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WO2017078972A1 - Procédé amélioré d'hydroformylation - Google Patents

Procédé amélioré d'hydroformylation Download PDF

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Publication number
WO2017078972A1
WO2017078972A1 PCT/US2016/058618 US2016058618W WO2017078972A1 WO 2017078972 A1 WO2017078972 A1 WO 2017078972A1 US 2016058618 W US2016058618 W US 2016058618W WO 2017078972 A1 WO2017078972 A1 WO 2017078972A1
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Prior art keywords
hydroformylation
process according
solvent
critical
petroleum gas
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Padmesh Venkitasubramanian
Gustavo DASSORI
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Archer Daniels Midland Co
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Archer Daniels Midland 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
    • 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
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • 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

  • the present invention broadly relates to processes for the
  • the present invention relates to a single solvent hydroformylation process of the type described in US 8,822,734 to Subramaniam et al. (hereafter, "Subramaniam et al.”).
  • Hydroformylation processes wherein unsaturated compounds are reacted with carbon monoxide and hydrogen to form carbonyl compounds, are well known.
  • One commercially important use of hydroformylation is in oxo synthesis, wherein olefins are hydroformylated to aldehydes, which in turn are commonly hydrogenated or undergo aldol condensation and hydrogenation to produce oxo alcohols such as n-butanol, 2-ethylhexanol, isononyl alcohol, isodecyl alcohol and the like.
  • Subramaniam et al. is concerned with another commercially important application of hydroformylation, namely, in the manufacture of 1,4-butanediol ("BDO") by the hydroformylation of allyl alcohol to 4-hydroxybutyraldehyde (“HBA”) and its branched isomer 4-hydroxy-2-methylpropionaldehyde (“HMPA”), followed by hydrogenation of the HBA to provide BDO.
  • BDO 1,4-butanediol
  • HBA 4-hydroxybutyraldehyde
  • HMPA 4-hydroxy-2-methylpropionaldehyde
  • the demand for this product is much more limited as compared to BDO so that a number of efforts have been made to developing catalysts and related processes that are more selective to the linear HBA product.
  • Rhodium catalysts came into favor for their improved selectivity beginning in approximately the late 1970s, and the need to avoid rhodium losses and to recover and reuse as much of the rhodium employed in these complexed rhodium carbonyl catalysts was quickly appreciated.
  • GB 2055367 to Cornils et al and assigned to Ruhrchemie Aktiengesellschaft published March 4, 1981
  • "a whole series of methods" had already been described for recovering active rhodium catalyst from residues of an oxo synthesis with complexed rhodium carbonyl catalysts.
  • the present invention in one aspect relates to an improved hydroformylation process of a type otherwise described in Subramaniam et al., wherein a compressed petroleum gas-expanded liquid is used as a solvent for an olefinic hydroformylation feed to a reactor, but wherein the improvement resides in the addition of a small amount of a second organic solvent for the complexed, homogeneous rhodium carbonyl catalyst, as well as in the combination of the crude hydroformylation product with an amount of water for extracting the aldehyde products of the
  • substantially all (meaning 95% or more) of the aldehyde products are extracted from an organic portion of the combination comprised of the compressed petroleum gas-expanded liquid and second organic solvent into an aqueous portion of the combination.
  • substantially all (95% or more) of the complexed, homogeneous rhodium catalyst remains with the organic portion.
  • an aqueous phase is produced containing the aldehyde hydroformylation products and is withdrawn, while the organic phase that results is in one embodiment recycled back to the reactor while maintaining sufficient pressure in the settling vessel to keep the petroleum gas as a liquid.
  • a depressurization takes place in the settling vessel so that the petroleum gas returns to a gaseous state before being recompressed for recycle to the reactor as a liquefied petroleum gas.
  • the invention concerns a process for hydroformylating an olefinic feedstock, comprising:
  • hydroformylation product mixture to separate into an aqueous phase comprising water and aldehyde products of the hydroformylation and an organic phase comprising at least second organic solvent and complexed, homogeneous rhodium carbonyl
  • step a) additionally comprises compressed near- critical petroleum gas solvent.
