WO1984003697A1 - Hydroformylation a haute temperature - Google Patents

Hydroformylation a haute temperature Download PDF

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Publication number
WO1984003697A1
WO1984003697A1 PCT/US1984/000423 US8400423W WO8403697A1 WO 1984003697 A1 WO1984003697 A1 WO 1984003697A1 US 8400423 W US8400423 W US 8400423W WO 8403697 A1 WO8403697 A1 WO 8403697A1
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rhodium
hydroformylation
olefin
phosphine
triarylphosphine
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PCT/US1984/000423
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English (en)
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Alexis A Oswald
Joseph S Merola
John C Reisch
Rodney V Kastrup
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Exxon Research Engineering Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
    • C07C5/2562—Catalytic processes with hydrides or organic compounds
    • C07C5/2593—Catalytic processes with hydrides or organic compounds containing phosphines, arsines, stibines or bismuthines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Definitions

  • This invention is related to triarylphosphine catalyzed a liquid phase hydroformylation process catalyzed by triarylphosphine rhodium carbonyl hydride complexes. More particularly, the improved process of the present invention converts olefinic reactants, preferably 1-n-olefins, by reacting them with CO and H 2 to the corresponding aldehydes, preferably n-aldehydes, in a highly selective manner. As such the selectivity of the process of the invention is dependent on favorable equilibria among the above type of catalyst complexes, in the presence of a certain large excess of triaryl or substituted triaryl phosphine ligand.
  • a major aspect of the Invention is concerned with controlling the catalyst equilibria preferably by maximizing the concentration of the desired tris-triarylphosphine rhodium carbonyl hydride catalyst precursor complex and generating the desired selective catalyst species therefrom.
  • the stabilization of the desired catalyst precursor by excess, free triaryl phosphine is disclosed.
  • a particular aspect of the present Invention is an improved continuous hydroformylation of olefins via the present catalyst systems, at elevated temperatures and under increased partial pressures of CO.
  • the continuous hydroformylation process of the present invention emphasizes the thermal and long term operational stability of the catalyst system, i.e. activity maintenance at high temperatures. For such stability the composition of the liquid reaction medium is important.
  • the process of the present Invention mainly relates to continuous hydroformylations in the liquid phase where the reactants are continuously fed into and the products plus unconverted reactants are continuously removed in the gas phase from the reaction mixture.
  • Beside primary products, aldehydes, these continuous hydroformylations produce secondary by-products, monoalcohols and their monoester derivatives. The latter become high boiling solvent components.
  • Such hydroformy! ations include the recirculation, in the vapor and/or l iquid phase, of some or all of the reactants and of the minor quantities of excess triarylphosphine l igands, removed in the vapor phase.
  • the present continuous process is particulary aimed at the selective hydroformylation of 1-butene and higher olefi ns wherein the control of olefin isomerization side reactions is important.
  • Triaryl phosphine rhodium complexes are also considered as batch and continuous catalysts for a combined isomerization hydroformyl ation of l inear Internal olefins, e.g. 2-butene.
  • U.S. Patent 4,227,627 by D. R. Bryant and E. Billig disclosed three critical parameters for activity maintenance in PFO hydroformylations.
  • the activity maintenance i.e. catalyst stability factor
  • the triphenylphosphfne to rhodium ratio is directly related to the triphenylphosphfne to rhodium ratio and indirectly related to the CO partial pressure and temperature. These parameters were correlated to maximize the stability of the trimer solvent based catalyst system.
  • Bryant and Billig state that in a commercial operation a realistic loss of catalyst activity is 0.5% per day. They point out that using their invention this loss can be reduced to below 0.3% per day.
  • Billig and Bryant obtained a catalyst activity loss of 2% or higher per day at 120°C or above, due to the strong adverse effect of temperature on stability. Consequently, the Billig and Bryant process is limited to temperatures from about 90° to about 130°C.
  • the selectivity of the known continuous hydroformyl ations was expected to be adversely affected by high reaction temperatures .
  • G. Montrasi et al published that the amount of by-product heavy ends, speci fically the "trimers,” is strongly proportional to the reaction temperature. See Volume 6, pages 737 to 742 of the La Chimica e L' Industrie journal in Milan, 1980. Irv further improvement patents, similar low temperature processes are claimed in excess triphenyl phosphine as a solvent.
  • U.S. Patent 4,108,905 by G. Wilkinson discloses the hydroformylation of propylene and other gaseous olefins with triphenyl phosphine rhodium complexes in liquid triphenyl phosphine medium, in the absence of liquid olefin using H 2 /CO reactant ratios of about 2 to 0.07.
  • Wilkinson notes that at 150oC and above his catalyst decomposes.
  • Wilkinson's examples Included experiments with continuous product removal by distillation and analysis by gas chromatography. However, he did not observe any aldolization products. The duration of his experiments is not disclosed. A short running time would explain the apparent absence of higher boiling by products.
  • McCracken and R. C. Williamson also discloses similar hydroformylation 1n triphenyl phosphine using varying H 2 /CO ratios but being limited to temperatures between 60o to 115°C and batch operation.
  • U.S. Patent 4,229,990 by H. Tumrnes, B. Cornils and H. Noeske describes the stabilization of triphenylphosphine rhodium complex catalysts in triphenylphosphine solvent by C 1 to C 5 paraffinic hydrocarbons employed as a component of the olefinic feed 1n a continuous PFO ooeration.
  • inactive phosphide complexes are formed at low propylene concentration.
  • triphenyl phosphine is oxidized to triphenylphosphine oxide by al dehydes, parti cularly by 2-ethylhexenal , according to Montrasi et al.
  • the scientifi c literature is highly pessimistic regarding a substantially complete stabilization of the homogeneous liquid catalyst systems based on triarylphosphine rhodium compl exes.
  • the hydroformylation catalyst system is much more stable and provides a higher n- to i-ratio of aldehyde products than at the lower concentrations disclosed In the Pruett and Smith patents. Furthermore, the present catalyst system also provides a higher ratio of n/i products than the triphenyl phosphine only process of the Wilkinson patent. In addition, it was found that the catalyst system is much less sensitive to higher partial pressures of carbon monoxide when the phosphine concentration is high. In effect, both the apparent rate of the hydroformylation and its selectivity to total aldehydes increases with increasing CO partial pressures. In contrast, the Pruett et al. and Bryant et al.
  • patents disclose a process limited to a top CO partial pressure of 55 psla.
  • the selectivity of the present catalyst system with regard to the n-versus i-ratio of the aldehyde products was found to be insensitive to the triaryl phosphine to rhodium ratio.
  • the selectivity is essentially determined by the triaryl phosphine concentration alone.
  • the rhodium concentration can be independently increased to achieve the desired reaction rate without affecting the n/i ratio of products.
  • trimer solvent formation by Pruett et al, and Montrasi et al. can be substantially eliminated.
  • the key intermediate of the secondary higher molecular weight by-products was found to be the u ⁇ saturated aldol aldehyde rather than the hydroxy aldol aldehyde.
  • the unsaturated aldol aldehyde by-product undergoes hydrogenation and subsequent aldolization, oxidation and esterification reactions. Consequently, the resulting monoalcohols and monoesters rather than the trimers are enriched in the liquid reaction mixture during product distillation and as such become the high boiling solvent components
  • the liquid reaction media of the continuous process of the present invention contains significant amounts of dissolved olefin in the liquid phase.
  • the reaction occurs in the liquid. phase.
  • the present reaction media also contain increased amounts of dissolved CO as a result of Increased CO partial pressures, in excess of 25 psia. The latter is in contrast to the minimum CO partial pressures preferred in the Pruett et al. and Bryant et al. patents.
  • the high temperature continuous hydroformyl ation process of the present Invention shows a unique combination of selectivity and maintenance of catalyst activity.
