CA1244053A - Process for the preparation of aldehydes - Google Patents
Process for the preparation of aldehydesInfo
- Publication number
- CA1244053A CA1244053A CA000482937A CA482937A CA1244053A CA 1244053 A CA1244053 A CA 1244053A CA 000482937 A CA000482937 A CA 000482937A CA 482937 A CA482937 A CA 482937A CA 1244053 A CA1244053 A CA 1244053A
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- Prior art keywords
- rhodium
- water
- reaction
- soluble
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A novel process for the preparation of aldehydes by reacting olefins with carbon monoxide and hydrogen in the presence of a catalyst system comprised of rhodium in metallic form or as a compound and a water-soluble quaternary ammonium salt of a mono, di or trisulfonated arylphosphine.
-A-
A novel process for the preparation of aldehydes by reacting olefins with carbon monoxide and hydrogen in the presence of a catalyst system comprised of rhodium in metallic form or as a compound and a water-soluble quaternary ammonium salt of a mono, di or trisulfonated arylphosphine.
-A-
Description
It is known that aldehydes and alcohols can be pre-pared by the reaction of olefin's with carbon monoxide and hydro-gen which reaction is catalyzed by hydridometal carbonyls, pr~-ferably those of the metals of the 8th ~roup of the Periodic Table. Apart from cobalt which i.s'widely used.in industry as a catalyst metal, rhodium has. a~so been gaining in:importance recently. In contrast to cobalt, xhodium makes it possible for the reacti.on to be carried out at low pressure and furthermore, the reaction takes place wi.th enhanced formation of stffight-chaine~ n-aldehydes with iso-aldehydes only being formed to a minor de~ree. Finally, the hydxogenation of olefins to saturated hydrocarbons is also appreciably lower w.ith rhodi.um catalysts than with cobalt catalysts.
In the commerical processes, the rhodium catalyst is in:the form of a modified h~drido~hodium.carbonyl containi~g addi.tional ligands, if'n.ecessary in'excess. Ter:tiary phosphines or phosphites ha~e pro~ed to be parti.cularly good as ligands and by using them~ it'is'p~ssible to reduce.the reac:tion pressure to values under 300'bar (3 x 104kPa). Howe~er,.the separati0n of the reaction products and the recovery of the catalysts dis-solved homo~eneously in the reaction product present problems in'this'process. Generally, the reaction product is distilled out of the reaction mixture, but this'method can only be used in'practice for the hyd~oformylation.of low molecular weight olefins, i.e. olefins with up to about 5 carbon atoms in the molecule due to the thermal sensiti~ity of:the aldehyd.es and alcohols formed. Furthermorer i.t.has been shown that the thexmal loading of the distillation product also leads to considerable catalyst losses due to decomposition of the rhodium complex compounds.
The said shortcomings are avoided by the use of catalyst systems which are soluble in'water and such catalysts are,for example, described in the DE 26 27 354. Solubility of the rhodium complex compounds is achieved by the use of sul-fonated triarylphosphines as complex components. In this ver-sion of the process, the catalyst is'separated ~rom the reac-tion product a~ter completion of the hydroformylation reaction simply by separation of the aqueous and organic'phases, i.e.
without distillation and thus without additional thermal process steps. A further characteristic'o~ this method is'that n-alde-hydes are formed with a high selecti~'ity from terminally unsatu-rated olefins and iso-aldeh~des are ormed only to a minor degree. Apart from sul~onated triarylphosphines, carboxylated triarylphosphines are also used as complex components of ~ater-soluble rhodium comple~ compounds.
The known processes have proved to be admirably suit-able for the hydroformylation o~ lower olefins, in'particular ethylene and propylene. However, if'higher oleEins such as hexene, octene or decene are used, the conversio~ and/or the selectivity towards n-compounds drop(s) appreciably. Thus, the reaction is often no longer economical on a com~ercial scale. The drop in'~ield is caused by the fact that higher olefins are less s~luble in water since the reaction between the two reactants takes place in'the aqueous phase.
Admittedly, DE 31 35 i27 does teach hydroformylation of olefinic compounds in a system containing an aqueous phase and an organic phase, which is ither immiscible or only sllg~tly miscible with it in the presence of solubili~ers. The practical performance of this'reaction is lim'ited exclusively to the use of monosulfonated or monocarboxylated triarylphosphines
In the commerical processes, the rhodium catalyst is in:the form of a modified h~drido~hodium.carbonyl containi~g addi.tional ligands, if'n.ecessary in'excess. Ter:tiary phosphines or phosphites ha~e pro~ed to be parti.cularly good as ligands and by using them~ it'is'p~ssible to reduce.the reac:tion pressure to values under 300'bar (3 x 104kPa). Howe~er,.the separati0n of the reaction products and the recovery of the catalysts dis-solved homo~eneously in the reaction product present problems in'this'process. Generally, the reaction product is distilled out of the reaction mixture, but this'method can only be used in'practice for the hyd~oformylation.of low molecular weight olefins, i.e. olefins with up to about 5 carbon atoms in the molecule due to the thermal sensiti~ity of:the aldehyd.es and alcohols formed. Furthermorer i.t.has been shown that the thexmal loading of the distillation product also leads to considerable catalyst losses due to decomposition of the rhodium complex compounds.
