxydiethyl ether and morpholine by reacting diethylene glycol with ammonia at from 180 to 230° C. in the presence of hydrogen and of a catalyst containing 24-36 mol % of Ni, 25-35 mol % of Cu, 1-7 mol % of Cr
2
O
3
and 27-51 mol % of Ti.
DE-A-27 58 769 discloses a process for the preparation of morpholine by reacting diethylene glycol with ammonia in the presence of H
2
in the vapor phase and in the presence of a catalyst composed of from 25 to 55% by weight of NiO, from 15 to 40% by weight of CuO, from 0.7 to 7% by weight of Cr
2
O
3
and from 20 to 40% by weight of TiO
2
.
The disadvantage of these catalysts is that, owing to their chromium content, they present problems with regard to environmental pollution.
DE-A-19 50 7007 reports a process for the amination of alcohols in the presence of catalysts consisting of from 0.001 to 25% by weight of Ru and from 0 to 5% by weight of promoters, for example Pd, Cu and Cr, on porous oxides, such as Al
2
O
3
, SiO
2
, TiO
2
or ZrO
2
.
WO 96/38226 relates to rhenium catalysts containing nickel, cobalt, boron and copper and/or ruthenium on a support and their use for the hydrogenation of alcohols under aminating conditions.
JP-A-07 323 226 (Derwent Abstract no. 96-064983/07) relates to Ni-Al catalysts for the amination of aliphatic alcohols.
U.S. Pat. No. 4 772 750 describes, in examples 3 and 4, the amination of monoethanolamine with ammonia in the presence of H
2
and a Cu-Co-TiO
2
catalyst which was prepared by a special salt melt impregnation method.
EP-A-320 074 relates to supported Cu catalysts having an Fe promoter, the support being, for example, SiO
2
, TiO
2
or Al
2
O
3
, and their use for, inter alia, hydrogenation of alcohols under aminating conditions.
EP-A-315 189 reports mixed oxide catalysts containing niobium oxide and titanium, aluminum, silicon and zirconium oxides and/or oxides of the elements of groups II A, V A, VI A, I B, II B, III B, V B, VI B, VII B or VIII of the Periodic Table and their use in the hydrogenation of alkanolamines under aminating conditions.
The prior German application no. 19809418.3 relates to a process for the catalytic hydrogenation of carbonyl compounds in the presence of a copper catalyst which contains TiO
2
, the copper catalyst as such and a process for its preparation.
The prior German applications no. 19742911.4 and 19826396.1 relate to processes for the preparation of amines by reacting primary or secondary alcohols with nitrogen compounds selected from the group consisting of ammonia and primary and secondary amines at from 80 to 250° C. and from 0.1 to 40 MPa and with hydrogen in the presence of a catalyst containing zirconium, copper and nickel.
It is an object of the present invention to provide an improved economical process for the preparation of amines from primary or secondary alcohols, aldehydes or ketones, the catalyst used being technically easy to prepare, permitting high conversions and selectivities, i.e. high space-time yields of the product, and having high chemical and mechanical stability and activity and a long life under the reaction conditions occurring in said process.
We have found that this object is achieved by a process for the preparation of amines by reacting primary or secondary alcohols, aldehydes or ketones with nitrogen compounds selected from the group consisting of ammonia and primary and secondary amines at elevated temperatures and superatmospheric pressures in the presence of hydrogen and of a catalyst containing copper and oxygen-containing compounds of titanium, wherein the catalyst is used in the form of moldings which have been prepared with the addition of metallic copper powder.
The admixing of metallic Cu powder before the shaping of the catalyst material into moldings, for example pellets, it being possible also to add conventional molding assistants, such as graphite, to the dried and powdered catalyst material, which comprises catalytically active material and, if required, inert material, before the shaping, leads
a) to shaping which is particularly easy to carry out,
b) to high activities and selectivities in the novel process and
c) to high chemical and mechanical stability of the catalyst molding both in the oxidic and in the reduced state.
The catalytically active material of the molded catalysts used in the novel process contains, after their final heat treatment and before their reduction with hydrogen,
from 20 to 83, preferably from 25 to 75, particularly preferably from 30 to 68, % by weight, calculated as TiO
2
, of oxygen-containing compounds of titanium,
from 15 to 60, preferably from 20 to 55, particularly preferably from 22 to 50, % by weight, calculated as CuO, of oxygen-containing compounds of copper, and
from 2 to 29, preferably from 5 to 25, particularly preferably from 10 to 22, % by weight of metallic copper, which was added before the shaping of the catalyst material.
A part, for example from 5 to 50, in particular from 30 to 50, % by weight of the oxygen-containing compounds of titanium (e.g. TiO
2
) can be replaced by oxygen-containing compounds of aluminum, e.g. alumina (Al
2
O
3
), and/or oxygen-containing compounds of zirconium, such as zirconium dioxide (ZrO
2
), and/or oxygen-containing compounds of silicon, e.g. silica (SiO
2
).
The catalytically active material of the catalysts used in the novel process may furthermore contain one or more elements, or the inorganic or organic compounds thereof, selected from the groups I A, II A, III B, IV B, V B, VI B, VIII, I B, II B, III A, IV A, V A and VI A.
In general, the catalysts are preferably used in the form of unsupported catalysts in the novel process. The term “unsupported catalyst” denotes a catalyst which consists only of catalytically active material and, if required, a molding assistant, e.g. graphite or stearic acid, if the catalyst is used in the form of moldings.
In this context, oxygen-containing compounds of titanium, e.g. TiO
2
, oxygen-containing compounds of aluminum, e.g. Al
2
O
3
, oxygen-containing compounds of zirconium, e.g. ZrO
2
, and oxygen-containing compounds of silicon, e.g. SiO
2
, are considered as belonging to the catalytically active material.
The catalysts are arranged as suitable moldings—for example as pellets, spheres, cylinders, rings or extrudates—in the reactor.
The stated concentrations (in % by weight) of the components of the catalyst relate in each case—unless stated otherwise—to the catalytically active material of the prepared cataly

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