U.S. patent application number 09/935330 was filed with the patent office on 2002-03-21 for hydroformylation process employing a catalyst based on cobalt and/or rhodium in a non-aqueous ionic solvent.
This patent application is currently assigned to Institut Francais du Petrole. Invention is credited to Commereuc, Dominique, Favre, Frederic, Olivier-Bourbigou, Helene, Saussine, Lucien.
Application Number | 20020035297 09/935330 |
Document ID | / |
Family ID | 8853751 |
Filed Date | 2002-03-21 |
United States Patent
Application |
20020035297 |
Kind Code |
A1 |
Favre, Frederic ; et
al. |
March 21, 2002 |
Hydroformylation process employing a catalyst based on cobalt
and/or rhodium in a non-aqueous ionic solvent
Abstract
In a process for hydroformylation of olefinically unsaturated
compounds using a catalyst based on cobalt and/or rhodium
coordinated by at least one ligand selected from the group formed
by nitrogen-containing or phosphorus-containing ligands used in a
non-aqueous ionic solvent, which catalyst is liquid at a
temperature of less than 90.degree. C., in which the aldehydes
formed are not or are only slightly soluble and which comprises at
least one quaternary ammonium and/or phosphonium cation Q.sup.+ and
at least one anion A.sup.-, the improvement of the invention
consists in that in the cobalt and/or rhodium complex, the ligand
also carries an ionic function (Q').sup.+(A').sup.- where Q and Q'
and/or A and A' are chemically identical.
Inventors: |
Favre, Frederic; (Saint
Fons, FR) ; Commereuc, Dominique; (Meudon, FR)
; Olivier-Bourbigou, Helene; (Rueil-Malmaison, FR)
; Saussine, Lucien; (Croissy Sur Seine, FR) |
Correspondence
Address: |
MILLEN, WHITE, ZELANO & BRANIGAN, P.C.
2200 CLARENDON BLVD.
SUITE 1400
ARLINGTON
VA
22201
US
|
Assignee: |
Institut Francais du
Petrole
4, avenue de Bois-Preau
Rueil-Malmaison
FR
|
Family ID: |
8853751 |
Appl. No.: |
09/935330 |
Filed: |
August 23, 2001 |
Current U.S.
Class: |
568/451 |
Current CPC
Class: |
C07C 45/50 20130101;
C07C 45/50 20130101; C07C 47/02 20130101 |
Class at
Publication: |
568/451 |
International
Class: |
C07C 045/49 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 23, 2000 |
FR |
00/10.971 |
Claims
1. A process for liquid phase hydroformylation of olefinically
unsaturated compounds in which the reaction is carried out in the
presence of at least one non-aqueous ionic solvent comprising at
least one salt with general formula Q.sup.+A.sup.-, where Q.sup.+
represents a quaternary ammonium and/or phosphonium cation, and
A.sup.- represents an anion, and at least one cobalt and/or rhodium
complex coordinated by at least one ligand selected from the group
formed by nitrogen-containing or phosphorus-containing ligands also
carrying an ionic function (Q').sup.+(A').sup.- where at least the
cation (Q').sup.+ or anion (A').sup.- has the same chemical nature
as the cation Q.sup.+ or anion A.sup.- of the non-aqueous ionic
solvent.
2. A process according to claim 1, wherein the non-aqueous ionic
solvent is selected from the group formed by liquid salts with
general formula Q.sup.+A.sup.- where Q.sup.+ represents a
quaternary ammonium and/or phosphonium cation and A.sup.-
represents any anion which can form a liquid salt at low
temperature, i.e., below 90.degree. C.
3. A process according to claim 1 or claim 2, wherein the A.sup.-
anions are selected from nitrate, sulfate, phosphate, acetate,
halogenoacetates, tetrafluoroborate, tetrachloroborate,
hexafluorophosphate, hexafluoroantimonate, fluorosulfonate,
perfluoroalkylsulfonates and arene-sulfonates, these latter
optionally being substituted by halogen or halogenoalkyl
groups.