The said shortcomings are avoided by the use of catalyst systems which are soluble in'water and such catalysts are,for example, described in the DE 26 27 354. Solubility of the rhodium complex compounds is achieved by the use of sul-fonated triarylphosphines as complex components. In this ver-sion of the process, the catalyst is'separated ~rom the reac-tion product a~ter completion of the hydroformylation reaction simply by separation of the aqueous and organic'phases, i.e.
without distillation and thus without additional thermal process steps. A further characteristic'o~ this method is'that n-alde-hydes are formed with a high selecti~'ity from terminally unsatu-rated olefins and iso-aldeh~des are ormed only to a minor degree. Apart from sul~onated triarylphosphines, carboxylated triarylphosphines are also used as complex components of ~ater-soluble rhodium comple~ compounds.
The known processes have proved to be admirably suit-able for the hydroformylation o~ lower olefins, in'particular ethylene and propylene. However, if'higher oleEins such as hexene, octene or decene are used, the conversio~ and/or the selectivity towards n-compounds drop(s) appreciably. Thus, the reaction is often no longer economical on a com~ercial scale. The drop in'~ield is caused by the fact that higher olefins are less s~luble in water since the reaction between the two reactants takes place in'the aqueous phase.
Admittedly, DE 31 35 i27 does teach hydroformylation of olefinic compounds in a system containing an aqueous phase and an organic phase, which is ither immiscible or only sllg~tly miscible with it in the presence of solubili~ers. The practical performance of this'reaction is lim'ited exclusively to the use of monosulfonated or monocarboxylated triarylphosphines
-2~
as a component of the rhodium complex compoundO It has been shown that the monosulfo~ted triphenylphosphine in particular leads only to a moderate conversion and that the selectivity towards straigHt-chained n-aldehydes is low.
Conversion and selectivity can be improved by using trisulfonated triarylphosphines instead of monosulfonated com-pounds. However, an unsa,ti$factory aspect of this.~process variant is that rhodi.um and water-soluble phosphine are removed w.ith the organi.c'reaction product - even if only in small amounts-so that in'many cases an additional working-up step is necessary.
A further disadvantage is.the related lowering of.the normal-iso ratio.
It is an object of.the invention to ov,ercome the dis-advantages of the prior art and develope , a procedure which also permits the hydroformylation of higher olefins in a multi-phase system consisting of aqueous catalyst solution and organic start-ing materials and in'so~e cases reactio,n products as well as gaseous reactants.
This'and other objects and advantages of the invention will become obvious from the following detailed description.
In the novel process of,the i'nvention fo~,pr~pa~ation of aldehydes by reacting olefins with carbon monoxide and hydrogen in the liquid'phase in'the presence of water and rhodium in metallic form or as a compound a.s well as a water-soluble aryl-phosphine at temperatures of 20 to 150C and l.to 200 bar~(100 to 2 x 104 kPa)j the improvement comprï.s'es that the water-soluble phosphin'e has the formula ~c~
A - N - C
L P \ Ar - Xx2 ¦ l D
where Ar is aryl and X is a sulfonic acid, xl, x2 and x 3 are 0 or 1 with the proviso that at least one of xl, x2 or x3 is 1, A
i5 selected from the group consisting o an alkyl o~ 1 to 18 carbon atoms and aralkyl of 7 to 18 carbon atoms and B,C,D are alkyl of 1 to 4 carbon atoms and n is a whole number between and 3.
Surprisingly, it has been proven that when waber-soluble phosphines are used in the process of the invention the high activity and selectivity of the catalyst system is maint-ained even when high olefins are hydro~rmylated. At the same time, however, the amount of phosphine removed with the organic reaction product is also reduced considerably.
The water-soluble phosphinesused in the new process obvi~usly improve the solubility of the organic substrate in the aqueous phase and thus contribute towards an increase in the conversion. Their extremely low solubility in the organic phase means that they themselves and~he metallic components of the catalyst system are either not removed with the reaction product from the reaction zone, or if so, only a negligibly small amount~
Thus there is no need for a separate working-up step for the recovery of rhodium from the aldehyde.
of the water-soluble phosphines of the above formula, preferred compounds are those wherein Ar is phenyl or naphthylJ
the sum of xl, x2 and x3 is 2 or 3 and B,C and D are the same alkyl of 1 to 4 carbon atoms.
Examples of water-soluble phosphines suitable for carrying out the new process are triphenyl trisulfonates and triphenyldi---sul~onates with.the~ollo~iny ca~i~ns: tr~hylc~tYla~oniu~ trimethyl-dodecylammonium, tributyldodecylammonium, dodecylethyl-dimethyl-ammonium, triethylbenzylammonium.
The phosphines used i.n:the claimed process are pre~
pared by treating sulfonated triar~lphosphines with oleum and it is possible to prepare mono, di or trisulfonated arylphos-phines by variation of the reaction conditions, particularly the.reaction time, reaction temperature and the.ratio of tri-arylphosphine to sulfuric: trioxide.
It is practical to first.reco~er amine s.alts from the sulfonation product which are in'soluble in'water but soluble in organic'solvents. They are then converted to the desired "onium" salt of.the triarylphosphine by treatment with a quater-nary ammonium hydroxi.de The reac.tion of the olefin'w.ith hydrogen. and carbon monoxid'e by the process o~ the inventi.oh takes place at tempera-ture of 20 to 150~C, particularly S0 to 120C and pressures of ..
