U.S. patent application number 12/546187 was filed with the patent office on 2010-04-22 for homogeneous process for the hydrogenation of carboxylic acids and derivatives thereof.
This patent application is currently assigned to Davy Process Technology Limited. Invention is credited to Simon Peter Crabtree, Melvyn Kilner, Derek Vincent Tyers, Michael Anthony Wood.
Application Number | 20100099550 12/546187 |
Document ID | / |
Family ID | 9936004 |
Filed Date | 2010-04-22 |
United States Patent
Application |
20100099550 |
Kind Code |
A1 |
Kilner; Melvyn ; et
al. |
April 22, 2010 |
Homogeneous Process for the Hydrogenation of Carboxylic Acids and
Derivatives Thereof
Abstract
A homogenous process for the hydrogenation of the carboxylic
acids and/or derivatives thereof in the presence of a catalyst
comprising ruthenium, rhodium, iron, osmium or palladium, and an
organic phosphine is described in which the hydrogenation is
carried out in the presence of at least about 1% by weight water. A
process for regenerating a catalyst comprising ruthenium, rhodium,
iron, osmium or palladium and an organic phosphine is also
described in which the regeneration is carried out in the presence
of hydrogen and water.
Inventors: |
Kilner; Melvyn; (Wilton
Gilbert, GB) ; Tyers; Derek Vincent; (Teesdale,
GB) ; Crabtree; Simon Peter; (Durham Moor, GB)
; Wood; Michael Anthony; (Hilton, GB) |
Correspondence
Address: |
MCDONNELL BOEHNEN HULBERT & BERGHOFF LLP
300 S. WACKER DRIVE, 32ND FLOOR
CHICAGO
IL
60606
US
|
Assignee: |
Davy Process Technology
Limited
|
Family ID: |
9936004 |
Appl. No.: |
12/546187 |
Filed: |
August 24, 2009 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10513290 |
Jun 20, 2005 |
|
|
|
PCT/GB03/01819 |
Apr 29, 2003 |
|
|
|
12546187 |
|
|
|
|
Current U.S.
Class: |
502/53 ;
252/182.12 |
Current CPC
Class: |
C07C 29/149 20130101;
Y02P 20/52 20151101; Y02P 20/584 20151101; B01J 31/4053 20130101;
B01J 2531/824 20130101; C07C 29/149 20130101; C07C 29/149 20130101;
C07C 27/04 20130101; B01J 2531/0258 20130101; B01J 2531/821
20130101; C07C 29/149 20130101; B01J 2531/822 20130101; B01J
31/4023 20130101; B01J 2531/842 20130101; B01J 2531/96 20130101;
B01J 31/2409 20130101; B01J 2531/825 20130101; B01J 2231/641
20130101; C07C 29/149 20130101; B01J 31/4046 20130101; B01J 31/24
20130101; C07C 31/207 20130101; C07C 31/04 20130101; C07C 31/10
20130101; C07C 31/205 20130101 |
Class at
Publication: |
502/53 ;
252/182.12 |
International
Class: |
B01J 38/10 20060101
B01J038/10; C09K 3/00 20060101 C09K003/00; B01J 38/06 20060101
B01J038/06 |
Foreign Application Data
Date |
Code |
Application Number |
May 2, 2002 |
GB |
0210143.4 |
Claims
1. A homogeneous process for the hydrogenation of carboxylic acids
and/or derivatives thereof in the presence of a catalyst
comprising: (a) ruthenium, rhodium, iron, osmium or palladium; and
(b) an organic phosphine; wherein the hydrogenation is carried out
in the presence of more than 1% by weight water.
2. A homogeneous process according to claim 1 wherein the
carboxylic acids and/or derivatives thereof are present as
solvent.
3. A homogeneous process according to claim 1 wherein a solvent is
present and the water is present as an additive therein.
4. A homogeneous process according to claim 3 wherein the water is
present in an amount of more than 1% to the solubility limit of the
water in the solvent.
5. A homogeneous process according to claim 3 wherein the water is
present in an amount greater than the solubility limit of the water
in the solvent and the excess water forms an aqueous phase.
6. A homogeneous process according to claim 1 wherein water is
generated in situ.
7. A homogeneous process according to claim 2 wherein the product
of the reaction forms the solvent.
8. A homogeneous process according to claim 1 wherein the water is
a solvent for the reaction.