  • the maintenance of catalyst activity in these systems is not due to either the presence of alkanes in the feed or the absence of high boiling organophosphorus by-products in the mixture.
  • the stability is believed to be mainly attributable to the maximization of the rhodium species present as the tris-triarylphosphine rhodium carbonyl hydride com plex via the special reaction medium and the above discussed operational parameters.
  • the present invention also provides an improved combined isomerization hydroformylation process for the selective conversion of Internal olefins to n-aldehydes at minimum CO partial pressure.
  • the present process does not require the presence of transition metals other than rhodium.
  • the present high temperature process is also applicable for the selective hydroformylation of internal linear olefins to i-aldehydes, at maximum CO partial pressures.
  • the hydroformylation process of the present invention comprises reacting dissolved olefinic feed with CO and H 2 in a homogeneous liquid phase medium at temperatures between about 120 and 200°C and at a total pressure in the range of 100 to 1500 psi to selectivity produce aldehydes in the presence of tris-triarylphosphine rhodium monocarbonyl hydride and bis-triarylphosphine rhodium dicarbonyl hydride complex catalysts free from halogen on the rhodium wherein said reaction medium comprises a minimum of 1 mole per kg, i.e.
  • Particul arly, tris-triphenyl phosphine rhodi um carbonyl hydride plus triphenyl phosphine are components of a widely used homogeneous catalyst system for the continuous hydroformyl ation of propylene to provide n- rather than i-butyraldehyde:
  • Hydroformylation at increased temperatures is advantageous because of the increased activity of the rhodium complex catalyst.
  • the increased reaction temperature is also important because under a given set of conditions, it largely determines the amount of the aldehyde product which can be removed by distillation from the reaction mixture ( Figure 1).
  • the boiling points of the corresponding aldehyde products are sharply elevated.
  • the boiling points of n-butyraldehyde and n-valeraldehyde are 75° and 103°C, respectively.
  • the superatmospheric pressures of commercial hydroformy!ations there are of course corresponding elevations of the atmospheric boiling points.
  • the present hydroformylation process is preferably practiced in a continuous mode of operation comprising reacting a dissolved C 2 to C 10 preferably a C 4 to C 10 olefinic feed with CO and hydrogen in the manner described.
  • This continuous hydroformy!ation is additionally characterized by the continuous introduction of reactants and the continuous removal and
  • the product removal by a flash-off type distillation can be effected either from the reaction vessel during the reaction (PFO) or from a separate flash-off vessel, usually at a reduced pressure.
  • the latter operation preferably comprises a continuous recycle of the reaction medium containing the nonvolatile catalyst (RFO).
  • RFO nonvolatile catalyst
  • a PFO operation removing the products from the medium during the reaction in the gas phase is preferred over RFO, especially with volatile olefin feeds.
  • the present process is preferably employed for the selective production of n-aldehydes from vinylically unsubstltuted terminal olefins.
  • the process preferably comprises selectively reacting a dissolved 1-n-olefin, preferably 1-butene, with CO and H 2 in a homogeneous liquid phase to selectively produce a n-aldehyde, preferably n-valer- aldehyde, wherein the ratio of H 2 to CO reactant is preferably in the range of about 2.5 to 10 to assure a ratio above 10 of the n- to i- aldehyde products.
  • the concentration of excess triphenylphosphine ligand and the partial pressure of CO reactant are kept appropriately high. Thus dally loss of catalyst activity is kept below about 0.5%, preferably 0.3%.
  • Preferred feeds for the production of n-aldehydes from 1-olefins via the present selective process include olefin mixtures.
  • a mixture of isomeric butenes, particularly a mixture of 1-butene and 2-butene can be used as a 1-olefinic feed to selectively produce n-valeraldehyde from 1-butene.
  • the relatively nonreactive olefin isomers of such a mixed feed mainly act as a striping gas to remove the products.
  • the present process is also applicable for homogeneous combined isomerization hydroformylation comprising isomerizing an internal linear olefin, preferably 2-butene, to a terminal 1-n-olefin, preferably 1-butene, and hydroformylating the 1-n-olefin component of the resulting isomeric
  • the overall reaction conditions of this combined process are the same as those of the direct hydroformylation.
  • the partial pressure of the CO hydroformylation reactant which inhibits the isomerization step is kept at a minimum, i.e. below 100 psi, preferably below 20 psi.
  • the present process can be also used for the production of iso-aldehydes from linear internal olefins. In this process, the role of the excess triarylphosphine is only that of a stabilizer.
  • the formation of n-valeraldehyde by-products is inhibited by a relatively high CO partial pressure, preferably above 100 psi most preferably above 300 psi.
  • the increased CO partial pressure also increases the activity of the catalytic complex of this process, primarily bistriarylphosphine rhodium dicarbonyl hydride.
  • Figure 1 shows an outline of the continuous hydroformylation unit of the present process with continuous product flashoff from the reactor (PFO).
  • Figure 2 illustrates, by 31 P NMR spectra, the effect of excess phosphine on the equilibrium between tris-triphenylphosphine rhodium carbonyl hydride and bis-triphenylphosphine rhodium dicarbonyl hydride.
  • Figure 3 illustrates, by 13 C NMR spectra, the effect of CO partial pressure on the equilibrium between tris-triphenylphosphine rhodium carbonyl hydride and bis-triphenylphosphine rhodium dicarbonyl hydride.
  • Figure 4 illustrates the temperature dependence of the reversible dissociation of tris-triphenylphosphine rhodium carbonyl hydride by the variable line shape of 31 P NMR signals.
  • Figure 5 outl ines the reaction profile of the triphenylphosphine rhodium carbonyl complex intermediates of olefin hydroformylation and thus shows the energetics of these catalytic intermediates.
  • Figure 6 shows the multiple equilibria among the triarylphosphine rhodium complex intermediates of 1-butene hydroformylation and their role in the formation of n- and/or i-valeroaldehyde products, and butane and 2-butane by-products.
  • Figure 7 outlines the alternate catalytic pathways of triarylphosphine rhodium complex catalyzed hydroformylation. Dependent on the carbonylation degree of the active complex species, these pathways lead to n- or n- plus i-aldehyde products of 1-n-olefin hydroformylation.
  • Figure 8 shows the oxygenated solvent components of the high temperature 1-butene hydroformylation catalyst system of the present invention.
  • CATALYST COMPLEXES The process of the present invention is based on a new understanding of the catalytic mechanism of hydroformyl ations catalyzed by triarylphosphine rhodium complexes.
  • the state of equilibrium between tris- and bis- triarylphosphine complexes also depends on the structure of the triarylphosphine l igand. Sterlcal ly crowded tris-triarylphosphine complexes are comparatively readily converted to the corresponding bis-phosphine complexes because of the smaller steric requirement of the carbonyl ligand. Increased steric crowding results from the ortho-substitution of the triarylphopsphine l igands.
  • neither the tris- nor the bis- phosphine complex is an effective hydroformylation catalyst. To become active, these coordi natively saturated compl exes are to dissociate to provide highly reactive coordi natively unsaturated species. These dissociation reactions leading to catalyst activation are temperature dependent and reversible.
  • the dissociation of tris- triarylphosphine rhodi um carbonyl hydride complexes and thus thei r catalytic activity depend not only on the temperature but on the structure of the triarylphophine l igand. For example, sterlcally crowded tris-phosphine complexes containing orthosubstituted triarylphosphines exhibit accelerated rates of dissociation and thus increased activity.
  • the main species in solution is the tris- phosphine monocarbonyl hydride.
  • Some of this complex dissociates to give the corresponding trans-bis-phoshine carbonyl hydride, which in turn reacts with the olefins to form the normal alkyl derivative.
  • the latter then reacts with CO and rearranges to a stable acyl rhodium derivative which leads to the n-aldehyde product.
  • Similar dissociation followed by olefin reaction forms the secondary alkyl derivative which leads to the isoaldehyde, in both cases by well establ ished sequence of reactions.