1 to 200 bar (100 to 2 x 104 kPa), particularly 10 to 100 bar (1 x 103 to 1 x 104 kPa)~
The catalyst can be added to the reaction system in a preformed state but it can also be successfully prepared in the reaction mixture from the components.rhodium or a rhodium com-pound and the aqueous solution of the quaternary ammonium salt of the sulfonated triarylphosphine under reaction conditions, i.e. in the presence of the olefin. In addit'ion to metallic rhodium in finely distributed ~orm, water-soluble rhodium salts such as rhodium chloride, rhodium sulfate, rhodium acetate or compounds soluble in organic media such as rhodium-2-ethylhex-anoate or insoluble compounds such as rhodium oxides can be used as sources of rhodium.
The rhodium concentration in the aqueous catalyst solution is 10 to 2000 ppm by weight based on the soluti~n. The quaternary ammonium salt of the sulfonated phosphine is added in such an amount that for 1 g atom of rhodium, 1 to 300 mol, pre-ferably 2 to 100 mol, of phosphine compouna are present. The pH
value of the aqueous catalyst solution should not be below 2 and generally, a pH value of 2 to 13, preferably 4 to 10 is established.
The composition of the sy~thesis ~as, i.e. the ratio of CO to hydrogen can be varied ~ithin wide limits. Generally, a synthesis gas is used where the ~olume ratio of CO to hydrogen is l : 1 or only deviates slightly from this value. The reaction can be carried out both as a batch process and continuously. The process of the invention is successfully used for hydroformyla-tion of stright-chained or branched oleins of four or more and in particular with six to twenty carbon atoms. The double bond in these atoms can be terminal or internal.
The following examples ser~e to illustrate the inven-tion more closely without limiting it to the embodiments dQscri-bed therein. To characterize the efficiency of the catalyst s,ystems, apart from the ratio of n-aldehyde to i-aldehyde, the term "activity" is de~ined as mol aldehyde g-atom Rh x min The formation of alcohols and hydrocarbons is minimal.
EXAMPLE 1 (Comparison) 420 g (corresponding to 355 ml3 of an aqueous solu-tion containing 15.5% by weight of the sodium salt of tri~m-sul-i3 fophenyl~ phosphine and 400 ppm of rhodium in the form of rhodium acetate were placed in a l liter autoclave with a dip-pipe and then, synthesis gas (CO/H2 = l:1) was orced in up to a pressure of 25 bar. The reaction solution was treated with the synthesis gas for 3 hours at 125C accompanied by stirring a~d it was then cooled to about 30C. The stirring was stopped and after a settling period of 15 minutes, the excess solution (~61 g) was forced out th~gh the dip-pipe and analyzed and the residual solution remained in the autoclave. After the resumption of .
stirring, 170 g of n-hexene-l were pumped through a pressure pipe into the autoclave and while the pressure was maintained at 25 bar, the mixture was heated to 125C over a period of 3 hours.
It was then allowed to cool to 30C and settle. After a 15 minute settling p.eriod,.the uppermost organic phase was forced out through the dip-pipe and was weighed and subjected to a gas chromatographic analysis.
Hydroormylation was repeated a.total o~ 6.times where-by more or less the same results were achieved. The activity values listed in Table I relate to the amounts oE aqueous and organic phase6present in the autoclave after each run.
~2~
lP~ o ¦ o i ~ ~ ~o~P G ~
1- u~ tn O
as a component of the rhodium complex compoundO It has been shown that the monosulfo~ted triphenylphosphine in particular leads only to a moderate conversion and that the selectivity towards straigHt-chained n-aldehydes is low.
Conversion and selectivity can be improved by using trisulfonated triarylphosphines instead of monosulfonated com-pounds. However, an unsa,ti$factory aspect of this.~process variant is that rhodi.um and water-soluble phosphine are removed w.ith the organi.c'reaction product - even if only in small amounts-so that in'many cases an additional working-up step is necessary.
A further disadvantage is.the related lowering of.the normal-iso ratio.
It is an object of.the invention to ov,ercome the dis-advantages of the prior art and develope , a procedure which also permits the hydroformylation of higher olefins in a multi-phase system consisting of aqueous catalyst solution and organic start-ing materials and in'so~e cases reactio,n products as well as gaseous reactants.
This'and other objects and advantages of the invention will become obvious from the following detailed description.
In the novel process of,the i'nvention fo~,pr~pa~ation of aldehydes by reacting olefins with carbon monoxide and hydrogen in the liquid'phase in'the presence of water and rhodium in metallic form or as a compound a.s well as a water-soluble aryl-phosphine at temperatures of 20 to 150C and l.to 200 bar~(100 to 2 x 104 kPa)j the improvement comprï.s'es that the water-soluble phosphin'e has the formula ~c~
A - N - C
L P \ Ar - Xx2 ¦ l D
where Ar is aryl and X is a sulfonic acid, xl, x2 and x 3 are 0 or 1 with the proviso that at least one of xl, x2 or x3 is 1, A
i5 selected from the group consisting o an alkyl o~ 1 to 18 carbon atoms and aralkyl of 7 to 18 carbon atoms and B,C,D are alkyl of 1 to 4 carbon atoms and n is a whole number between and 3.