9. A homogeneous process according to claim 1 wherein the catalyst
is a ruthenium/phosphine catalyst system
10. A homogeneous process according to claim 9 wherein the
phosphine component of the catalyst system is a tridentate
phosphine.
11. A homogeneous process according to claim 9 wherein the
phosphine component of the catalyst system is
tris-1,1,1-(diphenyl-phosphinomethyl)ethane.
12. A homogeneous process according to claim 1 wherein the reaction
is carried out in the absence of a promotor for the catalyst.
13. A homogeneous process according to claim 1 wherein the reaction
is carried out in the absence of halide.
14. A homogeneous process according to claim 1 wherein the reaction
temperature is in the range of from about 150.degree. C. to about
350.degree. C.
15. A homogeneous process according to claim 1 wherein the reaction
pressure is in the range of from about 250 psig to about 2000
psig.
16. A homogeneous process according to claim 10 wherein the
pressure is from about 800 psig to about 1200 psig.
17. A homogeneous process according to claim 1 wherein the catalyst
is regenerated in the presence of the water and hydrogen.
18. A process for regenerating a catalyst comprising: (a)
ruthenium, rhodium, iron, osmium or palladium; and (b) an organic
phosphine; wherein the regeneration is carried out in the presence
of hydrogen and water.
19. A process according to claim 18 wherein the regeneration is
carried out at a temperature of from about 150.degree. C. to about
350.degree. C.
Description
[0001] This application is a continuation of U.S. application Ser.
No. 10/513,290, filed Jun. 20, 2005, which is a National Stage of
International Application No. PCT/GB03/01819, filed Apr. 29, 2003,
which claims priority to Great Britain Application No. 0210143.4,
filed May 2, 2002.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a homogeneous process for
the hydrogenation of carboxylic acids and/or derivatives thereof.
More particularly it relates to a homogeneous hydrogenation process
which can be carried out in the presence of water.
[0003] Many catalyst systems are known which are suitable for use
in the hydrogenation of carboxylic acids, acid anhydrides, esters
or amides. Traditionally such reactions are carried out using
heterogeneous catalysts and often high temperatures and pressures.
A disadvantage of these heterogeneous catalyst systems is that many
are intolerant of acid feedstocks and therefore have limited
use.
[0004] In order to overcome this problem, catalysts have been
suggested for the hydrogenation of carboxylic acids and their
derivatives based on ruthenium/phosphine systems. Examples of these
catalyst systems include those described in U.S. Pat. No.
5,047,561, U.S. Pat. No. 5,079,372, U.S. Pat. No. 5,580,991, U.S.
Pat. No. 5,077,442, U.S. Pat. No. 5,021,589, U.S. Pat. No.
4,931,573, U.S. Pat. No. 4,892,955, "Hydrogenation reaction of
carboxylic anhydrides catalyzed by a new and highly active cationic
ruthenium complex", Y-Hara et al Chem Left (1991) 553, U.S. Pat.
No. 3,957,827, U.S. Pat. No. 4,485,245 and U.S. Pat. No. 4,480,115
which are incorporated herein by reference.
[0005] However, whilst the systems described in these document
provide processes which in general adequately enable hydrogenation
reactions to be carried out, they do suffer from certain
disadvantages and drawbacks. In particular, they require that the
hydrogenation reaction is carried out in the absence of water since
it is believed that any water present inhibits the catalyst or
significantly reduces the rate of reaction. For example, in U.S.
Pat. No. 5,047,561 an organic solvent is used and it is stated that
the amount of water present should be controlled and should be no
higher than 1% by weight. In "Hydrogenation reaction of carbonyl
compounds catalyzed by cationic ruthenium complexes", H-Inagaki et
al, Science and Technology of Catalysis (1994) 327 it is explained
that the presence of water retards the hydrogenation reaction of
succinic anhydride in the presence of a ruthenium trialkyl
phosphine complexes in the presence of a promotor and that it is
necessary to remove the water produced by hydrogenation in the gas
stream and in U.S. Pat. No. 3,957,827 and U.S. Pat. No. 4,485,245
scavengers are used to remove any water produced in the reaction
with the aim of improving yield and productivity.
[0006] Many of these known catalyst systems also require the
presence of a promotor to increase the selectivity and activity of
the ruthenium catalyst. Examples of this include U.S. Pat. No.
5,079,372 and U.S. Pat. No. 4,931,573 where reactions are carried
out in the presence of an organic solvent and a metal selected from
Group IVA, VA and III is required as a promotor.