4. A process according to any one of claims 1 to 3, wherein the
quaternary ammonium and/or phosphonium cations have general
formulae NR.sup.1R.sup.2R.sup.3R.sup.4+ and
PR.sup.1R.sup.2R.sup.3R.sup.4+ or general formulae
R.sup.1R.sup.2N.dbd.C R.sup.3R.sup.4+ or R.sup.1R.sup.2P.dbd.C
R.sup.3R.sup.4+ where R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which
may be identical or different, represent hydrogen with the
exception of the NH.sub.4.sup.+ cation, one single substituent
representing hydrogen, or hydrocarbyl residues containing 1 to 30
carbon atoms
5. A process according to any one of claims 1 to 3, wherein the
ammonium and/or phosphonium cation can also be derived from
nitrogen-containing and/or phosphorus-containing heterocycles
containing 1, 2 or 3 nitrogen and/or phosphorus atoms, in which the
cycles are constituted by 4 to 10 atoms, preferably 5 or 6
atoms.
6. A process according to any one of claims 1 to 3, wherein the
quaternary ammonium or phosphonium cation is constituted by a
cation with
formula:R.sup.1R.sup.2+N.dbd.CR.sup.3-R.sup.5-R.sup.3C.dbd.N.sup.+R.sup.1-
R.sup.2orR.sup.1R.sup.2+P.dbd.CR.sup.3-R.sup.5-R.sup.3C.dbd.P.sup.+R.sup.1-
R.sup.2where R.sup.1, R.sup.2 and R.sup.3, which may be identical
or different, are defined as above and R.sub.5 represents an
alkylene or phenylene residue.
7. A process according to any one of claims 1 to 6, wherein the
ammonium and/or phosphonium cation is selected from the group
formed by N-butylpyridinium, N-ethylpyridinium, pyridinium,
3-ethyl-1-methyl-imidaz- olium, 3-butyl-1-methyl-imidazolium,
diethylpyrazolium, N-butyl-N-methylpyrrolidinium,
trimethylphenylammonium, tetrabutyl-phosphonium and
tributyl-(tetradecyl)-phosphonium.
8. A process according to any one of claims 1 to 7, wherein the
non-aqueous ionic solvent is selected from the group formed by
N-butyl pyridinium hexafluorophosphate, N-ethylpyridinium
tetrafluoroborate, pyridinium fluorosulfonate, 3-butyl-1-methyl
imidazolium tetrafluoroborate, 3-butyl-1-methyl-imidazolium
hexafluoroantimonate, 3-butyl-1-methyl-imidazolium
hexafluorophosphate, 3-butyl-1-methyl-imidaz- olium
trifluoroacetate, 3-butyl-1-methyl-imidazolium
trifluoromethylsulfonate, trimethylphenylammonium
hexafluoro-phosphate and tetrabutylphosphonium
tetrafluoroborate.
9. A process according to any one of claims 1 to 8, wherein the
cobalt and/or rhodium precursor compounds of the catalyst are
selected from the group formed by cobalt and/or rhodium salts and
carbonyl complexes.
10. A process according to any one of claims 1 to 9, wherein the
cobalt and/or rhodium catalyst precursors are selected from the
group formed by acetylacetonates, carboxylates
dicobalt-octacarbonyl, cobalt-tetracarbonyl hydride,
rhodium-dicarbonyl acetylacetonate and carbonyl clusters.
11. A process according to any one of claims 1 to 10, wherein the
nitrogen-containing ligand is selected from the group formed by
monoamines, di-, tri- and polyamines, imines, di-imines, pyridines,
bipyridines, imidazoles, pyrroles and pyrazoles, all also
containing in their formula at least one substituent carrying an
ionic function (Q').sup.+(A').sup.- where at least the cation
(Q').sup.+ or anion (A').sup.- has the same chemical nature as
cation Q.sup.+ or anion A.sup.- of the non-aqueous ionic solvent
defined above.
12. A process according to any one of claims 1 to 10, wherein the
phosphorus-containing ligand is selected from the group formed by
phosphines, polyphosphines, phosphine oxides and phosphites, all
also containing in their formula at least one substituent carrying
an ionic function (Q').sup.+(A').sup.- such that at least the
cation (Q').sup.+ or anion (A').sup.- has the same chemical nature
as cation Q.sup.+ or anion A.sup.- of the non-aqueous ionic solvent
defined above.
13. A process according to any one of claims 1 to 12, wherein the
concentration of the cobalt and/or rhodium complex in the liquid
ionic solvent is in the range 0.1 mmoles per liter to 5 moles per
liter and the mole ratio between the nitrogen-containing ligand or
the phosphorus-containing ligand and the cobalt and/or rhodium
compound is in the range 0.1 to 500.