Surprisingly, it has been proven that when waber-soluble phosphines are used in the process of the invention the high activity and selectivity of the catalyst system is maint-ained even when high olefins are hydro~rmylated. At the same time, however, the amount of phosphine removed with the organic reaction product is also reduced considerably.
The water-soluble phosphinesused in the new process obvi~usly improve the solubility of the organic substrate in the aqueous phase and thus contribute towards an increase in the conversion. Their extremely low solubility in the organic phase means that they themselves and~he metallic components of the catalyst system are either not removed with the reaction product from the reaction zone, or if so, only a negligibly small amount~
Thus there is no need for a separate working-up step for the recovery of rhodium from the aldehyde.
of the water-soluble phosphines of the above formula, preferred compounds are those wherein Ar is phenyl or naphthylJ
the sum of xl, x2 and x3 is 2 or 3 and B,C and D are the same alkyl of 1 to 4 carbon atoms.
Examples of water-soluble phosphines suitable for carrying out the new process are triphenyl trisulfonates and triphenyldi---sul~onates with.the~ollo~iny ca~i~ns: tr~hylc~tYla~oniu~ trimethyl-dodecylammonium, tributyldodecylammonium, dodecylethyl-dimethyl-ammonium, triethylbenzylammonium.
The phosphines used i.n:the claimed process are pre~
pared by treating sulfonated triar~lphosphines with oleum and it is possible to prepare mono, di or trisulfonated arylphos-phines by variation of the reaction conditions, particularly the.reaction time, reaction temperature and the.ratio of tri-arylphosphine to sulfuric: trioxide.
It is practical to first.reco~er amine s.alts from the sulfonation product which are in'soluble in'water but soluble in organic'solvents. They are then converted to the desired "onium" salt of.the triarylphosphine by treatment with a quater-nary ammonium hydroxi.de The reac.tion of the olefin'w.ith hydrogen. and carbon monoxid'e by the process o~ the inventi.oh takes place at tempera-ture of 20 to 150~C, particularly S0 to 120C and pressures of ..
1 to 200 bar (100 to 2 x 104 kPa), particularly 10 to 100 bar (1 x 103 to 1 x 104 kPa)~
The catalyst can be added to the reaction system in a preformed state but it can also be successfully prepared in the reaction mixture from the components.rhodium or a rhodium com-pound and the aqueous solution of the quaternary ammonium salt of the sulfonated triarylphosphine under reaction conditions, i.e. in the presence of the olefin. In addit'ion to metallic rhodium in finely distributed ~orm, water-soluble rhodium salts such as rhodium chloride, rhodium sulfate, rhodium acetate or compounds soluble in organic media such as rhodium-2-ethylhex-anoate or insoluble compounds such as rhodium oxides can be used as sources of rhodium.
The rhodium concentration in the aqueous catalyst solution is 10 to 2000 ppm by weight based on the soluti~n. The quaternary ammonium salt of the sulfonated phosphine is added in such an amount that for 1 g atom of rhodium, 1 to 300 mol, pre-ferably 2 to 100 mol, of phosphine compouna are present. The pH
value of the aqueous catalyst solution should not be below 2 and generally, a pH value of 2 to 13, preferably 4 to 10 is established.
The composition of the sy~thesis ~as, i.e. the ratio of CO to hydrogen can be varied ~ithin wide limits. Generally, a synthesis gas is used where the ~olume ratio of CO to hydrogen is l : 1 or only deviates slightly from this value. The reaction can be carried out both as a batch process and continuously. The process of the invention is successfully used for hydroformyla-tion of stright-chained or branched oleins of four or more and in particular with six to twenty carbon atoms. The double bond in these atoms can be terminal or internal.
The following examples ser~e to illustrate the inven-tion more closely without limiting it to the embodiments dQscri-bed therein. To characterize the efficiency of the catalyst s,ystems, apart from the ratio of n-aldehyde to i-aldehyde, the term "activity" is de~ined as mol aldehyde g-atom Rh x min The formation of alcohols and hydrocarbons is minimal.
EXAMPLE 1 (Comparison) 420 g (corresponding to 355 ml3 of an aqueous solu-tion containing 15.5% by weight of the sodium salt of tri~m-sul-i3 fophenyl~ phosphine and 400 ppm of rhodium in the form of rhodium acetate were placed in a l liter autoclave with a dip-pipe and then, synthesis gas (CO/H2 = l:1) was orced in up to a pressure of 25 bar. The reaction solution was treated with the synthesis gas for 3 hours at 125C accompanied by stirring a~d it was then cooled to about 30C. The stirring was stopped and after a settling period of 15 minutes, the excess solution (~61 g) was forced out th~gh the dip-pipe and analyzed and the residual solution remained in the autoclave. After the resumption of .
stirring, 170 g of n-hexene-l were pumped through a pressure pipe into the autoclave and while the pressure was maintained at 25 bar, the mixture was heated to 125C over a period of 3 hours.
It was then allowed to cool to 30C and settle. After a 15 minute settling p.eriod,.the uppermost organic phase was forced out through the dip-pipe and was weighed and subjected to a gas chromatographic analysis.
Hydroormylation was repeated a.total o~ 6.times where-by more or less the same results were achieved. The activity values listed in Table I relate to the amounts oE aqueous and organic phase6present in the autoclave after each run.