  • the aqueous phase contains 95 percent or more of the aldehyde products of the hydroformylation.
  • the organic phase contains 95 percent or more of the complexed, homogeneous rhodium carbonyl hydroformylation catalyst.
  • the olefinic feedstock is allyl alcohol.
  • the compressed near-critical petroleum gas solvent is a mixture of compressed petroleum gases.
  • the compressed near-critical petroleum gas solvent is propane or butane.
  • the compressed near-critical petroleum gas solvent is propane.
  • the second organic solvent is selected from the group consisting of one or more of methyl octanoate, tetralin, 1-octanol, n-hexane, biodiesel and methyl palmitate.
  • the second organic solvent is selected to be tetralin, 1-octanol or a mixture of these.
  • the second organic solvent is 1-octanol.
  • the olefinic feedstock is allyl alcohol
  • the aqueous phase contains 95 percent or more of the HBA and HMPA products of hydroformylating the allyl alcohol feedstock and further wherein the organic phase contains 95 percent or more of the complexed, homogeneous rhodium carbonyl hydroformylation catalyst.
  • At least 98 percent of the hydroformylation catalyst is recycled back to step a) in the organic phase.
  • At least 99 percent of the hydroformylation catalyst is recycled back to step a) in the organic phase.
  • hydroformylation catalyst is recycled back to step a) in the organic phase.
  • Figure 1 is a partial schematic of a process of the present invention in one embodiment.
  • Figure 2 is a partial schematic of a process of the present invention in an alternative embodiment.
  • Allyl alcohol is supplied in feed 12a to a reaction vessel 14, wherein the allyl alcohol 12a is combined with carbon monoxide and hydrogen from syngas makeup 12b and from recycled, unconverted carbon monoxide and hydrogen in recycle stream 12c.
  • a compressed petroleum gas preferably in the form of liquefied petroleum gas (or LPG, CAS 68476-85-7), a liquefied gas from among those found in LPG or a liquefied mixture of gases found in LPG, is initially supplied to the reaction vessel 14 and resupplied in a continuous loop in organic phase recycle stream 16.
  • Propane and butane are more preferred petroleum gases, and dense propane is especially preferred, as used and exemplified in Subramaniam et al.
  • the allyl alcohol is hydroformylated in the reaction vessel 14 to provide 4-hydroxybutyraldehyde (“HBA”) and its branched isomer 4-hydroxy-2- methylpropionaldehyde (“HMPA”), using the compressed petroleum gas-expanded solvent and the complexed, homogeneous rhodium carbonyl catalyst and in a manner described more fully in Subramaniam et al.
  • HBA 4-hydroxybutyraldehyde
  • HMPA 4-hydroxy-2- methylpropionaldehyde
  • hydroformylation is well known in the art as a catalytic method for the conversion of an olefin into an aldehyde product having one carbon more than the starting olefin, by the addition of one molecule each of hydrogen and carbon monoxide to the carbon-carbon double bond. If the organic substrate contains more than one carbon-carbon double bond, more than one formyl group can be added to the substrate, thereby increasing the number of carbon atoms contained in the product molecule by more than one.
  • CGXLs compressed gas-expanded liquids
  • Such compressed gas-expanded liquids may be understood as a continuum of compressible media generated when various amounts of a compressed dense phase gas are added to a liquid to be expanded.
  • CGXLs provide a number of benefits in the context of carrying out certain chemical conversions such as the contemplated hydroformylation of allyl alcohol.
  • the reactant gases may be more fully and readily dissolved in the expanded liquid phase, thus enabling increased rates of reaction and milder conditions to be used generally, the higher hydrogen to carbon monoxide ratios made possible by Subramaniam et al' s dense petroleum gas process are desirable for avoiding an inhibitory effect with higher amounts of carbon monoxide and for tuning the process to achieve a desired product regioselectivity, under milder conditions and at lower system pressures.
  • a product ratio of the linear, n-aldehyde HBA to the branched, iso-aldehyde HMPA of 3 to 1, more preferably 8 to 1, and most preferably 10 to 1 will be possible, with a targeted chemoselectivity preferably greater than 70%, more preferably greater than 80%, and most preferably greater than 90%.