14. A process according to any one of claims 1 to 13, wherein at
least one olefinically unsaturated compound selected from the group
formed by mono-olefins, di-olefins, in particular conjugated
di-olefins, olefinic compounds comprising one or more heteroatoms,
in particular in unsaturated groups such as ketone and carboxylic
acid functions, undergoes the hydroformylation reaction.
15. A process according to any one of claims 1 to 14, wherein the
hydroformylation reaction is carried out with a partial pressure of
hydrogen and carbon monoxide of 10:1 to 1:10, at a temperature in
the range 30.degree. C. to 200.degree. C. and at a pressure in the
range 1 MPa to 20 MPa.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an improved process for
hydroformylation of olefinically unsaturated compounds using a
catalyst based on cobalt and/or rhodium used in a two-phase medium.
One of the phases is constituted by a non-aqueous ionic solvent
comprising at least one quaternary ammonium and/or phosphonium
cation Q.sup.+ and at least one anion A.sup.-. The catalyst
comprises at least one complex of cobalt and/or rhodium coordinated
with at least one ligand selected from the group formed by
nitrogen-containing or phosphorus-containing ligands also carrying
an ionic function (Q').sup.+(A').sup.- where Q and Q' and/or A and
A' are chemically identical.
[0003] 2. Description of the Prior Art
[0004] Hydroformylation of olefinic compounds is a reaction of
great industrial importance and the majority of processes use
homogeneous catalysts dissolved in an organic phase constituted by
the reactants, products and possibly an excess of ligand, although
difficulties are encountered in separating and recovering the
catalyst, in particular when it is used in relatively large
quantities, as is the case with catalysts based on cobalt, or with
a noble metal, as is the case with rhodium based catalysts.
[0005] One solution to resolving that problem has been suggested by
Bartik et al.: Organometallics (1993) 12 164-170, J. Organometal.
Chem. (1994) 480 15-21, and by Beller et al.: J. Molecular Catal.
A: Chemical (1999) 143 31-39. It consists of carrying out
hydroformylation in the presence of an aqueous solution containing
a cobalt complex which is rendered water-soluble by the presence of
a phosphine-sulfonate ligand such as the sodium salt of
trisulfonated triphenylphosphine or a trisulfonated
tris-(alkylphenyl)phosphine. International patent application
WO-A-97/00 132 describes clusters of cobalt substituted by
trialkoxysilylmethyl groups, which render them water-soluble. In
that manner, the organic phase containing the aldehydes is readily
separated from the aqueous phase containing the catalyst.
[0006] A further solution to the problem has been described in U.S.
Pat. No. 4,248,802. It consists of carrying out hydroformylation in
the presence of an aqueous solution containing a rhodium complex
which is rendered water-soluble by the presence of a sulfonated
phosphine ligand which is itself water-soluble, such as the sodium
salt of trisulfonated triphenylphosphine. In that manner, the
organic phase containing the aldehydes is readily separated from
the aqueous phase containing the catalyst. This technique has
formed the subject matter of a considerable number of studies which
have been discussed in an article by W. A. Herrmann in "Angewandte
Chemie International", 1993, volume 32, page 1524 ff.
[0007] Despite the huge industrial interest of such techniques in
the hydroformylation of propylene, such two-phase systems suffer
from a lack of solubility of the olefins in water, which leads to
relatively low reaction rates which renders them unsuitable for
long chain olefins.
[0008] Further, United States patent U.S. Pat. No. 3,565,823
describes a technique consisting of dispersing a transition metal
compound in a quaternary ammonium or phosphonium tin or germanium
salt with formula (R.sup.1R.sup.2R.sup.3R.sup.4Z)YX.sub.3, where
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are hydrocarbyl residues
containing up to 18 carbon atoms, Z is nitrogen or phosphorus, Y is
tin or germanium and X is a halogen, for example chlorine or
bromine. U.S. Pat. No. 3,832,391 describes a process for
carbonylating olefins using such a composition. Those compositions
have the disadvantage of having a relatively high melting point,
for example more than 90.degree. C., which complicates manipulation
of the solutions of catalyst and reaction products.