~2~
lP~ o ¦ o i ~ ~ ~o~P G ~
1- u~ tn O
3 ~ 4 ~ p o~ ~!
X ~. ~ o, r~
- ~D
I_ ~- W Cl~ ~ ~_ 1- I-p U~ ~ 1~
~t~ ,_~
1' 1' Ul ~ ~ ~
1~ ~P
~ O
~ o~
-;8 ~%~
To determine the total amount of rhodium and phos-phorus removed with the organic phase, the organic components drawn off from the reactor in the individual tests were combined, concentrated to about l/lOth of their original volume and analyzed.
0.017 ppm by weight of rhodium and 0.34 ppm by weight of phosphorus (in each case based on the original organic phase) were found.
Example 1 was repeated with the exception that 315 g (corresponding to 295 ml) of an aque~us solution of the trimethyl-benæylammonium salt of tri-(m-sulfophenyl)phosphine with a P(III) content of 0.308% hy weight and 158 g of n-hexene-l were used in the hydroformylation process instead o~ the sodium salt. The test results are reported in Table 2. The rhodium and phosphorus losses were determined by the method described in Example 1. An average of 0.029 ppm by weight of rhodium and 0.98 ppm by weight of phosphorus were removed with the organic product, i.e. only slightly more than when the normally employed sodium salt of tri-(m-sulfophenyl)phosphine was used.
-co ~ - ~o oo ~
~ o l`
a~
~1 ~D N
o Ln (5 ~) ~I N
C~ O
:) ~1 ~
~D .
a~ ~ ,I N
O U~ ~1 . el~ Ln ~ N Ln ,~
N 'r ,J Ln ~i ~ Ln ~ NN 1`
~ ~') ~¦ 00 ~
N
~ N Ln 1`
E-~ cn ~
00 ~ In O ~r ~1 ~ r~
, a~
_ ~
Ul O ~
~: a) ~ .~
rl h ~ ~`1 k _ a) ~ a) x ~1 C~ ~
ho ~ .~ ~ _,~ 8
X ~. ~ o, r~
- ~D
I_ ~- W Cl~ ~ ~_ 1- I-p U~ ~ 1~
~t~ ,_~
1' 1' Ul ~ ~ ~
1~ ~P
~ O
~ o~
-;8 ~%~
To determine the total amount of rhodium and phos-phorus removed with the organic phase, the organic components drawn off from the reactor in the individual tests were combined, concentrated to about l/lOth of their original volume and analyzed.
0.017 ppm by weight of rhodium and 0.34 ppm by weight of phosphorus (in each case based on the original organic phase) were found.
Example 1 was repeated with the exception that 315 g (corresponding to 295 ml) of an aque~us solution of the trimethyl-benæylammonium salt of tri-(m-sulfophenyl)phosphine with a P(III) content of 0.308% hy weight and 158 g of n-hexene-l were used in the hydroformylation process instead o~ the sodium salt. The test results are reported in Table 2. The rhodium and phosphorus losses were determined by the method described in Example 1. An average of 0.029 ppm by weight of rhodium and 0.98 ppm by weight of phosphorus were removed with the organic product, i.e. only slightly more than when the normally employed sodium salt of tri-(m-sulfophenyl)phosphine was used.
-co ~ - ~o oo ~
~ o l`
a~
~1 ~D N
o Ln (5 ~) ~I N
C~ O
:) ~1 ~
~D .
a~ ~ ,I N
O U~ ~1 . el~ Ln ~ N Ln ,~
N 'r ,J Ln ~i ~ Ln ~ NN 1`
~ ~') ~¦ 00 ~
N
~ N Ln 1`
E-~ cn ~
00 ~ In O ~r ~1 ~ r~
, a~
_ ~
Ul O ~
~: a) ~ .~
rl h ~ ~`1 k _ a) ~ a) x ~1 C~ ~
ho ~ .~ ~ _,~ 8
4~ o~O
o Y U~ U~ ,, h 1~ n~ h0 ~ O O ~ ~ $ ~ ~
U~
O ~ h ~>
.
O O ~ h Z ~ d O
__ ~1.0--' EXAMPhES 3 to 5 Examples 3 to 5 were carried ou-t by the method descri-bed in Example 1 with the exception that instead of the sodium salt of tri-(m-sulfophenyl)phosphine; 420:g (corresponding.to 390 ml) of an aqueous solution containing 46~ by weight of the dodecylethyldim.ethylammonium salt of tri-'(m-sul~phenyl)phosphine (Example 3); 820 g (corresponding to 740 ml) of an aqueous solu-tion contain'ing 25% by weight of the benzyltrimethylammonium salt of di-'~m-sulfophenyl)-phenylphosphine'(Example 4); 420 g (corres-ponding to 39Q:ml) of an aqueous solution contain'ing 23~ byweigh't of the benzyltriethylammonium salt of.tri.-:(m-sulfophenyl) phosphine (Example 5) were used. The.test.results are.reported in Table 3.
o Y U~ U~ ,, h 1~ n~ h0 ~ O O ~ ~ $ ~ ~
U~
O ~ h ~>
.