  • chemoselectivity refers to the moles of aldehydes or the allyl alcohol isomers (e.g., propionaldehyde) or hydrogenated derivatives (e.g., propanol) formed relative to the moles of substrate (e.g., allyl alcohol) converted during the hydroformylation process.
  • the dense propane preferably has a volume fraction in the liquid phase between 5% and 98%. In another aspect, more than 50% of the liquid phase volume is preferably replaced with the dense propane, more preferably replacing 80% or more and most preferably 95% or more of the liquid phase volume.
  • the reaction occurs at relatively mild temperatures and pressures.
  • temperatures of 80 degrees Celsius or less and especially 70 degrees Celsius or less are contemplated, with pressures overall from 5 MPa and lower and especially 4 MPa and lower.
  • Typical temperatures range between 50°C and 70°C, and typical pressures are less than 5 MPa, with pressures between 3 and 4 MPa being exemplary.
  • product regioselectivities (where "regioselectivity” or “n/i” refers to the ratio of linear to branched aldehydes in the hydroformylation product composition) and chemoselectivities can vary based on the pressures of syngas used versus of the dense gas serving both as a liquid expansion medium and as a solvent/diluent for the allyl alcohol substrate, and further based on the overall concentration or amount of the allyl alcohol supplied to be hydroformylated.
  • a liquefiable petroleum gas such as propane in a near critical state as the solvent/diluent for the allyl alcohol - so that the liquefiable petroleum gas (propane) readily transitions from a gaseous condition under ambient pressure and temperature conditions to being a liquid with modest cooling and compression, and from a liquid back to its ambient gaseous state with a release of pressure - then as allyl alcohol, carbon monoxide and hydrogen are respectively provided to a reactor 14 by means of allyl alcohol feed 12a and by means of synthesis gas makeup 12b and via unconverted carbon monoxide and hydrogen in recycle stream 12c and caused to react therein in the presence of a hydroformylation catalyst, recovery of the liquefiable petroleum gas from
  • hydroformylation product was described by Subramaniam et al. as accomplished by merely releasing superatmospheric pressure from the hydroformylation product.
  • the hydroformylation catalyst contemplated by Subramaniam et al. and preferred for use herein broadly comprises a transition metal capable of catalyzing the hydroformylation of an olefinic feed such as allyl alcohol, and may additionally contain labile ligands which are either displaced during the catalytic reaction, or take an active part in the catalytic transformation.
  • the preferred transition metals are those comprising Group 8 of the Periodic Table.
  • the preferred metals for hydroformylation are rhodium, cobalt, iridium, ruthenium, palladium, and platinum.
  • the Group 8 metal is still more preferably rhodium.
  • the amount of rhodium in the liquid reaction mixture can vary, but is generally from 10 to 500 ppm by weight, preferably from 30 to 350 ppm by weight and particularly preferably from 50 to 300 ppm by weight.
  • Group 8 catalysts suitable for hydroformylation can be prepared or generated according to techniques well known in the art, as described, for example, in WO 95 30680, U.S. Pat. No. 3,907,847; and J. Amer. Chem. Soc, 115, 2066 (1993).
  • Suitable Group 8 metal compounds are hydrides, halides, organic acid salts, acetylacetonates, inorganic acid salts, oxides, carbonyl compounds and amine compounds of these metals.
  • Preferred salts include, for example, rhodium salts such as rhodium acetate, rhodium chloride or rhodium nitrate, rhodium complexes such as rhodium acetyl acetonate and/or rhodium carbonyl compounds.
  • the catalyst may be achiral or chiral.
  • the ligands can be monodentate or polydentate, and in the case of chiral ligands, either the racemate or one enantiomer or diastereomer can be used.
  • Preferred ligands are ligands which contain nitrogen, phosphorus, arsenic, or antimony as donor atoms; particular preference is given to phosphorus-containing ligands, such as phosphines, phosphine oxides, phosphinanes, phosphinines, phosphinites, phosphites, and phosphonites.