  • the dihydride extrudes the normal aldehyde, the desired product, and regenerates the coordinatively unsaturated species.
  • a similar catalytic cycle involving a dicarbonyl hydride was found for nonselective hydroformylation as indicated by Figure 7.
  • the above understanding of selective and nonselective hydroformylation reactions can be summarized by stating that the tris-phosphine monocarbonyl hydride is the main catalyst proposed for selective hydroformylation to provide n-aldehydes. Reactions occur on dissociation of this species.
  • the relative amounts of the two coordinatively unsaturated complexes leading to different hydroformylation pathways can be controlled by the excess Ph 3 P and CO concentrations.
  • the above discussed active carbonyl hydride and inactive carbonyl dimer complexes are in an equilibrium. At increased temperatures, the control of the intermediates becomes more difficult due to their decreased stability.
  • a high concentration of Ph 3 P was essential for maintaining the stability of the overall catalyst system e.g. by increasing the concentration of the tris-phosphine complex which acts as a stable reversible reservoir of the active species.
  • the triarylphosphine rhodium complex based homogeneous liquid catalyst system contain the catalytic rhodium carbonyl hydride complexes and excess triaryl phosphine ligands plus oxygenated solvents. Together with the dissolved synthesis gas reactant these compositions constitute an essentially complete reaction medium.
  • the catalyst compositions of the present invention are mainly defined as coordinatively saturated tris- and/or bis- triaryl- phosphine rhodium carbonyl hydride complexes. On phosphine and CO dissociation, these major complexes provide minute concentrations of the active species already discussed.
  • the triaryl phosphine rhodium complex catalyst components are preferably of the formula [(Ar 2 P) y Q y ] g Rh(CO) z H wherein Ar is aryl, preferably an independently selected C 5 to C 18 , preferably C 6 to C 12 , unsubstituted or substituted aryl, preferably phenyl.
  • the number of aryl and phenyl substituents is 1 to 3, preferably 1.
  • the preferred position of phenyl substituents is para- or meta. In the case of internal linear olefin reactants ortho-substituted ligands are preferred.
  • the substituents are selected with the proviso that they must exclude groups which are reactive or chemically unstable under hydroformylation conditions.
  • the preferred substituents are selected from the group consisting of hydrocarbyl, preferably alkyl, hydrocarbyloxy, cyano, nitro, hydrocarbylthio, hydrocarbylsulfonyl, hydrocarbylamino, hydrocarbylamido, halo and fluoroalkyl groups. More preferred are hydrocarbyl particularly alkyl groups.
  • the meaning of the Q groups of the above formula is aryl or arylene.
  • the aryl group is as defined for the symbol Ar.
  • the arylene group is a C 5 to C 18 , preferably C 6 -C 12 , unsubstituted or substituted arylene more preferably phenylene, most preferably p-phenylene.
  • the arylene substituents are selected with the priviso excluding reactive groups. Alkyl substituents are preffered.
  • the arylene group is preferably unsubstituted. It is preferred that one of the Ar and Q groups be different.
  • the symbol y indicates that valency of the 0 groups; y is 1 or 2. if Q is aryl, y is 1; if 0 is arylene, y is 2.
  • the symbol g means 1 to 3, preferably 2 or 3, more preferably 3.
  • the symbol z is 1 or 2, preferably.
  • a preferred type catalyst complex is of the formula (Ar 3 P) g Rh(C0) z H wherein meaning of the symbol is the same.
  • Another preferred type catalyst complex, derived from arylene bis-phosphines is of the following formula (Ar 2 PQPAr 2 ) g Rh(CO) z H
  • aryl groups are phenyl, fluorophenyl, difluorophenyl, tolyl, xylyl, be ⁇ zoyloxphenyl, carboethoxyphenyl, acetylphenyl, ethoxyphenyl , phenoxyphenyl , biphenyl, napthyl, hydroxyphenyl , carboxyphenyl, trifluoromethylphenyl, tetrahydronaphthyl, furyl, pyrryl, methoxethylphenyl, acetamidophenyl , dimethyl carbamylphenyl , chlorophenyl, tbutylphenyl.
  • arylene groups are phenylene, naphthylene, biphenylene, methylene bis-phenyl, oxy bis-phenyl, propylidene bis-phenyl.
  • substituents of the aryl and arylene groups are methyl, dodecyl , t-butyl, ethoxy, phenoxy, tri fluoromethyl , acetyoxy, benzoyloxy, carboethoxy, acetamido, chloro, fluoro, bromo, hydroxy, carboxy, methylthlo, methylsulfonyl, trimethylsilyl.
  • the triarylphosphine rhodium carbonyl hydride catalyst complex compositions of the present invention include mixed ligand complexes containing one mole alkyl diaryl phosphine ligand per rhodium atom.
  • the broad general formula is the following:
  • R' is alkyl and substitued alkyl, preferably C 2 to C 10 alkyl, more preferably C 4 to C 10 n-alkyl; g is 1 to 3; ⁇ is 0 or 1, the other symbols being as described above.
  • such mixed ligand complexes are of the formula (Ar 3 P) 2 (Ar 2 PR , )Rh(CO)H and (Ar 3 P)(Ar 2 PR')Rh(CO) 2 H
  • such complexes are formed during continuous hydroformylation reactions via reversible l igand displacement, e.g.
  • the Ar 2 PR' reactants of such displacement reactions are continuously formed in trace quantities during hydroformylation.
  • n-butyldiphenylphosphine and n-amyldiphenyl phosphine are formed.
  • the carbon numbers of the alkyl groups of such ligands apparently correspond to that of the olefin reactant and main aldehyde product, respectively.
  • Morrell et al. In contrast to the previously discussed prior art processes of Paul et al., Morrell et al.
  • the formation of trace quantities of alkyldiary!phosphine ligands and their rhodium complexes of the above formula has no significant adverse effect on the present process. Due to the high temperature of the present process most of the free alkyldiarylphosphine ligand is usually effectively stripped. Also, the mixed ligand complexes have comparable activities to the pure triarylphosphine complexes. In effect, the presence of mixed ligand complexes can be advantageous due to the increased total aldehyde selectivity.
  • the mixed ligand complexes of the present invention are outside the scope of the inventions of copending applications of Serial No.120,971 and Serial No.
  • the phosphine rhodiun complex based catalyst systems of the process of the earlier application are primarily alkyldiarylphosphine rather than triarylphosphine ligand based and they are not distinguished by the presence of carboxylic acid monoester and free alcohol solvent components. While the concentration of the catalytic rhodiun complex obviously affects the hydroformylation, there is no critical catalyst concentration in the present process. In general, the catalyst concentration employed is sufficient to assure the desired rate. The concentration of the catalyst is best described on a rhodium basis.
  • the concentration is usually between about 0.1 and 1000 preferably 1 and 100nM rhodium complex in the liquid reaction medium.
  • the latter is in the range of 100 ppm and 10000 ppm. Since the hydroformylation rate is directly related to the olefin concentration by a first order dependency, lower rhodium concentrations are sufficient at high olefin concentrations. Conversely, higher rhodium concentrations are required at increased excess triarylphosphine concentration due to an inverse rate dependency on the phosphine concentration. In contrast to the prior art, the selection of rhodium concentration is not influenced by a desired phosphine to rhodium ratio.
  • the P/Rh ratio has no significant effect on the n/i ratio of the aldehyde products.
  • the rhodium concentrations employed are higher than those disclosed by the prior art.
  • the P/Rh ratios are generally relatively low in the present process, even though the absolute phosphine ligand concentration is high.
  • Ligand to rhodium ratios in the range of 10 to 3000, preferably 100 to 1000 are typical.
  • the free triaryl phosphine components of the present catalyst system are preferably of the same structure as those triaryl phosphine ligands which are complexed to the rhodiun.