[0007] Another example of the use of a promotor may be found in
U.S. Pat. No. 5,077,442. In this case a phosphorous compound is
used to promote selectivity and conversion. This document teaches
that any water produced in the reaction is removed from the
reaction zone as the presence of water is said to decrease
selectivity and conversion.
[0008] Another suitable promotor described is a conjugate base of
an acid and in this connection reference may be made to U.S. Pat.
No. 5,021,589 and U.S. Pat. No. 4,892,955. In this latter case, it
is noted that components of the catalyst system are susceptible to
hydrolysis under the reaction conditions and that a hydrogen purge
was required to remove water produced during the reaction.
[0009] Whilst these processes go some way to providing adequate
catalyst systems, there is still a need for alternative process
which allow for efficient hydrogenation of carboxylic acids and/or
derivatives thereof with good conversion and selectivity to the
desired products. Surprisingly, we have now established that the
presence of water is not only not disadvantageous but indeed offers
positive advantages.
SUMMARY OF THE INVENTION
[0010] Thus, according to the present invention there is provided a
homogeneous process for the hydrogenation of carboxylic acids
and/or derivatives thereof in the presence of a catalyst
comprising: [0011] (a) ruthenium, rhodium, iron, osmium or
palladium; and [0012] (b) an organic phosphine; wherein the
hydrogenation is carried out in the presence of more than 1% by
weight water.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] By "homogeneous process" we mean that the catalyst is
dissolved in the solvent for the reaction and that at least some of
the water present and at least some of the carboxylic acid and/or
derivatives thereof must be in phase with the catalyst. Where
excess water and/or carboxylic acid and/or derivatives thereof is
present, the excess may form a separate phase to that comprising
the catalyst. Additionally or alternatively, the product may form a
separate phase.
[0014] By carboxylic acids and/or derivatives thereof, we mean any
molecule containing a carboxylic acid functional group for example,
carboxylic acids, dicarboxylic acids, polycarboxylic acids, hydroxy
carboxylic acids, aromatic carboxylic acids, anhydrides, amides,
esters, monoesters of dicarboxylic acids and mixtures thereof.
[0015] Where the carboxylic acid and/or derivative thereof is water
soluble, the water may be present as the solvent for the reaction.
Alternatively a solvent may be used. Where a solvent is used, the
water will be present as an additive in the solvent or will be
generated in situ. In another alternative arrangement, the acid or
its derivative or the product of the reaction may be the
solvent.
[0016] Where the carboxylic acid and/or derivative thereof is
non-water soluble, such as for example for higher carbon content
carboxylic acids and esters, the reactant or product may be the
solvent for the reaction or an organic solvent may be used and the
water may be present as an additive. In this case, it may be
present in the solvent in an amount of from about 1% to the
solubility limit of the water in the solvent. Additional water may
be present in a separate aqueous phase.
[0017] In one alternative arrangement, the water may be produced in
situ as a by-product of the hydrogenation. Where the water is
generated in situ, if maximum benefits are to be achieved, the
water should be generated within the first few cycles of the
reaction. Where the water is to be generated in situ, an amount of
water may be added initially to cover the system's requirement
until sufficient water has been generated.
[0018] It will therefore be understood, that the process of the
present invention offers substantial advantages over the prior art
arrangements in that water need not be removed from any reactants
prior to the start of the reaction and may even be the solvent.
Further, any water produced in the reaction need not be removed
from the reactor. By this means, the known processes are simplified
which will have cost implications.
[0019] Further, we have found that the presence of water is
beneficial in terms of catalyst stability. It is noted that in
prior art systems, decarbonylation of, for example, the product
alcohols or intermediate aldehydes occurs and the carbon monoxide
formed strongly inhibits the catalyst. To overcome this it is
usual, in prior art arrangements, for the carbon monoxide to be
removed and a methanation unit to be included in the plant to deal
with recycling of vent gas to the reactor. However, this is
unnecessary in the process of the present invention.
[0020] Without wishing to be bound by any theory it is believed
that the presence of the water allows a side reaction to occur in
the hydrogenation reactor in which any carbon monoxide produced
reacts with the water to form carbon dioxide and hydrogen via the
water gas shift reaction. This carbon dioxide and hydrogen may be
further reacted to form methane. These gases can be readily removed
from the reaction system thereby reducing the costs of the
hydrogenation process. Thus, this system not only provides a
cost-effective hydrogenation process but also obviates the need to
have a separate methanation unit in the recycling system for vent
gases.