O O ~ h Z ~ d O
__ ~1.0--' EXAMPhES 3 to 5 Examples 3 to 5 were carried ou-t by the method descri-bed in Example 1 with the exception that instead of the sodium salt of tri-(m-sulfophenyl)phosphine; 420:g (corresponding.to 390 ml) of an aqueous solution containing 46~ by weight of the dodecylethyldim.ethylammonium salt of tri-'(m-sul~phenyl)phosphine (Example 3); 820 g (corresponding to 740 ml) of an aqueous solu-tion contain'ing 25% by weight of the benzyltrimethylammonium salt of di-'~m-sulfophenyl)-phenylphosphine'(Example 4); 420 g (corres-ponding to 39Q:ml) of an aqueous solution contain'ing 23~ byweigh't of the benzyltriethylammonium salt of.tri.-:(m-sulfophenyl) phosphine (Example 5) were used. The.test.results are.reported in Table 3.
5 `~
a o ~ o o ,~
~o ~ o . ~ o ~ o o ~
o ~ o V~ o ,' a) . O v~
.
. o o
a o ~ o o ,~
~o ~ o . ~ o ~ o o ~
o ~ o V~ o ,' a) . O v~
.
. o o
6~ . tu ~d ~t X . ~1 0 ~1 X rC ~ ~ ~
~ U~ o ~ o W , ' : ~ o .
., . " ~
; b4 1~ ~0 o o o ~ ~,, ~ ~ ~
. a~
.` ,1 ~ X ~ U~
a) r~ E~
~ ~ cn ~ . ~ .
E~ I t~ ~ .
E~
.
., ~ . .~ , .~ ~ o . ~
~ ~ ~ ~ , ~
,_ ~ X o ~ ;~ o ., ~ ~ o ~ ~ ~ a~
O
Ei ~ ~ .,~
' ~ o ~ V~ ~ .C
. ~I
~ ~ O ~ ~ a~ ~
~7 0 ~ ~ ' rC ~ C) ~ ~4 0 ~ ~ .r~ rl E~ O O h .~ u h h ~ U ~ ~ ~
,,~ V) ~ ~ ~ ~ ~1 ~1 u ~ :~
O ~ ~ Ei ~rl ~ td ~ o In O a>
E- ~ O ~ U ~ ~ .n a) u ~ ~d a o ~ ,~
E- O ~ ~ z ~ ~ ~ u~
' , , o ' ' ' , ' ,. . ~
ii3 EXAMPLES 6 and 7 Examples 6 and 7 were also carried out under the con-ditions of Example 1 but with stYrene as the olefin. In ~xample 6 (comparison), the Na-salt (420 g corresponding to 375 ml of a 22~ by weight solution) and in Example 7, the dodecylethyldi-methylammonium salt (420 g corresponding to 391 ml of a 23% by weight solution) of tri-(m-sulfophenyl)-phosphine were used. The results of the tests are reported in Table 4 and as can be clearly seen, the quaternary ammonium salt favored the formation of a-phenylpropionaldehyde.
o s`
O `D
u) o ~
: ~ o ~ o v~ o~o o`
.
:~
~d ~
~ ~ o ' ' a) o ~ u~ ~
l-' '' ~d ~ O ~ 11 ~0 ~ l x ~ o o ~o o o ~ ~
. ,:, E-.
' ' ' ' ,~ ,~ ~ O
,u~ ~
) X tl~ rt h t~
~ ~ O ~ ~
' '' ' O ~d ~ ~ O O
o~ O n~ h ~ ~ ~
~ ~ ~ 4~ cd td ~
E~ o ~ ~ ~ u O ~ H ~ U
-- O u) O
o ~ ~
O ~ ~SL ~ Z ~ ~O t i`3 Various modifications of the process o~ the in~ention may be made without departing rom the spirit or scope thereof and it is to be understood that the invention is intended to 4 be limited only as deined in the appended claims.
~ U~ o ~ o W , ' : ~ o .
., . " ~
; b4 1~ ~0 o o o ~ ~,, ~ ~ ~
. a~
.` ,1 ~ X ~ U~
a) r~ E~
~ ~ cn ~ . ~ .
E~ I t~ ~ .
E~
.
., ~ . .~ , .~ ~ o . ~
~ ~ ~ ~ , ~
,_ ~ X o ~ ;~ o ., ~ ~ o ~ ~ ~ a~
O
Ei ~ ~ .,~
' ~ o ~ V~ ~ .C
. ~I
~ ~ O ~ ~ a~ ~
~7 0 ~ ~ ' rC ~ C) ~ ~4 0 ~ ~ .r~ rl E~ O O h .~ u h h ~ U ~ ~ ~
,,~ V) ~ ~ ~ ~ ~1 ~1 u ~ :~
O ~ ~ Ei ~rl ~ td ~ o In O a>
E- ~ O ~ U ~ ~ .n a) u ~ ~d a o ~ ,~
E- O ~ ~ z ~ ~ ~ u~
' , , o ' ' ' , ' ,. . ~
ii3 EXAMPLES 6 and 7 Examples 6 and 7 were also carried out under the con-ditions of Example 1 but with stYrene as the olefin. In ~xample 6 (comparison), the Na-salt (420 g corresponding to 375 ml of a 22~ by weight solution) and in Example 7, the dodecylethyldi-methylammonium salt (420 g corresponding to 391 ml of a 23% by weight solution) of tri-(m-sulfophenyl)-phosphine were used. The results of the tests are reported in Table 4 and as can be clearly seen, the quaternary ammonium salt favored the formation of a-phenylpropionaldehyde.
o s`
O `D
u) o ~
: ~ o ~ o v~ o~o o`
.