  • a preferred group of triaryl phosphines is liquid at ambient temperature. Another preferred group possesses unsymmetrical structures. The boiling point of a preferred group is greater than 400oC. A further preferred group, has melting points from about 50° to 150°C and can be crystallized from the catalyst system. Finally, a preferred group is represented by bis-phosphines particularly those having less than 40 carbon atoms per molecule.
  • Suitable symmetrical triaryl phosphines are triphenyl phosphine, tritolyl phosphine, tri-chlorophenyl phosphine, tri-trifluoromethylphenyl phosphine, trifuryl phosphine, trithienyl phosphine, tricyanophenyl phosphine, tri-difluorophenyl phosphine.
  • Suitable unsymmetrical phosphines are phenyl bisethoxy-phenyl phosphine, phenyl bis-butylphenyl phosphine, diphenyl phenoxphenyl phosphine, diphenyl octyl phenyl phosphine, diphenyl chlorophenyl phosphine, diphenyl nitrophenyl phosphine, diphenyl methyl sulfonyl phenyl phosphine, diphenyl benzothienyl phosphine, diphenyl biphenyl phosphine, diphenyl terphenyl phosphine, diphenyl pyrryl phosphine.
  • bi s-phosphines and polyphosphines examples include bi s-diphenyl -phosphino benzene, bis-diphenylphosphlno napthalene, bis-diphenyl phosphino diphenyl oxide, bis-diphenyl biphenyl, bis-diphenyl-phosphino diphenyl methane, tris-diphenylphosphino napthalene.
  • the triaryl phosphine l igands and the rhodium carbonyl hydride l igand compl exes of the present invention are prepared via methods taught in the l iterature.
  • the catalytic compl exes are most advantageously prepared from their readi ly available precursors in situ.
  • Exempl ary precursors are acetyl acetonato dicarbonyl rhodium and hexarhodium hexadecacarbonyl.
  • the absolute concentration of the triaryl phosphine ligand in the reaction mixture must be high in the present process.
  • the ohosphine is a major component of the reaction mixture.
  • the phosphine concentration ranges from 1 to 3.5 phosphorus equi liter, preferably from about 1 to 2.7 equivalent per liter. In the case of triphenyl phosphine this means a weight concentration in the solvent alone ranging from about 32.9 to 95%.
  • a further preferred concentration range is 1.5 to 2.7 phosphine equivalent per liter, i.e., 49 to 88%.
  • the stabilization of the present catalyst system is directly proportional to the phosphine equivalency of the ligand. On a molar basis non-chelating bis-phosphine are twice as effective stabilizers. As previously discussed, the concentration of the excess triarylphosphine ligand is also directly related to the n/i ratio of aldehyde products.
  • OXYGENATED SOLVENTS employs simple oxygenated solvent components selected from the group consisting of monoalcohols, simple alkyl esters of carboxyl ic acids, branched aldehydes and acetals. These oxygenated solvents were not anticipated by the known prior art. Monoalcohols and alkyl esters of carboxyl ic acids, such as n-butanol and ethyl benzoate, did not provide homogeneous liquid mixtures throughout the full course of the rel ated Union Carbide hydroformyl ation process as disclosed in columns 11 and 12, Table I of U.S.
  • Patent 4,148,830 by Pruett and Smith Branched aldehydes and acetals were not suggested to our knowl edge as solvent components for triarylphosphine rhodium complex catalyst systems.
  • the monoalcohol solvent components of the present hydroformy lation process are preferably by-products of the process.
  • the preferred solvents include n-amyl alcohol and 2-propylheptanol. These are both derived from the main n-valeraldehyde product via a combination of hydrogenation and aldolization reactions:
  • the preferred carboxylic add esters are derived from carboxylic acid derivatives of hydroformylation products; e.g.
  • the branched aldehyde solvent components are minor hydroformylation products.
  • isovaleraldehyde, 2-propyl-2-heptenal and 2- propylheptanal are by-products of 1-butene hydroformylation
  • the acetal solvents are also derived from aldehyde products and alcohol by- products, e.g. in the case of 1-butene
  • These oxygenated solvent components are by-products of the present continuous high temperature hydroformylation process while in the prior art continuous process oxygenated solvents were the trimers and tetramers derived from the aldol adduct of the aldehyde product, e.g.
  • the aldol adduct molecule rapidly loses a mole of water to form the unsaturated aldehyde which is expected to inhibit hydroformylation, e.g.
  • the aldehyde is not an effective inhibitor and is largely hydrogenated to provide the corresponding saturated aldehyde and alcohol which are desirable solvent components.
  • the rate of formation of the main trimer solvent components increases with increasing temperature.
  • the present high temperature process produces different, generally lower boiling, oxygenated solvent compounds at a much reduced rate. This is advantageous because an unnecessary excess of oxygenated compounds reduces the useful reactor volume and too much nonvolatile formation hinders the maintenance of constant liquid volume due to more difficult product flash-off.
  • the present process operates at such temperatures that aldehyde product concentration and thus aldolization are kept at a minimum by a more effective flash-off.
  • the aldehydes concentration in the reactor is 35%, in the present process it is less than 15%.
  • the main reactive solvent of the present process is the triarylphosphine which is the major component of the reaction medium. As described this solvent ligand interacts with the catalytic complexes and thereby stabilizes them. Although the main function of the excess triaryl phosphine is that of a catalyst stabilizer, it also acts as a solvent.
  • the olefin reactant has preferably 4 or more carbons.
  • the preferred total pressure is preferably increased above 250 psi which is in contrast to the low pressure propylene hydroformylation disclosed in U.S. Patent 4,108,905 by Wilkinson.
  • the olefin is not a major solvent component in the continuous process and the dissolved olefin concentration is preferably between 1 and 10%.
  • the concentration of total hydrocarbons is preferably less than 15%.
  • Olefinic Reactants The preferred olefin reactants for the hydroformyl ation process of the present invention are ethylene and its mono and disubstituted derivatives.
  • the substituents are preferably alkyl and substituted alkyl , more preferably alkyl.
  • Mono-substituted derivatives, particularly ⁇ -olefins are preferred.
  • the preferred carbon number is 2 to 40.
  • Ol efins having 4 to 12 carbon atoms are particularly preferred.
  • the specifi cal ly preferred olefin reactant is 1-butene.
  • exemplary reactants are propylene, 2-methyl-pentene-1 , butene-2, octene-1 , pentene-1 , al ly! alcohol , al ly! acetate, al lyl t-butyl ether, acrolein dimethyl acetal, methyl oleate; 1 ,7-octadiene, dicycl opentadiene, trivinyl cyclohexane, 1 ,4-polybutadiene, acrylonitri le, methyl acryl ate, acetal derivatives of acrol ein, 2-butene, 4-octene.
  • n/i ratio of products is also facilitated by reduced CO partial pressure.
  • sufficiently high n/i ratios can be achieved at CO partial pressures above 25 psia and with equimolar mixtures of H 2 and CO reactants.
  • the size, i.e., steric demand of the T 1 substitutent also affects the selectivity.
  • the selectivity to the n-product is relatively small.
  • 1-Butene, with ethyl for T 1 is hydroformylated with surprisingly higher selectivity.
  • 3-Methyl -1-butene, where T 1 equals i-propyl reacts even much more selectively. Apparently, the bulkier and more branched T 1 groups hinder the attack on the internal, 5-vinylic carbon.
  • the preferred monosubstituted olefi ns are 4 to C 40 n-1-olefins, wherein T 1 is n-alkyl.
  • the most preferred reactant is 1-butene.
  • Ratios of n/i -products are preferably above 6, more preferably above 9.
  • the disubstituted compound is a highly specific but less reactive reagent in hydroformylation. It leads to mostly terminal , so cal led n-aldehydes:
  • T wherein the meaning of T is the same as described above.