  • phosphines are triphenylphosphine, tris(p-tolyl)phosphine, tris(m-tolyl)phosphine, tris(o-tolyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(p- fluorophenyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p- dimethylaminophenyl)phosphine, ethyldiphenylphosphine, propyldiphenylphosphine, t- butyldiphenylphosphine, n-butyldiphenylphosphine, n-hexyldiphenylphosphine, c- hexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tricyclopenty
  • phosphinanes examples include 2,6-bis(2,4-dimethylphenyl)-l-octyl- 4-phenylphosphinane, l-octyl-2,4,6-triphenylphosphinane and further ligands described in WO 02/00669.
  • phosphinines examples include 2,6-dimethyl-4-phenylphosphinine, 2,6-bis(2,4-dimethylphenyl)-4-phenylphosphinine and also further ligands described in WO 00/55164.
  • Examples of phosphites are trimethyl phosphite, triethyl phosphite, tri-n- propyl phosphite, tri-i-propyl phosphite, tri-n-butyl phosphite, tri-i-butyl phosphite, tri-t- butyl phosphite, tris(2-ethylhexyl)phosphite, triphenyl phosphite, tris(2,4-di-t- butylphenyl)phosphite, tris(2-t-butyl-4-methoxyphenyl)phosphite, tris(2-t-butyl-4- methylphenyl)phosphite, tris(p-cresyl)phosphite.
  • Triphenyl phosphites which are substituted by 1 or 2 isopropyl and/or tert- butyl groups on the phenyl rings, preferably in the ortho position relative to the phosphite ester group, are preferably used.
  • Bisphosphite ligands which are described, inter alia, in EP 1 099 677; EP 1 099 678; WO 02.00670; JP 10279587; EP 472017; WO 01/21627; WO 97/40001; WO 97/40002; U.S. Pat. No. 4,769,498; EP 213639; and EP 214622, are particularly preferably used.
  • Customary phosphinite ligands are described, inter alia, in U.S. Pat. No. 5,710,344; WO 95 06627; U.S. Pat. No. 5,360,938; and JP 07082281.
  • Examples are diphenyl(phenoxy)phosphine and its derivatives in which all or some of the hydrogen atoms are replaced by alkyl or aryl radicals or halogen atoms, diphenyl(methoxy)phosphine, diphenyl(ethoxy)phosphine, etc.
  • Examples of phosphonites are methyldiethoxyphosphine, phenyldimethoxyphosphine, phenyldiphenoxyphosphine, 6-phenoxy-6H-dibenz[c,e] [l,2]oxaphosphorin and their derivatives in which all or some of the hydrogen atoms are replaced by alkyl or aryl radicals or halogen atoms and ligands as described in WO 98/43935; JP 09-268152; and DE 198 10 794, and in the German patent applications DE 199 54 721 and DE 199 54 510.
  • rhodium catalysts include RhCb, Rh(N0 3 ) 3 , Rh(OAc) 3 , Rh 2 0 3 , Rh(acac)(CO) 2 , [Rh(OAc)(COD)] 2 , Rh 4 (CO)i 2 , Rh 6 (CO)i 6 , RhH(CO)(Ph 3 P) 3 , [Rh(OAc)(CO) 2 ], [RhCl(COD)] 2 , Rh(CO) 2 (acac), Rh(CO) 2 (C 4 H 9 COCHCO-t-C 4 H 9 ), Rh 2 0 3 , Rh(0 2 CCH 3 ) 2 , and Rh(2-ethylhexanoate), wherein "acac” is an acetyl acetonate group; "OAc” is an acetyl group; “COD” is 1,5-cyclooctadiene; "Ph” is a phenyl
  • phase transition switch whereby reactions are performed homogeneously, following which the catalysts are recovered from the product stream via phase transition triggered by a change in either the system temperature ⁇ see Horvath et al., Facile catalyst separation without water: fluorous biphasic hydroformylation of olefins, Science 266 (5182) 72-75 (1994); Zheng et al., Thermoregulated phase transfer ligands and catalysis. III.
  • Rh homogeneous rhodium
  • zeolites see Mukhopadhyay et al., Encapsulated HRh(CO)-(PPli3) 3 in microporous and mesoporous supports: novel heterogeneous catalysts for hydroformylation, Chemical Materials 15 1766-1777 (2003)), nanotubes (see Yoon et al., Rh-based olefin hydroformylation catalysts and the change of their catalytic activity depending on the size of immobilizing supporters, Inorganica Chimica Acta.