:~
~d ~
~ ~ o ' ' a) o ~ u~ ~
l-' '' ~d ~ O ~ 11 ~0 ~ l x ~ o o ~o o o ~ ~
. ,:, E-.
' ' ' ' ,~ ,~ ~ O
,u~ ~
) X tl~ rt h t~
~ ~ O ~ ~
' '' ' O ~d ~ ~ O O
o~ O n~ h ~ ~ ~
~ ~ ~ 4~ cd td ~
E~ o ~ ~ ~ u O ~ H ~ U
-- O u) O
o ~ ~
O ~ ~SL ~ Z ~ ~O t i`3 Various modifications of the process o~ the in~ention may be made without departing rom the spirit or scope thereof and it is to be understood that the invention is intended to 4 be limited only as deined in the appended claims.
Claims (5)
1. In a process for the preparation of aldehydes by reacting olefins with carbon monoxide and hydrogen in the liquid phase in the presence of water and rhodium in metallic form or as a compound as well as a water-soluble arylphosphine at tempera-tures of 20 to 150°C and 1 to 200 bar (100 to 2 x 104 kPa), the improvement comprising that the water-soluble phosphine has the formula where Ar is aryl and X is a sulfonic acid x1, x2 and x3 are 0 or 1 with the proviso that at least one of x1, x2 or x3 is 1, A is selected from the group consisting of an alkyl of 1 to 18 carbon atoms and aralkyl of 7 to 18 carbon atoms and B,C,D are alkyl of 1 to 4 carbon atoms and n is a whole number between 1 and 3.
2. The process of claim 1 wherein Ar is phenyl or naphthyl.
3. The process of claim 1 wherein the sum of x1, x2 and x3 is 2 or 3.
4. The process of claim 2 wherein the sum of x1, x2 and x3 is 2 or 3.
5. The process of claim 1 wherein B,C and D denote the same alkyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3420491.1 | 1984-06-01 | ||
| DE19843420491 DE3420491A1 (en) | 1984-06-01 | 1984-06-01 | METHOD FOR PRODUCING ALDEHYDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1244053A true CA1244053A (en) | 1988-11-01 |
Family
ID=6237409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000482937A Expired CA1244053A (en) | 1984-06-01 | 1985-05-31 | Process for the preparation of aldehydes |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0163234B1 (en) |
| JP (1) | JPS611633A (en) |
| KR (1) | KR880001353B1 (en) |
| AT (1) | ATE50556T1 (en) |
| AU (1) | AU577382B2 (en) |
| BR (1) | BR8502451A (en) |
| CA (1) | CA1244053A (en) |
| DE (2) | DE3420491A1 (en) |
| HU (1) | HU204249B (en) |
| PL (1) | PL253588A1 (en) |
| RO (1) | RO91880B (en) |
| SU (1) | SU1537134A3 (en) |
| ZA (1) | ZA853971B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3420493A1 (en) * | 1984-06-01 | 1985-12-05 | Ruhrchemie Ag, 4200 Oberhausen | QUARTERS OF AMMONIUM SALTS OF SULPHONED TRIARYLPHOSPHINS |
| DE3534314A1 (en) * | 1985-09-26 | 1987-04-02 | Ruhrchemie Ag | METHOD FOR PRODUCING ALDEHYDES |
| DE3546123A1 (en) * | 1985-12-24 | 1987-06-25 | Ruhrchemie Ag | METHOD FOR PRODUCING ALDEHYDES |
| DE3616057A1 (en) * | 1986-05-13 | 1987-11-19 | Ruhrchemie Ag | METHOD FOR PRODUCING ALDEHYDES |
| US4716250A (en) * | 1986-07-10 | 1987-12-29 | Union Carbide Corporation | Hydroformylation using low volatile/organic soluble phosphine ligands |
| US4825003A (en) * | 1986-09-17 | 1989-04-25 | Mitsui Toatsu Chemicals, Incorporated | Production process of 2-chloropropionaldehyde |
| US4731486A (en) * | 1986-11-18 | 1988-03-15 | Union Carbide Corporation | Hydroformylation using low volatile phosphine ligands |
| US5113022A (en) * | 1988-08-05 | 1992-05-12 | Union Carbide Chemicals & Plastics Technology Corporation | Ionic phosphites used in homogeneous transition metal catalyzed processes |
| DE3942954A1 (en) * | 1989-12-23 | 1991-06-27 | Hoechst Ag | PROCESS FOR THE PREPARATION OF ALDEHYDE |
| FR2671078A1 (en) * | 1990-12-31 | 1992-07-03 | Rhone Poulenc Chimie | REAGENT AND METHOD FOR THREE - PHASE HYDROCARBONYLATION. |
| US5288818A (en) * | 1991-08-20 | 1994-02-22 | Exxon Chemical Patents Inc. | Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
| US5215667A (en) * | 1991-08-20 | 1993-06-01 | Exxon Chemical Patents Inc. | Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
| DE4242725A1 (en) * | 1992-12-17 | 1994-06-23 | Hoechst Ag | Process for the production of higher, predominantly unbranched, primary alcohols |