[0021] A further advantage of the present invention is that the
removal of the carbon monoxide as detailed above allows for
effective regeneration of the catalyst. Thus the process offers
extended catalyst life which in turn improves the economics of the
reaction.
[0022] The water gas shift reaction does require heat for its
initiation. Where the carboxylic acid and/or derivatives thereof or
the product of the hydrogenation is not thermally stable at the
initiation temperature, the process of the present invention can be
operated whereby the catalyst is allowed to be inhibited by the
presence of generated carbon monoxide, the thermally unstable
moiety is removed and the heat is then increased in the presence of
the hydrogen such that the water gas shift reaction can operate to
reactivate the catalyst for further reaction. By this means the
process can be applied to a broad range of acids with prolonged
catalyst life.
[0023] A still further advantage of the present invention is that
there is no requirement to add buffer salts of the kind used in the
prior art to stabilise the catalyst and further, promotors are not
generally required and may, in some circumstances, even be
deleterious. The reaction is preferably carried out in the absence
of halides.
[0024] As described above, where the carboxylic acids and/or
derivatives thereof are soluble in water, the water may act as the
solvent. However, the method of the present invention may be
conducted in the absence of a solvent, ie the starting material or
reaction product may be a solvent for the reaction. However, if a
solvent is used, any suitable solvent may be selected and examples
of suitable solvents include, but are not limited to, diethyl
ether, tetrahydrofuran, ethylene glycol dimethyl ether, dioxane,
2-propanol, 2-butanol, secondary alcohols, tertiary alcohols, or
toluene with tetrahydrofuran and other ethers being particularly
preferred.
[0025] The preferred catalyst of the present invention is a
ruthenium/phosphine catalyst. The ruthenium is generally provided
as a ruthenium salt although halides are not preferred. Suitable
salts are those which can be converted to active species under the
reaction conditions and include nitrates, sulphates, carboxylates,
beta diketones, and carbonyls. Ruthenium oxide, carbonyl ruthenates
and complex compounds of ruthenium, including
hydridophosphineruthenium complexes, may also be used. Specific
examples include, but are not limited to, ruthenium nitrate,
ruthenium dioxide, ruthenium tetraoxide, ruthenium dihydroxide,
ruthenium acetylacetonate, ruthenium acetate, ruthenium maleate,
ruthenium succinate, tris-(acetylacetone)ruthenium,
pentacarbonylruthenium, dipotassium tetracarbonyl-ruthenium,
cyclo-pentadienyldicarbonyltriruthenium,
tetrahydridedeca-carbonyltetraruthenium, tetraphenylphosphonium,
ruthenium dioxide, ruthenium tetraoxide, ruthenium dihydroxide,
bis(tri-n-butylphosphine)tricarbonylruthenium,
dodecacarbonyl-triruthenium,
tetrahydridedecacarbonyltetraruthenium, tetraphenylphosphonium,
undecacarbonylhydridetriruthenate.
[0026] The ruthenium compound may be present in any suitable
amount. However, it is preferably present in an amount of from
0.0001 to 100 mol, preferably 0.005 to 5 mol, as ruthenium per
liter of reaction solution.
[0027] Any suitable phosphine may be used. Compounds which provide
tridentate, bidentate and monodentate ligands may be used. Where
the metal is ruthenium, tridentate phosphines are particularly
preferred. Examples of suitable phosphine compounds include
trialkylphosphines, dialkylphosphines, monoalkylphosphines,
triarylphosphines, diarylphosphine, monoarylphosphines,
diarylmonoalkyl phosphines and dialkylmonoaryl phosphines. Specific
examples include but are not limited to
tris-1,1,1-(diphenylphosphinomethyl)methane,
tris-1,1,1-(diphenylphosphinomethyl)-ethane,
tris-1,1,1-(diphenylphosphinomethyl)propane,
tris-1,1,1-(diphenylphosphino-methyl)butane,
tris-1,1,1-(diphenylphosphino-methyl)2-ethane-butane,
tris-1,1,1-(diphenylphosphinomethyl)2,2-dimethylpropane,
tris-1,3,5-(diphenylphosphino-methyl)cyclohexane,
tris-1,1,1-(dicyclohexylphosphinomethyl)ethane,
tris-1,1,1-(dimethylphosphinomethyl)ethane,
tris-1,1,1-(diethylphosphinomethyl)ethane,
1,5,9-triethyl-1,5-9-triphosphacyclododecane,
1,5,9-triphenyl-1,5-9-triphosphacyclododecane,
bis(2-diphylephosphinoethyl)phenylphosphine, bis-1,2-(diphenyl
phosphino)ethane, bis-1,3-(diphenyl phosphino)propane,
bis-1,4-(diphenyl phosphino)butane, bis-1,2-(dimethyl
phosphino)ethane, bis-1,3-(diethyl phosphino)propane,
bis-1,4-(dicyclohexyl phosphino)butane, tricyclohexylphosphine,
trioctyl phosphine, trimethyl phosphine, tripyridyl phosphine,
triphenylphosphine with tris-1,1,1-(diphenylphosphinomethyl)-ethane
being particularly preferred.