[0009] The Applicant's patent U.S. Pat. No. 5,874,638 describes
benefiting both from the advantages of two-phase processing and
avoiding the disadvantages connected firstly with using water and
secondly with using compounds with high melting points, by
dissolving certain catalytic compounds of transition metals from
groups 8, 9 or 10, known to catalyze hydroformylation, in
non-aqueous ionic solvents which are constituted by
organic-inorganic salts which are liquid at ambient
temperature.
SUMMARY OF THE INVENTION
[0010] It has now been discovered that, in the hydroformylation
reaction catalyzed by complexes based on cobalt and/or rhodium
carried out in a non-aqueous ionic solvent comprising at least one
quaternary ammonium and/or phosphonium cation Q.sup.+ and at least
one anion A.sup.-, which catalyst is liquid at a temperature of
less than 90.degree. C., the amount of metal retained in the ionic
solvent is greatly improved when the catalyst comprises at least
one cobalt and/or rhodium complex coordinated by at least one
ligand selected from the group formed by nitrogen-containing or
phosphorus-containing ligands also carrying an ionic function
(Q').sup.+(A').sup.- where Q and Q' and/or A and A' are chemically
identical.
[0011] More precisely, the invention provides a process for liquid
phase hydroformylation of olefinically unsaturated compounds in
which the reaction is carried out in the presence of at least one
non-aqueous ionic solvent comprising at least one salt with general
formula Q.sup.+ A.sup.-, where Q.sup.+ represents a quaternary
ammonium and/or phosphonium cation, and A represents an anion, and
at least one cobalt and/or rhodium complex coordinated by at least
one ligand selected from the group formed by nitrogen-containing or
phosphorus-containing ligands also carrying an ionic function
(Q').sup.+(A').sup.- where at least the cation (Q').sup.+ or anion
(A').sup.- has the same chemical nature as the cation Q.sup.+ or
anion A.sup.- of the non-aqueous ionic solvent.
[0012] The non-aqueous ionic solvent is selected from the group
formed by liquid salts with general formula Q.sup.+ A.sup.- where
Q.sup.+ represents a quaternary ammonium and/or phosphonium and N
represents any anion which can form a liquid salt at low
temperature, i.e., below 90.degree. C., advantageously at most
85.degree. C., preferably below 50.degree. C. Preferred anions
A.sup.- are nitrate, sulfate, phosphate, acetate, halogenoacetates,
tetrafluoroborate, tetrachloroborate, hexafluorophosphate,
hexafluoroantimonate, fluorosulfonate, perfluoroalkylsulfonates and
arene-sulfonates, these latter optionally being substituted by
halogen or halogenoalkyl groups.
[0013] The quaternary ammonium and/or phosphonium cations Q.sup.+
preferably have general formula NR.sup.1R.sup.2R.sup.3R.sup.4+ and
PR.sup.1R.sup.2R.sup.3R.sup.4+ or general formulae
R.sup.1R.sup.2N.dbd.C R.sup.3R.sup.4+ or R.sup.1R.sup.2P.dbd.C
R.sup.3R.sup.4+ where R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which
may be identical or different, represent hydrogen (with the
exception of the NH.sub.4.sup.+ cation for
NR.sup.1R.sup.2R.sup.3R.sup.4+), preferably a single substituent
represents hydrogen, or hydrocarbyl residues containing 1 to 30
carbon atoms, for example saturated or unsaturated, cycloalkyl or
aromatic alkyl groups, or aryl or aralkyl groups, which may be
substituted, containing 1 to 30 carbon atoms. The ammonium and/or
phosphonium cation can also be derived from nitrogen-containing
and/or phosphorus-containing heterocycles containing 1, 2 or 3
nitrogen and/or phosphorus atoms, in which the cycles are
constituted by 4 to 10 atoms, preferably 5 or 6 atoms.
[0014] The quaternary ammonium and/or phosphonium cation can also
be a cation with formula:
R.sup.1R.sup.2+N.dbd.CR.sup.3-R.sup.5-R.sup.3C.dbd.N.sup.+R.sup.1R.sup.2
or
R.sup.1R.sup.2+P-CR.sup.3-R.sup.5-R.sup.3C-P.sup.+R.sup.1R.sup.2
[0015] where R.sup.1, R.sup.2 and R.sup.3, which may be identical
or different, are defined as above and R.sup.5 represents an
alkylene or phenylene residue.