  • preferred reagents of this type are isobutene, 2-methyl butene, 2-methylpentene, 2-ethylhexene, 2,4,4,-trimethylpentene. It was found that in the case of these unsymmetrical olefins it is advantageous to use a nearly equimolar mixture of synthesis gas.
  • the preferred range of H 2 /CO is from about 3/2 to 2/3.
  • CO partial pressures preferably above 25 psia, more preferably above 60 psia, are used.
  • the symmetrical ly disubstitued olefins such as linear internal olfeins, slowly react at their internal vinyl ic carbons to provide the corresponding branched aldehydes, e.g. ,
  • T wherein the meaning of T is as previously stated.
  • Preferred reagents of this type are butene-2 and pentene-2.
  • high CO partial pressures are preferred.
  • the preferred process conditions are those described for the unsymmetrical ly substituted olefins.
  • these l inear nonsubstituted internal olefins can be also used for the production of straight chain aldehydes preferably via a combined i somerization, hydroformylation process. The course of such a process in the case of 2-butenes feed is indicated by the followi ng scheme.
  • T wherein the meaning of T is as previously stated.
  • Preferred reagents of this type are butene-2 and pentene-2.
  • high CO partial pressures are preferred.
  • the process conditions are those described for the unsymmetrically substituted olefins.
  • these linear, nonsubstituted, internal olefins can be also used for the production of straight chain aldehydes preferably via a combined isomerization, hydroformylation process. The course of such a process in the case of 2-butenes feed is indicated by the followinq scheme.
  • the present hydroformylation process can be advanta ⁇ eously operated using a mixed olefinic feed. Using mixtures of three different types of preferred olefins, the most reactive 1 -n-olefin component could be selectively converted to the corresponding n-aldehyde.
  • the 1-butene component of a mixture of isomeric butenes preferably of 1- and 2-butenes can be selectively hydroformylated to provide n-valeraldehyde.
  • 1-pentene and 3- methyl -butene can be terminally hydroformylated using an isomeric mixture of pentenes such as those present in light catalytically cracked naphtha.
  • the Isomerization rates of linear olefin reactants and/or the rates of branched aldehyde product isomer formation can be accelerated by using sterically crowded triarylphosphine ligands preferably those substituted in the ortho-position such as tri-o-tolyphosphine. Using these ligands, aldehyde products having comparable n/i ratios can be produced from 1-olefin feeds, such as propylene, and mixtures of isomeric linear olefins such as n-butenes.
  • the synthesis gas reactant mixture of H 2 and CO of the present process can be employed at varying pressures and in varying H 2 to CO ratios, preferably ranging from 0.67 to 15.
  • H 2 /CO ratios preferably ranging from 0.67 to 15.
  • the present high temperature process ooerates under conditions wherein the hydroformylation rate is directly rather than inversely proportional to the CO partial pressure. Additionally, the selectivity to the n- plus i-aldehyde products i.e. total aldehyde selectivity is significantly increased at higher CO partial pressures.
  • the increased CO partial pressure significantly reduces the rate of l-olefin isomerization to the more stable, but less reactive internal olefins.
  • Increased CO partial pressure is particularly important in the hydroformylation of C 4 and higher l-n-olefins.
  • a preferred range of CO partial pressures is between 25 and 500 psia.
  • a more preferred range is between 60 and 500 psia.
  • the partial pressure of hydrogen is usually not critical in the present process.
  • the preferred H 2 range is between 25 and 500 psia.
  • the total pressure is important to maintain sufficient dissolved olefin concentration in the liquid phase, thereby providing a satisfactory reaction rate.
  • An upper ceil ing of the total pressure is established in the continuous product flash-off process where the difficulties of product removal in the vapor phase increase with added pressure.
  • the range of total pressure in the present. process is from about 100 to a 1500 psia , preferably from 150 to 700 psia, more preferably from 250 to 500 psia.
  • the present hydroformylations are carried out at temperatures between about 120oC and 200°C, preferably between about 130°C and 200°C.
  • the high concentration of excess phosphine ligand and the high partial pressure of CO allow high temperature selective operation more preferably ranging from 140 to 200oC even from 150 to 200oC.
  • the selection of hydroformylation temperature depends on the molecular weight of the olefin feed and the preferred mode of operation. Higher temperatures are desired when higher olefins, such as C 4 and higher, are to be reacted to a high olefin conversion in a continuous product flash-off operation.
  • the present hydroformylation process is preferably carried out in the liquid state. The process can be operated batchwise, semicontinuously and continuously.
  • the reactor is charged with the triaryl phosphine, additional solvent and/or olefin and the rhodium catalyst complex or its precursor and brought to reaction condltions.
  • the reactants i.e., olefin, CO and H 2 are then introduced at the required pressure as the reaction proceeds.
  • the H 2 /CO ratio is kept approximately constant during the reaction by appropriate H 2 /CO feed.
  • some of the reaction mixture is removed when a certain olefin conversion is reached.
  • the products are then separated from this mixture, preferably in the vapor phase.
  • the rest is returned to the hydroformylation reactor.
  • products are continuously removed from the reactor in the liquid and/or in the gaseous state.
  • a continuous operation of the present process is preferred.
  • One mode of the continuous operation removes the product in the gas phase.
  • the product is removed in the liquid phase and then separated from the ligand/catalyst and reactants, the latter being returned to the reactor. Distillation is the preferred method for product separation.
  • the triarylphosphine ligand is less volatile than the product and remains in the distillation residue with the catalyst compiex and stabilizes the catalyst complex.
  • the triaryl phosphine can contain minor amounts of other t-phosphines such as alkyl diaryl phosphines.
  • the continuous product removal is in the gas phase, it is preferred to have a primary flash-off operation in which the product, condensation by-products, reactants and optionally some of the ligand and inert feed components are removed without fractionation.
  • This mixture is then cooled with or without a pressure drop to provide a crude separation of the product as a liquid condensate and a gaseous mixture of H 2 /CO for recirculation.
  • This condensate is then distilled, preferably at a reduced pressure to provide the pure product.
  • a potential overhead fraction of the distillation is unconverted olefin which can be returned to the reactor either as a gas or as a liquid.
  • a potential bottom fraction of the distillation is the triaryl phosphine ligand which can be recirculated to the reactor in the liquid phase.
  • the reactor volume is controlled by triarylphosphine ligand addition. Other factors determing the reactor volume are: the relative product formation and purge rates and the amount of the higher boiling by products. It is particularly suprising that while the amount of "trimer" by-products is sharply reduced in the present process, small amounts of other aldehyde derivatives are formed which are advantageously used as the main nonreactive solvent components.
  • the new solvent medium of the present process comprises monoalcohols, simple alkyl esters, acetals and branched aldehydes.
  • one aspect of the present invention defines an improved method for continuous hydroformylation with a catalyst system of improved stability and selectivity comprising reacting, dissolved C 2 to C 10 olefin i.e.
  • reaction maximun comprises a minimun of 1 mole per kg phosphorus equivalent of excess triaryl phosphine ligand as a catalyst stabilizer modifier and oxygenated solvents mainly comprising carboxylic acid esters of monohydric alcohols, free monohydric alcohols, acetals and branched aldehydes and wherein the reactants are continuously introduced into the liquid reaction mixture and at least some of the aldehyde products are continuously removed in the gas phase medium duri ⁇ g the reaction.
  • the improvement in the sta bility and selectivity is effected by an appropriate combination of high triarylphosphine concentration and increased CO partial pressure.
  • this process includes the recirculation of some unreacted feed and volatile by products, particularly, synthesis gas catalyst and ligand and wherein at least some of the aldehyde products are continuously removed, said improvement being effected by using an appropriately high H 2 /CO ratio in the range of about 2.5 to 10 and an appropriately high concentration of free triaryl phosphine as the major stabilizing component of the reaction mixture.