[0028] The phosphine compound may be present in any suitable
amount. However, it is preferably present in an amount of from
0.0001 to 100 mol, preferably 0.005 to 5 mol, as ruthenium per
liter of reaction solution.
[0029] Any suitable reaction temperature may be used. However, in
the process of the present invention, particular advantages may be
noted if the hydrogenation is carried out at temperatures in the
region of from about 150.degree. C. to about 350.degree. C.
[0030] Any suitable pressure may be used with a reaction pressure
of from about 250 psig to about 2000 psig, preferably of from 800
psig to 1200 psig and most preferably 1000 psig.
[0031] The process may be carried out either in a batch system or
in a continuous system. However, it will be understood that the
process of the present invention is particularly suitable for use
in a continuous system since the catalyst is not poisoned by carbon
monoxide or if poisoning in this way occurs, the catalyst can be
regenerated by reaction with the water.
[0032] Where the catalyst is removed from the reactor, for example,
with a product removal stream, it may be recycled by any suitable
means to the reactor.
[0033] It will be understood that the process of the present
invention relating to regenerating the catalyst may be applied to
catalysts which have been inhibited during processes carried out
under conventional processes such as those described in the prior
art and in particularly in the documents detailed above. Thus,
according to a second aspect of the present invention there is
provided a process for regenerating a catalyst comprising: [0034]
(a) ruthenium, rhodium, iron, osmium or palladium; and [0035] (b)
an organic phosphine; wherein the regeneration is carried out in
the presence of hydrogen and water, preferably via the water gas
shift reaction.
[0036] The regeneration may be carried out at any suitable
temperature with temperatures of from about 150.degree. C. to about
350.degree. C. being preferred.
[0037] The present invention will now be described with reference
to the following examples which are not intended to be limiting on
the scope of the invention.
Example 1
[0038] illustrates that maleic acid may be successfully
hydrogenated in the presence of water.
[0039] Ruthenium(III)acetylacetonate (0.46 mmols, 0.181 g) and
1,1,1 tris(diphenyl-phosphinomethyl)ethane (triphos) (6.1 mmols,
0.38 g), water (71 g) and maleic acid (ex Fluka, 20.2 g) were
transferred into a 300 ml Hastelloy Parr autoclave. This was sealed
and purged with hydrogen before being pressurised to 700 psig with
hydrogen and heated to 241.degree. C. Once 241.degree. C. had been
achieved, the reactor was topped up with hydrogen to 1000 psig and
this pressure was maintained throughout the reaction via a mass
flow meter, which recorded the amount of hydrogen added. At the end
of the reaction the hydrogen supply was isolated and the reactor
cooled. At room temperature the headspace gas was analysed using a
Pye-Unicam refinery gas analyser, before being vented. The product
was removed from the reactor and weighed (91.42 g). The maleic
conversion was determined by titration of the liquid product
against 0.1M sodium hydroxide. (>99.9%). The water and organic
analysis was determined using an HP gas chromatograph equipped with
a micro TCD (wt %): water (86.52), propanol (0.84), tetrahydrofuran
(7.02) propionic acid (0.14), .gamma.-butyrolactone (2.47)
butanediol (2.83); giving an overall molar selectivity to
tetrahydrofuran of 51.1%, to .gamma.-butylractone of 15.1%, and to
butanediol of 16.5%, others 17.3%.
Comparative Example 1
[0040] illustrates the effect of the presence of insufficient water
to maintain the activity of the reaction.