[0016] groups R.sup.1, R.sup.2, R.sup.3 and R.sup.4 include the
following radicals: methyl, ethyl, propyl, isopropyl, butyl,
secondary butyl, tertiary butyl, amyl, methylene, ethylidene,
phenyl or benzyl; R.sup.5 can be a methylene, ethylene, propylene
or phenylene group.
[0017] The ammonium and/or phosphonium cation Q.sup.+ is preferably
selected from the group formed by N-butylpyridinium,
N-ethylpyridinium, pyridinium, 3-ethyl-1-methyl-imidazolium,
3-butyl-1-methyl-imidazolium, diethylpyrazolium,
N-butyl-N-methylpyrrolidinium, trimethylphenyl-ammoniu- m,
tetrabutylphosphonium and tributyl-(tetradecyl)-phosphonium.
Examples of salts which can be used which can be cited are N-butyl
pyridinium hexafluorophosphate, N-ethylpyridinium
tetrafluoroborate, pyridinium fluorosulfonate, 3-butyl-1-methyl
imidazolium tetrafluoroborate, 3-butyl-1-methyl-imidazolium
hexafluoroantimonate, 3-butyl-1-methyl-imidazolium
hexafluorophosphate, 3-butyl-1-methyl-imidaz- olium
trifluoroacetate, 3-butyl-1-methyl-imidazolium
trifluoromethylsulfonate, trimethylphenylammonium
hexafluorophosphate and tetrabutylphosphonium tetrafluoroborate.
These salts can be used alone or as a mixture.
[0018] The cobalt and/or rhodium compound precursors of the
catalyst are selected from the group formed by cobalt and/or
rhodium salts such as acetylacetonates, carboxylates, in particular
formate or acetate, and carbonyl compounds, such as
dicobalt-octacarbonyl, cobalt-tetracarbonyl hydride,
rhodium-dicarbonyl acetylacetonate and carbonyl clusters. The
choice of cobalt and/or rhodium compound precursor is not critical
but it is generally preferable to avoid halides.
[0019] The nitrogen-containing ligand is selected from the group
formed by monoamines, di-, tri- and polyamines, imines, di-imines,
pyridines, bipyridines, imidazoles, pyrroles and pyrazoles, all
also containing in their formula at least one substituent carrying
an ionic function (Q').sup.+(A').sup.- where at least the cation
(Q').sup.+ or anion (A').sup.- has the same chemical nature as
cation Q.sup.+ or anion A.sup.- of the non-aqueous ionic solvent
defined above.
[0020] The phosphorus-containing ligand is selected from the group
formed by phosphines, polyphosphines, phosphine oxides and
phosphites, all also containing in their formula at least one
substituent carrying an ionic function (Q').sup.+(A').sup.- such
that at least the cation (Q').sup.+ or anion (A').sup.- has the
same chemical nature as cation Q.sup.+ or anion A.sup.- of the
non-aqueous ionic solvent defined above.