  • a unique advantage of the present process is that it can be operated at high temperatures without losing its selectivity and activity. The activity loss is typically less than 0.5% per day, preferably less than 0.3% per day.
  • the present invention provides an improved method for the continuous hydroformylation of butene-1 with a catalyst system of improved stability and selectivity comprising reacting a butene-1 feed with CO and H 2 in a homogeneous liquid phase medium at temperatures between about 120 and 160oC and at a total pressure in the range of 100 to 700 psi to selectively produce n-valeraldehyde in the presence of tris-triphenylphosphine rhodium carbonyl hydride complex catalyst free from halogen on the rhodiun wherein said reaction medium comprises a minimum of 2.2 mole per kg excess triphenylphosphine as a catalyst stabilizer modifier and oxygenated solvents comprising amyl alcohol, amyl propylheptanoate, valeraldehyde dlamyl acetal and propyl heptanal , wherein the reactants are continuously introduced Into the liquid reaction mixture and wherein some of the aldehyde products are continuously removed in the gas
  • triphenylphosphine and other triarylphosphine l igands of the present catalyst system must be essential ly free from halogen, especially chlorine. Chloride impurities were usually removed e.g. by washing a toluene solution of the ligand with 10% aqueous sodium hydroxide solution. Triphenylphosphine, and other crystalline triarylphosphine ligands were preferably purified e.g. from phosphine oxides, by recrystall ization from polar solvents such as C 1 to C 4 alcohols.
  • Chl oride free tris-triphenyl phosphine rhodiun carbonyl hydride and other triarylphosphine complexes were preferably prepared starting with acetyl acetonato rhodiun dicarbonyl or tetrakis-triaryl phosphine rhodium hydride; e.g.
  • both atmospheric and superatomospheric hydrogen readily provide the monocarbonyl hydride.
  • the tetrakis-phosphine hydride leads to the monocarbonyl hydride if atmospheric CO is used for a short period. Under CO pressure the dicarbonyl hydride is formed.
  • Beside triphenylphosphine compounds complexes of trifluorophenylphosphine, trimethoxyphenylphosphine, ortho and para- tritolylphosphine, bi s-chl orophenyl-phenylphosphine, bi s-diphenylphosphinobenzene, ortho-tolyl diphenyl phosphine and ortho-methoxyphenyl diphenyl phosphine were prepared.
  • isolati on of the crystal l ine carbonyl hydrides preferably ethanol ic soluti ons of the starti ng reactants were used. The products were crystal lized in the pure form as the reaction proceeded.
  • the compl exes were usual ly fai rly sol uble in toluene. Two per cent toluene solutions were readily prepared at room temperature in the absence of oxygen. Excess triaryl phosphine l igand had a stabil i zing effect.
  • NMR characteristics of the rhodium carbonyl hydride complexes of triphenylphosphine and other triarylphosphine ligands were determined to allow their structural characterization in solution and to predict their catalytic behavior. In general, these studies started with an about 3% solution in a 90/10 mixture of toluene and deuterotoluene of the monocarbonyl hydride compl ex. The solutions were placed into pressure NMR tubes equipped with Teflon values. Varying excess of triarylphosphine l igand and varying pressure of H 2 /CO were used. The mixtures were equilibriated fay shaking prior to study. NMR parameters were usual ly determined at -30°C.
  • the tris-triphenylphosphine rhodium monocarbonyl hydride has a 31 P chemical shift, of 38.7 ppm and a coupling constant, J p-Rh , of 153 cps.
  • the parameters of the bis-triphenylphoshine rhodiun monocarbonyl hydride are : ⁇ 34.8 ppm; J p-Rh , 137 cps.
  • the hydroformylation of 1-butene to provide linear pentanal and branched 2-methyl -butanal products was selected as the main reaction for the study of the present process.
  • the main triaryl phosphine catalyst l igand empl oyed was triphenyl phosphine.
  • a 300 ml Hastelloy autoclave was used. The autoclave was equipped with baffl es and a highly effective, impeller type sti rrer. During the experimental runs, the sti rrer was operated at 1500 rpm.
  • the H 2 /CO reactant was introduced into the liquid reaction mixture at the bottom, close to the stirrer through a sintered inductor to assure small bubble size and instantaneous mixing.
  • catalyst precursors pure, halide free rhodium dicarbonyl acetylacetonate, RhAcac(CO) 2 , from Engelhard Industries, and triphenylphosphine, from Aldrich Chemical Co., Inc., were used. These precursors reacted readily and, in the presence of hydrogen, were converted to the desired tris-phosphine rhodium complex.
  • the amount of the rhodium complex used provided 5 x 10 -4 mole/liter, 0.5 mM, rhodium concentration after the addition of the olefin reactant in the starting reaction mixture. This corresponds to about 54 ppm Rh, or 54 mg Rh per kg.
  • the autoclave could be closed after the addition of the ligand. With higher ligand quantitles, the prior heating of the autoclave under N 2 to produce a liquid mixture was necessary. The charged autoclave was closed, flushed by nitrogen and heated to the reaction temperature.
  • the olefin reactant usually 1-butene
  • the initial gas was added until a total pressure of 2500 kPa was reached.
  • the autoclave was then connected to the approximately 1 to 1 H 2 /CO run gas provided at the same pressure. Up to this point, the autoclave was not stirred to avoid reaction. On starting the stirrer, the hydroformylation proceeded without any induction period.
  • Synthesis gas feed was provided at the bottom of the reactor, through a pressure regulating valve. This valve was set to maintain the starting pressure, usually 2500 kPa.
  • H 2 /CO ratio of the feed gas was varied from 50/50 to 56/44 to maintain the initial H 2 /CO ratio in the autoclave.
  • H 2 /CO ratios above one were required to maintain the initial H 2 /CO ratios. This was, in part, due to the hydrogenation side reaction of the olefin. The other factor was the decreasing 1-butene partial pressure during the reaction.
  • Higher H 2 /CO feed ratios were needed at the higher reaction temperatures, apparently due to the increased relative rate of olefin hydrogenation and increased butene partial pressure.
  • the present hydroformy!ations were run at approximately constant H 2 /CO rate, i.e. constant pCO, in a manner distinct above all the known batch processes of the prior art.
  • the progress of the hydroformylation was followed on the basis of the amount of 1:1 CO/H 2 consumed. The latter was calculated on the basis of the pressure drop in a 1 liter CO/H 2 cylinder. Reactant conversion, calculated on the basis of CO consumption, was plotted against the reaction time to determine the reaction rate. The reaction rate was expressed as the fraction of the theoretical CO/H 2 requirement consumed per minute
  • the final H 2 /CO ratio was thus determined using a Carle 111 H gas chromatograph.
  • the cold residual liquid was analyzed after opening the autoclave.
  • the overall analysis of the liquids was carried out using a Hewlett Packard 5840 gas chromatograph.
  • An SP 2100 column and a flame ionization detector were used.
  • the more volatile hydrocarbon components were determined as a group.
  • the individual higher boiling aldehydes and other compounds were separated. Due to the lower response of this detector to aldehydes, the intensity of the hydrocarbon peaks was multiplied by a factor of 0.7 to obtain the relative weight percentages of hydrocarbon by products versus aldehydes.
  • n- and i- aldehyde isomers were usually well separated to allow a quantitative determination of the n/i ratios.
  • the Individual volatile hydrocarbons were separated by the Carle111 H chromatograph system. The first column of this system retained the higher boiling components of the liquid sample. The hydrocarbon components of the exiting gases were separated on another column and determined by a thermal conductivity detector.
  • the results of the 1-butene hydroformylation studies will be presented and discussed mainly to show three factors in rhodium hydroformylation. These factors are the concentration of the excess Ph 3 P ligand, the temperature of the reaction mixture and the partial pressure of CO reactant.
