Preparing amines

Details Preparing amines Preparing amines

2000-03-07

2002-07-09

Shah, Mukund J. (Department: 1624)

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

Organic compounds

Unsubstituted hydrocarbyl chain between the ring and the -c-...

C540S467000, C540S470000, C540S533000, C540S544000, C540S575000, C540S596000, C540S610000, C540S612000, C544S088000, C544S106000, C544S242000, C544S392000, C544S410000, C546S184000, C546S192000, C546S207000, C548S215000, C548S300100, C548S577000, C548S578000, C548S579000, C548S950000, C564S373000, C564S374000, C564S384000, C564S397000

Reexamination Certificate

active

06417353

ABSTRACT:

The present invention relates to a process for preparing amines by reacting aldehydes or ketones at elevated temperature under elevated pressure with nitrogen compounds selected from the group of ammonia, primary and secondary amines, and with hydrogen in the presence of a catalyst containing copper.
EP-A-514 692 discloses catalysts containing oxides of copper, nickel and/or cobalt, zirconium and/or aluminum for the catalytic amination of alcohols in the gas phase with ammonia or primary amines and hydrogen. This patent application discloses that the atomic ratio of nickel to copper in these catalysts must be from 0.1 to 1.0, preferably 0.2 to 0.5 (cf. loc. cit.: Example 1) since, otherwise, yield-reducing byproducts are formed to an increased extent in the amination of alcohols (loc. cit.: Examples 6 and 12). Aluminum oxide is preferably used as support (loc. cit.: Examples 1 to 5 and 7 to 11).
EP-A-382 049 discloses catalysts containing oxygen-containing zirconium, copper, cobalt and nickel compounds, and processes for the hydrogenating amination of alcohols. The preferred zirconium oxide content of these catalysts is 70 to 80% by weight (loc. cit.: page 2, last paragraph; page 3, 3
rd
paragraph; Examples). Although these catalysts have good activity and selectivity, their useful lives are in need of improvement.
EP-A-696 572 and EP-A-697 395 disclose catalysts containing oxides of nickel, copper, zirconium and molybdenum for the catalytic amination of alcohols with nitrogen compounds in the presence of hydrogen.
The earlier German applications Nos. 19742911.4 of Sep. 29, 1997 and 19826396.1 of Jun. 12, 1998, relate to processes for preparing amines by reacting primary or secondary alcohols with nitrogen compounds selected from the group of ammonia, primary and secondary amines, at temperatures of from 80 to 250° C. under pressures of from 0.1 to 40 MPa with hydrogen in the presence of catalysts containing zirconium, copper and nickel.
DE-A-28 38 184 describes a process for preparing tertiary amines by reacting secondary amines with alcohols or carbonyl compounds under hydrogenating conditions in the gas phase, by undertaking the reaction of a copper catalyst which has been obtained by thermal decomposition and reduction of a basic copper aluminum carbonate.
It is an object of the present invention to improve, by remedying the disadvantages of the prior art, the economics of the processes used to date for the hydrogenating amination of aldehydes and ketones. It was intended to find catalysts which can be prepared industrially in a simple manner and which permit the hydrogenating amination of aldehydes and ketones to be carried out with high conversion and good yield, selectivity and catalyst life. The catalysts ought accordingly to have a high activity and a high mechanical stability under the reaction conditions.
We have found that this object is achieved by a process for preparing amines by reacting aldehydes or ketones at elevated temperature under elevated pressure with nitrogen compounds selected from the group of ammonia, primary and secondary amines, and with hydrogen in the presence of a catalyst containing
copper, wherein the catalytically active mass of the catalyst contains, before the reduction with hydrogen,
20 to 85% by weight of oxygen-containing compounds of zirconium, calculated as ZrO
2
,
1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO,
14 to 70% by weight of oxygen-containing compounds of nickel, calculated as NiO,
0 to 5% by weight of oxygen-containing compounds of molybdenum, calculated as MoO
3
,
and 0 to 10% by weight of oxygen-containing compounds of aluminum, calculated as Al
2
O
3
.