[0041] Example 1 was repeated except that the water and maleic acid
were replaced by methyl propionate (64 g) and the reaction
conducted at 164.degree. C. After 15 hours, at the end of the
reaction, 59.4 g of product was recovered as a yellow solution with
a small amount of yellow solid. The solution was analysed and found
to be (wt %) methanol (7.15), water (2.10), propanol (8.46), methyl
propionate (75.62), propionic acid (0.25) propyl propionate (4.99);
giving a selectivity to propanol of 75.2 mol % and to propyl
propionate of 23.0 mol %. The molar conversion was 16.9%. It can
therefore be seen that the absence of added water, insufficient
water is generated in the initial hydrogenation of the ester to
allow the reaction to continue to completion. The solid component
from this reaction was analysed and found to be
[Ru(triphos)(CO)(H).sub.2] and thus it was concluded that the
catalyst had been poisoned with the carbon monoxide.
Comparative Example 2
[0042] demonstrates that in the absence of water the isolated solid
is not active for the reduction and in particular that in the
absence of added water the deactivated catalyst
[Ru(triphos)(CO)H.sub.2] is effectively inactive.
[0043] Several reactions were performed in the manner of
Comparative Example 1 and the solid product,
[Ru(triphos)(CO)(H).sub.2] was collected, washed and dried (0.2263
g) then returned to the reactor with a fresh charge of methyl
propionate (17.7 g) and isopropanol (38.6 g). This was then heated
at 164.degree. C. for 15.5 hours, at the end of this time the
reactor was cooled and 52.2 g of product recovered. The liquid
product was analysed and found to be methanol (1.04), isopropanol
(73.02), water (0.62), propanol (1.23), methyl propionate (23.53)
and propyl propionate (0.08); giving molar selectivities of 92.5%
for propanol and of 3.1% for propyl propionate and a molar
conversion of 7.3%
Examples 2 and 3
[0044] demonstrate hydrogenation of an ester in the presence of
water. These examples demonstrate that in the presence of water
ester hydrogenation proceeds to effectively 100% conversion.
[0045] In Example 2, Example 1 was repeated using 48.64 g of water
and 23.26 g of dimethyl maleate as feed. The reaction was conducted
at 191.degree. C. After 53 hours the liquid and gaseous products
were cooled and the liquid product analysed by gas chromatography
and found to be off gas (mol %) hydrogen (98.9), carbon monoxide
(0.08), methane (0.01) and carbon dioxide (0.113) liquid (wt %)
methanol (15.37) water (67.11) tetrahydrofuran (27.43),
.gamma.-butyrolactone (0.333) and butanediol (12.29) giving a molar
conversion of 99.5 mol % and a selected activity to desired
products of (mol %) tetrahydrofuran (27.43) .gamma.-butylractone
(1.88) butanediol of (66.24).
[0046] In Example 3, Example 1 was again repeated using 48.4 g of
water and 20.1 g of methyl propionate as feed. The reaction was
conducted at 192.degree. C. After 15 hours the reactor was cooled
and the liquid product analysed by gas chromatography and found to
be methanol (10.25) water (70.75) propanol (18.27) methyl
propionate (<0.1) propionic acid (<0.1) propyl propionate
(<0.1), giving a molar selectivity and conversion of
>99.5%
Example 4
[0047] illustrates the reactivation of the deactivated catalyst by
the use of water In particular to establish that the effect of
water on the deactivated catalyst is to cause a change in the
nature of the species and to cause carbon dioxide to be
released.
[0048] A sample of the deactivated catalyst,
[Ru(triphos)(CO)H.sub.2] (0.3536 g), deionised water (49.05 g) and
tetrahydrofuran (17.47 g) were loaded into the autoclave used
previously, which was then sealed, purged with hydrogen,
pressurised with hydrogen to 714 psig then heated to 193.degree. C.
for 15.5 hours. At the end of this time the reactor was cooled and
the head space gas purged through a CO.sub.2 Draeger tube, this
slowly turned pale blue indicating the presence of CO.sub.2. the
solution from the reaction was analysed by proton decoupled
phosphorus NMR and found to be different when compared with the
spectrum obtained from [Ru(triphos)(CO)H.sub.2] dissolved in
tetrahydrofuran.
[0049] The [Ru(triphos)(CO)H.sub.2] in tetrahydrofuran gives a
characteristic doublet and triplet at 25 and 34 ppm respectively.
In the case of the sample that had been heated under hydrogen in
water, these signals had completely disappeared, to be replaced by
a complex array of other signals illustrating that the deactivated
species had been removed.