[0021] Non limiting examples of associations between the ligands
and molten salts which can be cited are:
[0022] 1-(4-pyridyl)-2-(dicyclopentyl-methyl-phosphonium)-ethane
tetrafluoroborate (1) and
1-(N-imidazolyl)-2-(dicyclopentylmethyl-phospho- nium)-ethane
tetrafluoroborate (2) ligands, used in ionic solvents constituted
by quaternary ammonium or phosphonium tetrafluoroborates and by
salts comprising dicyclopentyl-methyl-alkyl-phosphonium
cations;
[0023] 1-(diphenylphosphino)-2-(4-N-methyl-pyridinium)-ethane
hexafluorophosphate (3) ligand, used in ionic solvents constituted
by quaternary ammonium or phosphonium hexafluorophosphates and by
salts comprising 4-alkyl-N-methyl-pyridnium cations, the
1-(dicyclopentylphosphino)-2-(3-methyl-1-imidazolium)-ethane
hexafluorophosphate (4), used in ionic solvents constituted by
quaternary ammonium or phosphonium hexafluorophosphates and by
salts comprising 3-alkyl-1-methyl-imidazolium cations; 1
R.dbd.Me,X.dbd.BF.sub.4,Y.dbd.PF- .sub.6
[0024] N-(3-diphenylphosphinophenyl)-N'-dimethyl-guanidinium
tetrafluoroborate ligand (5), used in ionic solvents constituted by
quaternary ammonium or phosphonium tetrafluoroborates and by salts
comprising N-phenyl-N'-dialkyl-guanidinium cations;
[0025] tris-(tetrabutylammonium 3-phenylsulfonate)-phosphine
(tetrabutylammonium triphenylphosphine trisulfonate) (6), used in
ionic solvents constituted by tetrabutylammonium salts and by salts
comprising sulfonate anions, such as tosylates and triflates;
[0026] tris-(sodium 3-phenyl sulfonate)-phosphine ((sodium
triphenylphosphine trisulfonate) (7), used in ionic solvents
constituted by salts comprising sulfonate anions, such as tosylates
and triflates; 2
[0027] and the ligand
(di-t-butyl-3,5-catecholato)-(tetrabutylammonium
4-phenoxy-sulfonate)-phosphite (8), used in ionic solvents
constituted by tetrabutylammonium salts and by salts comprising
sulfonate anions, for example tosylates and triflates. 3
[0028] The catalytic composition is obtained by mixing, in any
manner, the liquid salt with the cobalt and/or rhodium salt and the
ligand. The transition metal compound and/or the ligand can
initially be dissolved in an organic solvent.
[0029] The complex between the cobalt and/or rhodium precursor and
the ligand can be prepared prior to the reaction by mixing the
cobalt and/or rhodium precursor with the ligand in a suitable
solvent, for example an organic solvent or the non-aqueous ionic
solvent which will subsequently be used in the catalytic reaction.
The complex can also be prepared in situ by mixing the cobalt
and/or rhodium precursor and the ligand directly in the
hydroformylation reactor.
[0030] The concentration of the cobalt and/or rhodium complex in
the liquid ionic solvent is not critical. It is advantageously in
the range 0.1 mmoles to 5 moles per liter of liquid ionic solvent,
preferably in the range 1 mmole to 1 mole per liter, and more
preferably in the range 10 to 500 mmoles per liter. The mole ratio
between the ligand and the cobalt and/or rhodium compound is in the
range 0.1 to 500, preferably in the range 1 to 100.
[0031] The components in the composition of the invention can be
mixed in any order, at a temperature in the range -20.degree. C. to
200.degree. C., preferably in the range 0.degree. C. to 140.degree.
C. and advantageously in the range 20.degree. C. to 90.degree.
C.
[0032] The olefinically unsaturated compounds which can be
hydroformylated are selected from the group formed by mono-olefins,
di-olefins, in particular conjugated di-olefins, olefinic compounds
comprising one or more heteroatoms, in particular from unsaturated
groups such as ketone and carboxylic acid functions. Examples that
can be cited are the hydroformylation of pentenes to hexanal and
methylpentanal, of hexenes to isoheptanals, of isooctenes to
isononanals and of C.sub.10 to C.sub.16 olefinic cuts to C.sub.11,
to C.sub.17 aldehydes. These olefinic compounds can be used in the
pure form or diluted with saturated hydrocarbons or other
unsaturated hydrocarbons.
[0033] The ratio of the partial pressures of hydrogen and carbon
monoxide used in the reaction medium for hydroformylation can be
10:1 to 1:10, preferably in a ratio of 1:1, but any other ratio can
be used depending on the process.
[0034] The temperature at which hydroformylation is carried out is
in the range 30.degree. C. to 200.degree. C., advantageously the
temperature is less than 150.degree. C., preferably in the range
50.degree. C. to less than 150.degree. C. The pressure can be in
the range 1 MPa to 20 MPa, preferably in the range 2 MPa to 15
MPa.
[0035] The catalytic unsaturated compound hydroformylation reaction
can be carried out on a closed system, in a semi-open system or
batchwise using one or more reaction stages. At the reaction
outlet, the organic phase containing the reaction products is
advantageously separated by simple decanting of the ionic solvent
phase containing the "molten salt" and the major portion of the
catalyst. At least a portion of this ionic solvent phase, which
contains at least a portion of the catalyst, is returned to the
reactor, the other portion being treated to eliminate the catalyst
residues.
[0036] The following examples illustrate the invention without
limiting its scope.