| DE4440552A1 (en) * | 1994-11-12 | 1996-05-15 | Hoechst Ag | Process for the preparation of formyl carboxylic acid esters |
| US6756411B2 (en) | 1995-06-29 | 2004-06-29 | Sasol Technology (Proprietary) Limited | Process for producing oxygenated products |
| KR100451631B1 (en) * | 2002-05-17 | 2004-10-08 | 주식회사 바름인 | Preparation of fermented soybean product enriched γ-aminobutylic acid and phytoestrogens using Bifidobacterium breve K-110 of korean-type lactic acid bacteria |
| KR100460697B1 (en) * | 2002-06-01 | 2004-12-09 | 고을빛 생식마을 (주) | Manufacturing Method for Soaking and Germinated Soybean Containing High Isoflavone |
| DE102008044783B4 (en) | 2008-08-28 | 2012-05-16 | Oxea Gmbh | Process for the recovery of aliphatic C3 to C10 aldehydes from high boilers by thermal treatment |
| DE102009004655B4 (en) | 2009-01-15 | 2013-02-14 | Oxea Gmbh | Process for the preparation of aldehydes |
| DE102009016651B4 (en) | 2009-04-07 | 2011-11-17 | Oxea Gmbh | Process for the preparation of aldehydes |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3928232A (en) * | 1972-10-24 | 1975-12-23 | Chevron Res | Aryl sulfonate stabilized cobalt carbonyl complex compounds |
| US4248802A (en) * | 1975-06-20 | 1981-02-03 | Rhone-Poulenc Industries | Catalytic hydroformylation of olefins |
| FR2314910A1 (en) * | 1975-06-20 | 1977-01-14 | Rhone Poulenc Ind | Aldehyde prepn. by olefine hydroformylation in liquid phase - using catalyst system contg. sulphonated aryl phosphine and rhodium (NL 22.12.76) |
| NO156742C (en) * | 1979-03-28 | 1987-11-18 | Union Carbide Corp | PROCEDURE FOR THE PREPARATION OF A HYDROFORMAL MEDIUM AND THE PROCESS FOR THE PREPARATION OF ALDEHYDES. |
| FR2473504A1 (en) * | 1979-10-31 | 1981-07-17 | Rhone Poulenc Ind | Aldehyde prepn. from hydrogen, carbon mon:oxide - and olefin, in presence of cobalt cpd. and water soluble phosphine |
| GB2085874B (en) * | 1980-09-04 | 1984-08-08 | Johnson Matthey Plc | Hydroformylation of olefins |
| DE3234701A1 (en) * | 1982-09-18 | 1984-04-05 | Ruhrchemie Ag, 4200 Oberhausen | METHOD FOR PRODUCING ALDEHYDES |
| DE3413427A1 (en) * | 1984-04-10 | 1985-10-17 | Ruhrchemie Ag, 4200 Oberhausen | METHOD FOR PRODUCING ALDEHYDES |
-
1984
- 1984-06-01 DE DE19843420491 patent/DE3420491A1/en not_active Withdrawn
-
1985
- 1985-04-26 SU SU853884106A patent/SU1537134A3/en active
- 1985-04-30 KR KR1019850002900A patent/KR880001353B1/en not_active IP Right Cessation
- 1985-05-21 EP EP85106184A patent/EP0163234B1/en not_active Expired - Lifetime
- 1985-05-21 AT AT85106184T patent/ATE50556T1/en not_active IP Right Cessation
- 1985-05-21 DE DE8585106184T patent/DE3576150D1/en not_active Expired - Fee Related
- 1985-05-24 RO RO118874A patent/RO91880B/en unknown
- 1985-05-24 BR BR8502451A patent/BR8502451A/en not_active IP Right Cessation
- 1985-05-24 PL PL25358885A patent/PL253588A1/en unknown
- 1985-05-24 ZA ZA853971A patent/ZA853971B/en unknown
- 1985-05-27 HU HU852000A patent/HU204249B/en not_active IP Right Cessation
- 1985-05-30 JP JP60115555A patent/JPS611633A/en active Granted
- 1985-05-31 CA CA000482937A patent/CA1244053A/en not_active Expired
- 1985-05-31 AU AU43218/85A patent/AU577382B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| RO91880B (en) | 1987-07-31 |
| JPH0140019B2 (en) | 1989-08-24 |
| SU1537134A3 (en) | 1990-01-15 |
| EP0163234A3 (en) | 1987-05-27 |
| DE3420491A1 (en) | 1985-12-05 |
| KR860000237A (en) | 1986-01-27 |
| BR8502451A (en) | 1986-01-28 |
| PL253588A1 (en) | 1986-02-11 |
| EP0163234B1 (en) | 1990-02-28 |
| AU577382B2 (en) | 1988-09-22 |
| DE3576150D1 (en) | 1990-04-05 |
| HU204249B (en) | 1991-12-30 |
| ZA853971B (en) | 1986-01-29 |
| RO91880A (en) | 1987-07-30 |
| EP0163234A2 (en) | 1985-12-04 |
| JPS611633A (en) | 1986-01-07 |
| ATE50556T1 (en) | 1990-03-15 |
| HUT39703A (en) | 1986-10-29 |
| AU4321885A (en) | 1985-12-05 |
| KR880001353B1 (en) | 1988-07-28 |
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