Example 5
[0050] illustrates the direct hydrogenation of a simple (propionic)
acid, producing sufficient water in-situ to maintain the reaction.
This further demonstrates that acids may be hydrogenated directly
with the water produced in the reaction causing the in-situ
reactivation of the catalyst.
[0051] The method of Example 1 was repeated except that the water
and maleic acid were replaced with propionic acid (69.7 g, 98% pure
ex Aldrich). After 5 hours at temperature, the reactor was cooled
to room temperature and the off gas analysed and found to contain
(mol %) carbon dioxide (0.29), methane (0.95), carbon monoxide
(0.73), ethane (2.21) and propane (0.31). The liquid product was
recovered from the autoclave and found to be two phase, 64.8 g of
an upper (organic layer) and 5.6 g of a lower (aqueous layer).
These layers were analysed and found to be (wt %) upper, water
(17.0), propanol (38.59), propionic acid (11.9), propyl propionate
(31.9); lower water (83.66) propanol (11.73), propionic acid (3.47)
and propyl propionate (0.6). These gave an overall molar
selectivity to propanol of 64.5%, propyl propionate 27.0% which in
itself would afford 1-propanol and a conversion of 79.3%.
Example 6
[0052] relates to the hydrogenation of fumaric acid and
demonstrates that other diacids may be hydrogenated.
[0053] The method of Example 1 was repeated except that the maleic
acid was replaced with fumaric acid (20.3 g, 98%). After 12 hours
at temperature, the reactor was cooled to room temperature The
liquid product was recovered from the autoclave (90.1 g) and
analysed (wt %), water (82.74), propanol (0.13), propionic acid
(0.04), tetrahydrofuran (6.00), .gamma.-butylractone (2.19),
butanediol (8.35); giving an overall molar selectivity to
tetrahydrofuran of 40.0%, .gamma.-butyrolactone of 12.2%, and to
butanediol of 44.53%. Titration against 0.01M sodium hydroxide gave
>98% conversion of the fumaric acid
Example 7
[0054] illustrates the direct hydrogenation of lactic acid. This
further demonstrates that organic acids may be hydrogenated.
[0055] The method of Example 1 was repeated except that the water
and maleic acid were replaced with lactic acid, 85+%, solution in
water, (93.34 g, ex Aldrich). After 6 hours at 190.degree. C., the
reactor was cooled to room temperature. The liquid product was
recovered from the autoclave and found to be single phase, 94.47 g.
The analysis found (wt %): water (26.25), and propylene glycol
(72.74) which represented a conversion of >99.5%.
Example 8
[0056] illustrates the direct hydrogenation of an acid in the
presence of a solvent. The method of Example 1 was repeated except
that maleic acid was replaced with succinic acid (20.03 g),
1-methyl-2-pyrrolidinine (20.61 g) was included as a solvent and
the amount of water (49.86 g) included, was reduced. At the end of
the reaction the products were analysed and found to be (wt %):
water (61.43), propanol (0.14), tetrahydrofuran (3.69), propionic
acid (0.15), .quadrature.-butyrolactone (3.87), butanediol (5.22);
giving an overall selectivity to tetrahydrofuran of 30.49%, to
.quadrature.-butyrolactone of 26.81%, and to butanediol of 34.57%,
and a conversion of .quadrature.99%.
Example 9
[0057] illustrates the direct hydrogenation of an anhydride in
accordance with the present invention
[0058] The method of Example 5 was repeated except that propionic
anhydride (39.23 g) and propionic acid (33.9 g) were used as feed.
After 5 hours at temperature, the reactor was cooled to room
temperature and the off gas analysed and found to contain (mol %)
carbon dioxide (0.29), methane (0.95), CO (0.73), ethane (2.21),
propane (0.31). The liquid product was recovered from the autoclave
and found to be two phase, 73.2 g of an upper (organic layer) and
1.8 g of a lower (aqueous layer). These layers were analysed and
found to be (wt %) upper, water (15.91), propanol (40), propionic
acid (9.54), propyl propionate (33.88); lower water (63.25)
propanol (21.89), propionic acid (4.59), propyl propionate (10.15).
These gave an overall molar selectivity to propanol of 65.8%,
propyl propionate 28.7% and a conversion of 80.87%.