EXAMPLE 1
[0037] The hydroformylation reaction was carried out in a 100 ml
capacity stainless steel autoclave provided with a double envelope
enabling the temperature to be regulated by circulating a heat
exchange fluid. The following were introduced into this autoclave,
initially purged of air and moisture and placed under a
hydrogen/carbon monoxide mixture (1/1 molar) at atmospheric
pressure: 0.0193 g of rhodium dicarbonyl acetylacetonate (i.e.,
0.075 mmoles of rhodium), 4 mole equivalents of sodium
triphenylphosphinetrisulfonate, 4 ml of 3-butyl-1-methyl-imidazoli-
um trifluoromethylsulfonate, 2 ml of heptane (standard) and 7.5 ml
of hexene-1. In this example, the sulfonate anion was the common
ion of the ligand and the non-aqueous ionic solvent. The pressure
of the hydrogen-carbon monoxide mixture (1/1 molar) was raised to 2
MPa and the temperature to 80.degree. C. and stirring was
commenced. After 2 hours, stirring was stopped and the reaction
mixture was allowed to decant and cool, then the pressure was
released. After removal from the autoclave, the upper organic phase
was colorless. The hexene-l conversion was 99% by weight. The
selectivity for C7 aldehydes was 93% and the n/iso
(n-heptanal/isoheptanals) ratio was 3.5. Analysis of the upper
organic phase showed that it contained less than 5 ppm of rhodium
metal (ppm: parts per million, by weight).
EXAMPLE 2 (comparative)
[0038] The hydroformylation reaction was carried out in the same
apparatus and using the same procedure as that described for
Example 1. The following were introduced into this autoclave,
initially purged of air and moisture and placed under a
hydrogen/carbon monoxide mixture (1/1 molar) at atmospheric
pressure: 0.0193 g of rhodium dicarbonyl acetylacetonate (i.e.,
0.075 mmoles of rhodium), 4 mole equivalents of sodium
triphenylphosphine trisulfonate, 4 ml of 3-butyl-1-methyl-imidazol-
ium fluorophosphate, 2 ml of heptane (standard) and 7.5 ml of
hexene-1. In this comparative example, there was no common ion
between the ligand and the non-aqueous ionic solvent. The pressure
of the hydrogen-carbon monoxide mixture (1/1 molar) was raised to 2
MPa and the temperature to 80.degree. C. and stirring was
commenced. After 3 hours, stirring was stopped and the reaction
mixture was allowed to decant and cool, then the pressure was
released. After removal from the autoclave, the upper organic phase
was colorless. The hexene-1 conversion was 74% by weight. The
selectivity for C7 aldehydes was 48% and the n/iso
(n-heptanal/isoheptanals) ratio was 2.7. Analysis of the upper
organic phase showed that it contained 195 ppm of rhodium metal
(ppm: parts per million, by weight).
EXAMPLE 3
[0039] The hydroformylation reaction was carried out in the same
apparatus and using the same procedure as that described for
Example 1. 0.0193 g of rhodium dicarbonyl acetylacetonate (i.e.,
0.075 mmoles of rhodium), 4 mole equivalents of sodium
triphenylphosphine-disulfonate, 4 ml of
3-butyl-1-methyl-imidazolium trifluoromethanesulfonate, 2 ml of
heptane (standard) and 7.5 ml of hexene-1 were introduced. In this
example, the sulfonate anion was the common ion between the ligand
and the non-aqueous ionic solvent. The pressure of the
hydrogen-carbon monoxide mixture (1/1 molar) was raised to 2 MPa
and the temperature to 80.degree. C. and stirring was commenced.
After 2 hours, stirring was stopped and the reaction mixture was
allowed to decant and cool, then the pressure was released. After
removal from the autoclave, the upper organic phase was colorless.
The hexene-1 conversion was 98% by weight. The selectivity for C7
aldehydes was 96% and the n/iso (n-heptanal/isoheptanals) ratio was
3.5. Analysis of the upper organic phase showed that it contained
less than 5 ppm of rhodium metal (ppm: parts per million, by
weight).
