Method for preparing a catalyst and catalysts prepared...

Details Method for preparing a catalyst and catalysts prepared... Method for preparing a catalyst and catalysts prepared...

2000-05-31

2002-02-26

Richter, Johann (Department: 1621)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Plural component system comprising a - group i to iv metal...

C502S154000, C502S174000, C502S344000, C502S345000, C564S471000, C564S487000, C564S503000, C568S855000, C568S865000

Reexamination Certificate

active

06350714

ABSTRACT:

The present invention relates to a process for preparing a catalyst by activating a catalytic composition which comprises at least one compound of a metal of group IB or IIB of the Periodic Table, where appropriate bismuth or a compound thereof, and where appropriate a carrier, and to the catalysts obtainable by this process. The invention further relates to a process for preparing alkynols and to a process for preparing aminoalkynes using these catalysts.
The preparation of alkynols by addition of a carbonyl compound onto an alkyne and, in particular, onto acetylene with retention of the triple bond, and the preparation of aminoalkynes by reacting an alkyne with a carbonyl compound and an amine in a Mannich-type condensation have been known for a long time and used industrially. Both reactions can be catalyzed homogeneously or heterogeneously, generally employing heavy metal acetylides and, in particular, catalysts based on copper(I) acetylide.
U.S. Pat. No. 3,496,232 describes the preparation of N-alkyl-substituted aminoalkynes in a homogeneously or heterogeneously catalyzed Mannich reaction, the catalysts employed being salts of metals of group IB or IIB, such as, for example, the chlorides, acetates, formates and acetylides and, specifically, copper acetylide. These can, in the case of the heterogeneously catalyzed process variant, be employed on an inert carrier. The copper acetylide catalyst is prepared in this case before the actual Mannich reaction by reacting copper(II) chloride with paraformaldehyde and acetylene in an autoclave.
DE-A-23 14 693 describes a process for preparing butynediol by reacting acetylene and formaldehyde, employing a supported heavy metal acetylide catalyst which is obtained by impregnating a carrier with a heavy metal salt solution and subsequently treating with gaseous acetylene.
DE-A-24 21 407 likewise describes a process for preparing butynediol, employing supported copper acetylide catalysts.
DE-A-26 02 418 describes a process for preparing butynediol, employing a supported catalyst which is obtained by reacting a copper(II) compound with acetylene and formaldehyde in aqueous solution at a pH below 5.5.
U.S. Pat. No. 3,650,985 describes the prepartion of unsupported copper acetylide catalysts of the general formula (CuC
2
)
w
(CH
2
O)
x
(C
2
H
2
)
y
(H
2
O)
z
with 1≦w, x, y<100, preferably w=4, x=0.24 to 4, y=0.24 to 4 and z=0.67 to 2.8. These catalysts may additionally contain a bismuth compound and can be prepared by formaldehyde and acetylene acting simultaneously on the particulate, water-insoluble copper compound, preferably basic copper carbonate, such as, for example, synthetically prepared malachite. They are used as aqueous catalyst suspension for the ethynylation of acetylenically unsaturated hydrocarbons. Similar malachite catalysts are described in U.S. Pat. No. 3,560,576.
U.S. Pat. No. 4,110,249 describes a process for preparing bismuth-modified spheroidal malachites and their reaction with acetylene and formaldehyde to give unsupported ethynylation catalysts. U.S. Pat. No. 4,127,734 describes a process for preparing 1,4-butynediol by reacting acetylene and formaldehyde in the presence of these catalysts.
U.S. Pat. No. 4,536,491 describes agglomerates of spheroidal malachites which comprise bismuth and silica. These malachites can be converted into copper acetylide complexes by reacting in the form of an aqueous suspension with acetylene and formaldehyde. U.S. Pat. No. 4,584,418 describes a process for preparing 1,4-butynediol by reacting acetylene with formaldehyde in the presence of these catalysts.
U.S. Pat. No. 4,119,790 describes a continuous, multistage low-pressure ethynylation process for preparing 1,4-butynediol, employing an ethynylation catalyst based on a water-insoluble copper acetylide complex. This ethynylation catalyst is prepared by reacting a precursor which comprises between 20 and 35% by weight of copper and 0 to 3% by weight of bismuth on a magnesium silicate carrier with formaldehyde in the presence of acetylene.
EP-A-0 080 794 describes a heterogeneously catalyzed process for preparing N,N-disubstituted propynylamines, the catalysts employed being copper acetylides on a magnesium silicate carrier doped with bismuth oxide. These are conventional ethynylation catalysts which must be activated before they are used with acetylene and formaldehyde.
The disadvantage of the catalysts described above is that they are prepared by activating a catalytic composition using acetylene. Operations with acetylene, which is a thermally unstable gas which easily explodes even under atmospheric pressure, are industrially complicated because considerable safety measures are necessary in the design of the reactors. This particularly applies to operations with liquefied acetylene and/or manipulation thereof under high pressures. The heavy metal catalysts obtained on activation of the catalytic composition with acetylene are also generally prone to explosive decomposition and can therefore be manipulated only with difficulty. Processes in which catalysts of these types are employed are therefore at a commercial disadvantage. This particularly applies when acetylene is employed only in the preparation or activation of the catalyst, while the subsequent ethynylation or aminoalkylation reaction takes place with use of a different alkyne.
It is an object of the present invention to provide a process for preparing a catalyst by activating a catalytic composition allowing the use of acetylene to be dispensed with.
We have found that this object is achieved by a process in which a catalytic composition which comprises at least one metal of group IB or IIB of a compound thereof, where appropriate bismuth or a compound thereof, and where appropriate a carrier, is activated with an alkyne different from acetylene and with a carbonyl compound.
It has also been found, surprisingly, that the use of acetylene in activating the catalytic composition can generally also be dispensed with if the following alkynylation or aminoalkylation reaction is carried out in the presence of acetylene, because the alkyne employed for the activation can generally be different from the alkyne employed for the following reaction.
The invention therefore relates to a process for preparing a catalyst by activating a catalytic composition which comprises
a) at least one metal of group IB or IIB or a compound thereof,
b) where appropriate a carrier
which comprises treating the composition with an alkyne of the general formula I
R
1
—C≡C—R
2
  (I)
in which
R
1
is alkyl, cycloalkyl, aryl, hydroxyalkyl, haloalkyl, alkoxy or alkoxyalkyl,
R
2
is a hydrogen atom, alkyl, cycloalkyl or aryl, and a carbonyl compound of the general formula II
in which
R
3
and R
4
are, independently of one another, a hydrogen atom, alkyl, haloalkyl, cycloalkyl or aryl.
For the purpose of the present invention, halogen is fluorine, chlorine, bromine and iodine and, in particular, chlorine and bromine.
The term “alkyl” comprises straight-chain and branched alkyl groups. These are preferably straight-chain or branched C
1
-C
12
-alkyl and, in particular, C
1
-C
6
-alkyl groups. Examples of alkyl groups are, in particular, methyl, ethyl, propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl and dodecyl.
Haloalkyl is an alkyl group as defined above which is halogenated with one or more halogen atoms, in particular chlorine and bromine, partially or completely, preferably with one to three halogen atoms.
The above statements

Affiliated with

Also associated with

Rating

Method for preparing a catalyst and catalysts prepared... does not yet have a rating. At this time, there are no reviews or comments for this patent.

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

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2983486