Example 10
[0059] illustrates the direct hydrogenation of an amide in
accordance with the present invention. It also illustrates that the
catalyst is stable in the presence of nitrogen containing compounds
such as ammonia and amines
[0060] The method of Example 5 was repeated at 164_C, except that
the propionic acid was replaced by propionamide (20.14 g), water,
20.26 g and tetrahydrofuran (solvent, 44.22 g). After 14 hours the
reactor was cooled and vented and the contents analysed (area %)
water+ammonia (9.81), propanol (10.57), tetrahydrofuran (53.76),
dipropylamine (0.57) propyl propionate (1.32) propanamide (15.92)
N-propyl propanamide (7.33).
Examples 11 to 20
[0061] demonstrate that whilst
tris-1,1,1-diphenylphosphinomethyl)ethane is the preferred
phosphine compound under these conditions, other phosphines are
also suitable.
[0062] The method of Example 5 was repeated except that the
tris-1,1,1-diphenyl-phosphinomethyl)ethane was replaced by a
variety of other phosphines in various ruthenium:phosphine ratios.
the results are summarised in Table 1
TABLE-US-00001 TABLE 1 Exam- phosphine: Conver- Selectivity ple
phosphine ruthenium sion (propanol + propyl No. compound ratio (mol
%) propionate) (mol %) 11 tris-1,1,1- 1 76.4 93.7
diphenylphosphino- methyl)ethane 12 Triphenylphosphine 1.01 11.6
40.4 13 Triphenylphosphine 6 8.8 40.7 14 Tricyclohexyl- 3.09 16.0
68.2 phosphine 15 Tricyclohexyl- 6.02 21.0 87.2 phosphine 16
Trioctylphosphine 6.1 39.3 89.0 17 1,2 bis(diphenyl- 2 24.8 81.5
phosphino) ethane 18 1,2 bis(diphenyl- 1 14.3 67.0 phosphino)
ethane 19 1,2 bis(diphenyl- 1 10.0 54.6 phosphino) propane 20 1,2
bis(diphenyl- 2 16.7 79.1 phosphino) propane
Comparative Example 3
[0063] demonstrates the unsuitability of a catalyst system
comprising phosphine plus a strong acid promoter under the
conditions preferred in this invention. This demonstrates that
under these conditions the addition of strong acids is detrimental
to the reaction and the strong acid can itself be reduced. Example
14 was repeated except that two molar equivalents of p-toluene
sulphonic acid monohydrate were added. At the end of the reaction
when the products were analysed, a sulphurous odour was detected
indicative of H.sub.2S and the conversion had fallen to 10.2 mol %
and the selectivity to propanol and propyl propionate to 68.2%.
Comparative Example 4
[0064] demonstrates that under the preferred reaction conditions
the addition of sodium salts of strong acids is detrimental to the
reaction reducing both the conversion and the selectivity. Example
1 was repeated except that two molar equivalents of
sodium-p-toluene sulphonate were added. At the end of the reaction
a white solid (succinic acid, 13.9 g) was recovered and the liquid
products (82.5 g) were analysed by gas chromatography and found to
be (wt %): water (95.90), propanol (0.10), tetrahydrofuran (0.09),
propionic acid (1.478) .quadrature.-butyrolactone (1.67),
butanediol (0.38); giving an overall selectivity to tetrahydrofuran
of 2.43%, to .quadrature.-butyrolactone of 38.25%, and to
butanediol of 8.26%. The conversion had fallen to 33.49 mol %.
Example 21
[0065] relates to catalyst recycle and demonstrates the
recyclability of the ruthenium-phosphine catalyst.
[0066] The method of Example 5 was repeated except that the
reaction was conducted at 241.degree. C. for 4 hours. At the end of
the reaction, the product liquor was placed in a rotary evaporator
and reduced down to a minimal volume (.about.5 mls) at
70-80.degree. C. and 60 Torr. The overheads were then analysed for
acid conversion. The residual solution containing the catalyst was
returned to the autoclave and made up to a total weight of 70 g
with propionic acid and the reaction repeated. The results are
summarised in Table 2 below. For recycle number seven the catalyst
was not returned to the autoclave, instead 70 g of propionic acid
was used on its own to demonstrate that the activity was not due to
the precipitation of ruthenium on the reactor walls etc.
TABLE-US-00002 TABLE 2 Recycle Number Conversion (mol %) 0 42 1 46
2 44 3 46 4 56 5 46 6 51 7 0 blank run 8 44
[0067] It can therefore be seen that the conversion rate is
maintained during recycle.
* * * * *