EXAMPLE 4
[0040] The hydroformylation reaction was carried out in the same
apparatus and using the same procedure as that described for
Example 1. 0.0193 g of rhodium dicarbonyl acetylacetonate (i.e.,
0.075 mmoles of rhodium), 10 mole equivalents of
N-(3-diphenylphosphinophenyl)-N'-dimethyl-guanidinium
tetrafluoroborate, 4 ml of 3-butyl-1-methyl-imidazolium
tetrafluoroborate, 2 ml of heptane (standard) and 7.5 ml of
hexene-1 were introduced. In this example, the tetrafluoroborate
anion was the common ion between the ligand and the non-aqueous
ionic solvent. The pressure of the hydrogen-carbon monoxide mixture
(1/1 molar) was raised to 2 MPa and the temperature to 80.degree.
C., and stirring was commenced. After 2 hours, stirring was stopped
and the reaction mixture was allowed to decant and cool, then the
pressure was released. After removal from the autoclave, the upper
organic phase was colorless. The hexene-1 conversion was 77% by
weight. The selectivity for C7 aldehydes was 74% and the n/iso
(n-heptanal/isoheptanals) ratio was 3. Analysis of the upper
organic phase showed that it contained less than 5 ppm of rhodium
metal (ppm: parts per million, by weight).
EXAMPLE 5
[0041] The hydroformylation reaction was carried out in the same
apparatus and using the same procedure as that described for
Example 1. 0.0193 g of rhodium dicarbonyl acetylacetonate (i.e.,
0.075 mmoles of rhodium), 7 mole equivalents of
1-(diphenylphosphino)-2-(4-N-methyl-pyridinium)-ethan- e
tetrafluoroborate, 4 ml of 3-butyl-1-methyl-imidazolium
tetrafluoroborate, 2 ml of heptane (standard) and 7.5 ml of
hexene-1 were introduced. In this example, the tetrafluoroborate
anion was the common ion between the ligand and the non-aqueous
ionic solvent. The pressure of the hydrogen-carbon monoxide mixture
(1/1 molar) was raised to 2 MPa and the temperature to 80.degree.
C., and stirring was commenced. After 4 hours, stirring was stopped
and the reaction mixture was allowed to decant and cool, then the
pressure was released. After removal from the autoclave, the upper
organic phase was colorless. The hexene-1 conversion was 84% by
weight. The selectivity for C7 aldehydes was 99% and the n/iso
(n-heptanal/isoheptanals) ratio was 2.6. Analysis of the upper
organic phase showed that it contained less than 10 ppm of rhodium
metal (ppm: parts per million, by weight).
EXAMPLE 6
[0042] The hydroformylation reaction was carried out in a 300 ml
capacity stainless steel autoclave provided with a double envelope
enabling the temperature to be regulated by circulating a heat
exchange fluid, and provided with an efficient mechanical stirrer
with blades and counter-blades. The following were introduced into
this autoclave, initially purged of air and moisture and placed
under a hydrogen/carbon monoxide mixture (1/1 molar) at atmospheric
pressure: 0.4 g of dicobalt-octacarbonyl (i.e., 2.3 mmoles of
cobalt), 1 mole equivalent of
1-(4-pyridyl)-2-(dicyclopentyl-methyl-phosphonium)-ethane
tetrafluoroborate, 10 ml of 3-butyl-1-methyl-imidazolium
tetrafluoro-borate, 30 ml of heptane and 30 ml of hexene-1. The
pressure of the hydrogen-carbon monoxide mixture (1/1 molar) was
raised to 9 MPa and the temperature to 95.degree. C. and stirring
was commenced. After 6 hours, stirring was stopped and the reaction
mixture was allowed to decant and cool, then the pressure was
released. After removal from the autoclave, the upper organic phase
was slightly colored, indicating that only traces of cobalt had
been extracted. The hexene-1 conversion was 80% by weight. The
selectivity for C7 aldehydes was 96.4% and the n/iso
(n-heptanal/isoheptanals) ratio was 3.6.
[0043] The preceding examples can be repeated with similar success
by substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in the
preceding examples. Also, the preceding specific embodiments are to
be construed as merely illustrative, and not limitative of the
remainder of the disclosure in any way whatsoever.
[0044] The entire disclosure of all applications, patents and
publications cited above and below, and of corresponding French
application 00/10971, filed Aug. 23, 2000, are hereby incorporated
by reference.
[0045] From the foregoing description, one skilled in the art can
easily ascertain the essential characteristics of this invention
and, without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
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