Process for preparing amines

Details Process for preparing amines Process for preparing amines

2000-12-05

2003-02-25

Raymond, Richard L. (Department: 1624)

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

Organic compounds

Amino nitrogen containing

C564S347000, C564S397000, C564S446000, C564S480000, C564S401000, C564S447000, C564S349000, C564S479000, C546S184000, C546S246000, C544S059000, C544S106000

Reexamination Certificate

active

06525222

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.
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 (page 2, lines 47 to 48; cf. also 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 or carbonyl compounds. The preferred zirconium oxide content of these catalysts is 70 to 80% by weight (loc. cit.: page 2, last paragraph; page 3, 3rd 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.
Earlier German application No. 19910950.5 of Mar. 12, 1999 discloses catalysts containing oxides of nickel, copper and zirconium for the catalytic amination of aldehydes or ketones with nitrogen compounds in the presence of hydrogen. The catalysts preferably contain no catalytically active amounts of cobalt. Although these catalysts have a good activity, their mechanical stabilities and selectivities require improvement.
EP-A-905 122 relates to a process for preparing amines by reacting primary or secondary alcohols with nitrogen compounds selected from the group of ammonia and primary and secondary amines at elevated temperatures and pressures with hydrogen in the presence of catalysts containing zirconium, copper and nickel but no cobalt.
The earlier European application No. 99111282.2 of Jun. 10, 1999, relates to a process for preparing amines by reacting primary or secondary alcohols with nitrogen compounds selected from the group of ammonia, primary and secondary amines, at elevated temperatures and pressures with hydrogen in the presence of catalysts containing zirconium, copper, nickel and cobalt.
Earlier German application No. 19859776.2 of Dec. 23, 1998 describes a process for preparing amines by reacting primary or secondary alcohols, aldehydes or ketones with nitrogen compounds at elevated temperatures and pressures in the presence of hydrogen and a catalyst containing copper and oxygen-containing titanium compounds, the catalyst being employed in the form of shaped articles produced with the addition of metallic copper powder.
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 on a copper catalyst which has been obtained by thermal decomposition and reduction of a basic copper aluminum carbonate.
Disadvantages of prior art processes are that the selectivities and yields achieved in the aminating hydrogenation of aldehydes and ketones are too low and/or the catalysts show inadequate activity and/or stability under the reaction conditions.
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 of aldehyde or ketone, in particular conversions of 90 to 100%, high yield, high selectivity, in particular selectivities of 95 to 100% (based on the aldehyde or ketone) and long catalyst life with, at the same time, high mechanical stability of the catalyst shaped article (e.g. measured as side crushing strength). The catalysts ought accordingly to have a high activity and a high chemical and 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, wherein the catalytically active mass of the catalyst contains, after its preparation and before the treatment with hydrogen,
22 to 45% 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,
5 to 50% by weight of oxygen-containing compounds of nickel, calculated as NiO, where the molar ratio of nickel to copper is greater than 1,
5 to 50% by weight of oxygen-containing compounds of cobalt, calculated as CoO,
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 and/or manganese, calculated as Al
2
O
3
or MnO
2
.
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 inactive constituents.
The catalytically active mass can be introduced into the reaction vessel after grinding as powder or as chips or, preferably, introduced into 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 prepared catalyst after its last heat treatment and before the treatment with hydrogen.
The catalytically active mass of the catalyst after its last heat treatment and before the treatment with hydrogen is defined as the total of the masses of the catalytically active constituents and of the support materials and essentially comprises oxygen-containing compounds of zirconium, oxygen-containing compounds of copper, oxygen-containing compounds of nickel, oxygen-containing compounds of cobalt and, optionally, oxygen-containing compounds of molybdenum and/or oxygen-containing compounds of aluminum and/or oxygen-containing compounds of manganese.
The total of the abovementioned catalytically active constituents and of the abovementioned support materials in the catalytically active mass, calculated as ZrO
2
, CuO, NiO, CoO, MoO
3
, Al
2
O
3
and MnO
2
, 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 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 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

Affiliated with

Also associated with

Rating

Process for preparing amines does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for preparing amines, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for preparing amines will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3120879