The catalysts in the process according to the invention are generally employed preferably in the form of catalysts which consist only of catalytically active mass and, where appropriate, a molding auxiliary (such as graphite or stearic acid) if the catalyst is employed as shaped articles, that is to say contain no other catalytically active constituents.
In this connection, the oxygen-containing compounds of zirconium and of aluminum which are used as support materials are regarded as belonging to the catalytically active mass.
The catalysts are employed in such a way that the catalytically active mass which has been ground to a powder is introduced into the reaction vessel, or that the catalytically active mass is arranged in the reactor after grinding, mixing with shaping auxiliaries, shaping and heat-treating as catalyst shaped articles—for example as tablets, beads, rings, extrudates (e.g. ribbons).
The concentrations (in % by weight) stated for the components of the catalyst are in each case—unless stated otherwise—based on the catalytically active mass of the finished catalyst after its last heat treatment and before its reduction with hydrogen.
The catalytically active mass of the catalyst after its last heat treatment and before its reduction with hydrogen is defined as the total of the masses of the catalytically active constituents and of the abovementioned catalyst support materials and essentially comprises the constituents of oxygen-containing compounds of zirconium, oxygen-containing compounds of copper, oxygen-containing compounds of nickel and, optionally, oxygen-containing compounds of molybdenum and/or oxygen-containing compounds of aluminum.
The total of the abovementioned constituents in the catalytically active mass, calculated as ZrO
2
, CuO, NiO, MoO
3
and Al
2
O
3
, is normally from 70 to 100% by weight, preferably 80 to 100% by weight, particularly preferably 90 to 100% by weight, in particular 95 to 100% by weight, very particularly preferably 100% by weight.
The catalytically active mass of the catalysts employed in the process according to the invention may furthermore comprise one or more elements (oxidation state 0) or their inorganic or organic compounds selected from groups I A to VI A and I B to VII B and VIII of the periodic table. Examples of such elements or compounds thereof are: transition metals such as Co or CoO, Mn or manganese oxides, Re or rhenium oxides, Cr or chromium oxides, W or tungsten oxides, Ta or tantalum oxides, Nb or niobium oxides or niobium oxalate, V or vanadium oxides or vanadyl pyrophosphate; lanthanides such as Ce or CeO
2
, or Pr or Pr
2
O
3
; alkali metal oxides such as Na
2
O; alkali metal carbonates; alkaline earth metal oxides such as SrO; alkaline earth metal carbonates such as MgCO
3
, CaCO
3
and BaCO
3
; boron oxide (B
2
O
3
).
The catalytically active mass of the catalysts employed in the process according to the invention contains after the last heat treatment thereof and before the reduction with hydrogen 20 to 85% by weight, preferably 20 to 84.9% by weight, particularly preferably 22 to 65% by weight, very particularly preferably 25 to 49.7% by weight, of oxygen-containing compounds of zirconium, calculated as ZrO
2
, 1 to 30% by weight, particularly preferably 5 to 25% by weight, very particularly preferably 10 to 25% by weight, of oxygen-containing compounds of copper, calculated as CuO, 14 to 70% by weight, particularly preferably 29.7 to 70% by weight, very particularly preferably 40 to 60% by weight, of oxygen-containing compounds of nickel, calculated as NiO, 0 to 5% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.3 to 3.5% by weight, of oxygen-containing compounds of molybdenum, calculated as MoO
3
, and 0 to 10% by weight, very particularly preferably 0 to 5% by weight, of oxygen-containing compounds of aluminum, calculated as Al
2
O
3
.
The content of oxygen-containing compounds of aluminum, calculated as Al
2
O
3
, in the catalytically active mass can be up to 10% by weight, and the ratio by weight of oxygen-containing compounds of zirconium, calculated as ZrO
2
, to the oxygen-containing compounds of aluminum, calculated as Al
2
O
3
, is at least 2.2, preferably at least 2.5, particularly preferably at least 5.
The catalysts preferably employed in the process according to the invention have a catalytically active mass after the last

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