  • reaction rate showed a simple first order relationship in the olefin reactant and the rhodium catalyst concentration. Neither the olefin nor the rhodium concentration affected the selectivity of the reaction. The observed rates showed an excellent rate correlation with the rhodium concentration. Therefore, rates normalized for 1 M rhodium concentration could be used to compare catalyst activities.
  • Triphenyl phosphine rhodium complex catalyst systems were studied in 2-ethylhexyl acetate solvent.
  • the triphenylphosphine concentration was 0.14 and 0.56 FT, i.e.4.7 and 18.5 wt. by wt%, in the solvent.
  • the previously described standard batch hydroformylation procedure was used with a 5/1 H 2 /CO reactant ratio under 350 psia (about 2500 kPa) pressure at temperatures ranging from 115 to 160°C.
  • the rhodium concentration was varied from 0.1 to 0.25 to achieve 50% olefin conversion between 8 and 28. minutes reaction time.
  • the work was aimed at determining the effect of the Ph 3 P concentration at different temperatures. The data obtained are shown by Table I.
  • Example Nos. 24-27 shows an extension of determining the effect of double 5/1 H 2 /CO pressure. These experiments were carried out at 145 or 160oC.
  • Example Nos. 24-31 shows the effect of changing H 2 /CO ratios at a total pressure of 2500 kPa (350 psia) and a reaction temperature of 145oC.
  • Ph 3 P concentration (for comparison see Table II, Example Nos. 22 to 25).
  • Table III The second group of experiments of Table III (Example Nos. 30-33) shows that, at constant pressure, the ratio of H 2 /CO has a complex effect on the rate. In contrast, a consistent decrease of n/i ratio and increase of the percentage of n + i aldehydes is observed when the H 2 /CO ratio is dropped from 5 to 0.1.
  • the normalized reaction rate Is substantially Increased, from 92 to 128, as the H 2 /CO ratio is decreased from 5 to 1.5 (Example Nos. 28, 30, and 31). This decrease of H 2 /CO ratio corresponds to an Increase of CO partial pressure from 417 to 1000 kPa as it is shown by the table.
  • the data show that surprisingly lower n/i ratios of the aldehyde products are obtained with propylene than with 1-butene.
  • the effects of process parameters are qualitatively similar.
  • the high triphenylphosphine concentrations of the present high temperature process are particularly required to provide the desired high n/i ratios butyraldehydes.
  • the effect of temperature on rate acceleration is pronounced without any significant adverse effect on selectivity.
  • the effect of doubled pressure which increases the pCO from about 1250 kPa (175 psia) to about 2500 kPa (350 psia), also results in definite rate acceleration.
  • the adverse effect of increased pCO on the n/i ratio is minimized at the maximum Ph 3 P concentration (Example 54).
  • 1-Octene was hydroformylated in two experiments at 350 psi in the manner described in the previous examples.
  • the starting solvent catalyst mixture contained 59% (2.2 ) of triphenyl phosphine and 5 mM acetyl acetonato dicarbonyl rhodium.
  • the 1-octene reactant (20 g) was pressured into the mixture by CO/H 2 at the reaction temperature, i.e., at 155°C.
  • Example 63 a 5/1 H 2 /CO ratio of initial feed was used while a 1/1 H 2 /CO feed was empl oyed in Example 64. In both cases, a run gas of 54/46 H 2 /CO was used.
  • Example 65 (Run No. 839) , a mixture of 1- and 2- butenes was hydroformy! ated to a 25% conversion of the total butenes.
  • the normalized rate constant at 1 M Rh was 110, an expected value on the basis of the concentration of the 1-butene component.
  • the starting mixture of the olefin reactants and the remaining dissolved hydrocarbons in the final reaction mixture were analysed for isomer distribution.
  • the percentages of isomeric butenes were the following: Composition of 1 -butene cis-2-butene trans-2-butene Reactants 46.3 21 .2 30.3 Unreacted Reactants 27.7 30.3 44.0
  • Example 66 (Run No. 826) , an approximately equimolar mixture of 1-,2- and i-butenes was similarly hydroformy! ated. However, in this case the reaction was carried out to 25% conversion of all the butenes, i .e. only slightly less than the approximate percentage of the 1-butene in the reactant mixture. In contrast to the previous example, the rate of the reaction was not maintained throughout the experiment, but dropped to about half of the initial rate.
  • the concentration of the highly reactive 1-butene because too low.
  • the 2-butenes and some of the i-butene also reacted but at a low rate.
  • the comparative percentages of the isomers of the reactant and unreacted butenes were the following: Composition of 1 -butene 2-butenes i -butene
  • n/i ratio of the aldehyde products was only 3.9.
  • the tri phenyl phoshine rhodium complex catalyst system was used at a rhodium concentration of 0.25 mM (25 ppm) and 0.05 mM (5 ppm), respectively.
  • the triphenylphosphine concentration was (32.9%) in the solvent) in both experiments,
  • the reactions were carried out at 145oC at total pressures of 2500 kPa (350 psia) and 1250 kPa (175 psia), respectively.
  • Example 67 (Run No. 789), the reaction was run at a 5/1 H 2 /CO reactant ratio using a feed gas ratio of 53/47. At the 0.25 m Rh concentration, 50% conversion was reached in 90 seconds. On this basis, the normalized rate constant of this reaction is 2500, an extremely high value.
  • n + i aldehyde selectivity was 77.1%.
  • the n/i ratio was 5.8.
  • the main side reaction was isomerization to internal ci s-and trans- olefinic derivatives:
  • Example 68 (Run No. 803) , lower rhodium concentration (0.025 mM) and lower pressure (1250 kPa) were used with 1/1 H 2 /CO ratio and 51/49 feed. The reaction was nevertheless very fast. It took 10 minutes to reach 50% conversion. The normal ized rate was about 1480. Analyses of the reaction mixture indicated generally improved selectivity percentages: n + i , 92.2; n/i, 5.9; isomerization, 7.5; hydrogenation, 0.3. Thus the results indicate a highly unusual but generally advantageous behavior for oxygen substituted olefins in the present process.
  • 1-Butene was also selectively hydroformylated in the present high temperature process using catalyst systems based on rhodium complexes of substituted triphenylphosphine liquids as follows: trifluorophenylphosphine, trimethoxyphenyl phosphine ortho- and para-trltolylphosphine, bis- chlorophenyl-phenylphosphine, bis-diphenylphosphino-benzene, orthotolyl diphenyl phosphine, ortho-methoxy diphenyl phosphine.
  • the excess triphenylphosphine concentration was further increased.
  • the added timer solvent and aldehyde recycle were eliminated. This resulted not only in a stable PFO operation but in a different catalyst system containing unexpectedly advantageous oxygenated compounds.
  • the two liter reactor was charged with a warm, 930 ml toluene solution of about 524g (2 moles) of triphenylphosphine and 2.34 g (10 mllimoles) of rhodium dicarbonyl acetylacetonate.
  • the reaction was run at 140oC under a total pressure of 1275 kPa (185 psia).
  • the reactants were introduced at the following feed rates in moles per hour: 1-butene, 2.95; H 2 , 21.2 and CO, 7.18.
  • the large excess of synthesis gas feed acted as a plentiful purge gas to minimize the aldehyde concentration.
  • the toluene component of the reaction mixture was flashed off together with most of the valeraldehydes formed in the catalyst system. Some of the valeraldehydes remained as reactive sol vent components. Surprisingly, they formed monohydric alcohol s
  • the results show that 1-butene feed conversion and aldehyde production was ful ly maintained for 160 hours.
  • the selectivity of the catalyst system was also analyzed and is shown in Table XI. The results show that both the total aldehyde percentage and the n/i aldehyde ratio remained essentially constant. The selectivity to hydrocarbon by-products 1n this run is high, due to the relatively low CO partial pressure (255 kPa, i .e. , 37 psi a).
  • the composition of the residual catalyst system was analyzed by gas chromatography. The approximate total weight of the system was about 500 g, indicating a highly efficient flash-off operation.
  • the residual catalyst system contained only about 0.5% of n-butyl diphenylphosphine and n-pentyl diphenylphosphine degradation products of triphenylphosphine.
  • the distillate product had in the range of 1-2 ppm of the same conversion products. Therefore, it is estimated that in a month operation only about 2.5-3% of the triphenylphosphine ligand is converted to alkyl diphenyl phosphines. Also, some of the triphenylphosphine is flashed off, there is about 15 ppm Ph 3 P in the distillate product.
  • the oxygenated solvent components formed in the continuous process described in the previous example were studied by combined gas chromatography and mass spectroscopy. These GC/MS studies with the help of authentic compounds resulted in the structural identification of most of the components.
  • the starting material for this work was a distillate product obtained during the second day of the PFO operation. The product was concentrated 62 fold by fractional distillation to remove the hydrocarbons and valeraldehydes. The remaining "heavies" were then analyzed by GC/MS. The reconstructed ion chromatogram of the components is shown by Figure 8, together with the fdentlfication of the major components. It is noted that n-pentanol constitutes about 56% of the oxygenates of this mixture.
  • 2-Propylheptanal is second in amount with about 7%.
  • the less volatile C 15 valeraldehydes diamyl acetal and the three isomeric C 15 monocarboxylic add esters are smaller components In the range of 1%. Only traces of the Isomeric trimers of the prior art were detected. None of the tetramer was found. Thus these studies showed the different character of the present system.
  • the n/i ratio of the aldehyde product was about 3.4 and remained about constant.
  • the total aldehyde selectivity was low, about 53%.
  • the main by-product was butane with a selectivity of 26%.
  • the alcohol selectivity was also high, 8%; presumably due to the high rhodium concentration.
  • the total pressure was doubled, the other operational parameters stayed the same.
  • the increased pressure resulted in an increased aldehyde production rate, about 70 g/hr, and improved activity maintenance.
  • the total aldehyde selectivity was also improved to about 65%.
  • the n/i ratio dropped to 1.1, apparently due to the increased CO partial pressure.

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Abstract

Certains complexes d'hydrure de carbonyle de triarylphosphine rhodium (I) et (II) sont des catalyseurs sélectifs et stables pour l'hydroformylation à haute température des oléfines. Les facteurs critiques sont le maintien d'une pression partielle de CO suffisante, supérieure à 25 psia, ainsi qu'une concentration fortement excédentaire par ligand de triarylphosphine, à un minimum de 1 mole par kg. Afin d'obtenir un fort rapport entre les produits de n-aldéhyde et les produits i-aldéhyde de l'hydroformylation de 1-oléfine, on rend la concentration du complexe tris-phosphine (I) maximale. Dans une opération continue du présent procédé consistant dans le séchage instantané du produit, les principaux composants du solvant à point d'ébullition élevé sont les ligands de phosphine excédentaire, ainsi que les produits mono-alcool et et mono-ester dérivés. Un procédé combiné d'isomérization et d'hydroformylation est également décrit pour la conversion sélective d'oléfines linéaires internes en n-aldéhydes terminaux. Dans ce procédé, on rend la concentration du complexe bis-phosphine (II) minimale. On rend par contraste la concentration du complexe bis-phosphine maximale dans un procédé convertissant des oléfines linéaires internes en i-aldéhydes ramifiés correspondants.
PCT/US1984/000423 1983-03-16 1984-03-16 Hydroformylation a haute temperature WO1984003697A1 (fr)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
WO1988000179A2 (fr) * 1986-07-01 1988-01-14 Davy Mckee (London) Limited Procede de production d'aldehydes par hydroformylation
EP0659725A1 (fr) * 1993-12-23 1995-06-28 Hoechst Aktiengesellschaft Procédé pour la préparation d'aldehydes substitués par un radical alkyl en position alpha
WO2002020448A1 (fr) * 2000-09-05 2002-03-14 Dynea Chemicals Oy Procédé d'hydroformylation d'alcènes
WO2008065171A1 (fr) * 2006-11-30 2008-06-05 Basf Se Procédé pour l'hydroformulation d'oléfines
CN114522740A (zh) * 2020-11-23 2022-05-24 中国科学院大连化学物理研究所 一种由醋酸乙烯酯制备3-乙酰氧基丙醇的方法
EP4161893A4 (fr) * 2020-06-05 2024-03-13 Scion Holdings LLC Production d'alcools
US11993565B2 (en) 2020-12-17 2024-05-28 SCION Holdings LLC Branched products

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US3965192A (en) * 1967-05-29 1976-06-22 Union Oil Company Of California Hydrocarbonylation process
GB1440413A (en) * 1973-09-21 1976-06-23 Mitsubishi Chem Ind Process for producing butyraldehydes
US4148830A (en) * 1975-03-07 1979-04-10 Union Carbide Corporation Hydroformylation of olefins
GB2077259A (en) * 1980-06-06 1981-12-16 Davy Mckee Oil & Chem Methacrylic Acid and its Esters

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US3965192A (en) * 1967-05-29 1976-06-22 Union Oil Company Of California Hydrocarbonylation process
DE1939322A1 (de) * 1968-08-02 1970-02-12 Johnson Matthey Co Ltd Hydroformylierungskatalysatoren
GB1440413A (en) * 1973-09-21 1976-06-23 Mitsubishi Chem Ind Process for producing butyraldehydes
US4148830A (en) * 1975-03-07 1979-04-10 Union Carbide Corporation Hydroformylation of olefins
GB2077259A (en) * 1980-06-06 1981-12-16 Davy Mckee Oil & Chem Methacrylic Acid and its Esters

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988000179A2 (fr) * 1986-07-01 1988-01-14 Davy Mckee (London) Limited Procede de production d'aldehydes par hydroformylation
WO1988000179A3 (fr) * 1986-07-01 1988-01-28 Davy Mckee London Procede de production d'aldehydes par hydroformylation
US5053551A (en) * 1986-07-01 1991-10-01 Davy Mckee (London) Limited Process for the production of aldehydes by hydroformylation
EP0659725A1 (fr) * 1993-12-23 1995-06-28 Hoechst Aktiengesellschaft Procédé pour la préparation d'aldehydes substitués par un radical alkyl en position alpha
CN1040100C (zh) * 1993-12-23 1998-10-07 赫彻斯特股份公司 α位被烷基取代的醛类的制备方法
WO2002020448A1 (fr) * 2000-09-05 2002-03-14 Dynea Chemicals Oy Procédé d'hydroformylation d'alcènes
WO2008065171A1 (fr) * 2006-11-30 2008-06-05 Basf Se Procédé pour l'hydroformulation d'oléfines
JP2010511015A (ja) * 2006-11-30 2010-04-08 ビーエーエスエフ ソシエタス・ヨーロピア オレフィンのヒドロホルミル化法
CN101600674B (zh) * 2006-11-30 2013-09-11 巴斯夫欧洲公司 烯烃的加氢甲酰化方法
KR101495929B1 (ko) * 2006-11-30 2015-02-25 바스프 에스이 올레핀의 하이드로포르밀화 방법
US9266808B2 (en) 2006-11-30 2016-02-23 Basf Se Method for the hydroformylation of olefins
EP4161893A4 (fr) * 2020-06-05 2024-03-13 Scion Holdings LLC Production d'alcools
CN114522740A (zh) * 2020-11-23 2022-05-24 中国科学院大连化学物理研究所 一种由醋酸乙烯酯制备3-乙酰氧基丙醇的方法
CN114522740B (zh) * 2020-11-23 2023-10-13 中国科学院大连化学物理研究所 一种由醋酸乙烯酯制备3-乙酰氧基丙醇的方法
US11993565B2 (en) 2020-12-17 2024-05-28 SCION Holdings LLC Branched products

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