  • SAPC supported aqueous phase catalysis
  • SAPC supported aqueous phase catalysis
  • polymers see Lu et al., Hydroformylation reactions with recyclable rhodium complexed dendrimers on a resin, Journal of American Chemical Society 125 13126-13131 (2003) and Lopez et al., Evaluation of polymer-supported rhodium catalysts in 1-octene hydroformylation in supercritical carbon dioxide, Industrial & Engineering Chemistry Research 42 3893-3899 (2003)), and smectite, especially montmorillonite, clays wherein the rhodium or other transition metal catalyst is intercalated into the clay (see Lee and Alper, Regioselective hydroformylation of allyl acetates catalyzed by rhodium-montmorillon
  • Subramaniam et al's preferred approach to the problem involved the use of soluble polymer-supported rhodium catalysts having a narrow molecular weight distribution as prepared according to WO2010/057099A1, which could be retained within Subramaniam et al's hydroformylation reactor by use of a nanofiltration membrane substantially as described in the WO'099 publication. Leaching of rhodium was to be counteracted by binding the Rh to the polymer support in a multidentate fashion. Targeted losses of the transition metal were described as preferably being less than 10%, still more preferably being less than 5%, and most preferably being less than 2%.
  • the improved hydroformylation process of the present invention seeks to substantially reduce losses of the preferred but costly rhodium catalyst to at least a comparable degree, but preferably to a greater degree.
  • rhodium losses will be no greater than 2 percent, more preferably will be 1 percent and less and still more preferably will approach 0.5 percent and less - while still benefiting from Subramaniam et al's use of a compressed, near-critical petroleum gas solvent for the allyl alcohol.
  • the improved hydroformylation process of the present invention accomplishes this objective by the addition of preferably just enough of a second organic solvent to dissolve the hydroformylation catalyst, and further through the addition of water to effect a separation of the HBA and HMPA hydroformylation products from allyl alcohol into an aqueous phase, with the compressed, near-critical petroleum gas solvent, the second organic solvent and hydroformylation catalyst forming an organic phase.
  • reaction vessel 14 Following the hydroformylation of the allyl alcohol 12a in reaction vessel 14 to provide hydroformylation products inclusive of HBA and HMPA, the contents of reaction vessel 14 are transferred in line 20 to settling vessel 18 along with a volume of water (shown by stream 22) into which the HBA and HMPA will effectively partition.
  • settling vessel 18 a volume of water (shown by stream 22) into which the HBA and HMPA will effectively partition.
  • at least 90 percent of the desired HBA and HMPA hydroformylation products will be separated into an aqueous phase in this manner, though more preferably at least 95 percent of the HBA and HMPA will be separated into the aqueous phase and still more preferably at least 98 percent of the HBA and HMPA hydroformylation products formed in reaction vessel 14 will be partitioned into an aqueous phase.
  • the contents of the reaction vessel 14 and the water added via stream 22 are very thoroughly intermixed in the transfer line 20 so that the HBA and HMPA are thoroughly and quickly extracted into the water.
  • this mixing can be accomplished by the manner in which the water in stream 22 is introduced into the transfer line 20, for example, through nozzles, valves and the like, while in other embodiments in-line mixing devices (for example, interfacial surface generator s/static mixers) may be used.
  • in-line mixing devices for example, interfacial surface generator s/static mixers
  • Those skilled in the art will be well able in any event to accomplish the thorough intermixing that is desired before the settling vessel 18.
  • aqueous phase 24 comprising the HBA and HMPA hydroformylation products
  • organic phase 26 comprising the compressed near critical petroleum gas solvent, the small amount of the second organic solvent for keeping the complexed, homogeneous rhodium carbonyl hydroformylation catalyst in solution and the homogeneous rhodium carbonyl catalyst
  • gas phase 28 comprising unreacted carbon monoxide and hydrogen.
  • the aqueous phase 24 is then withdrawn for undertaking an aqueous phase hydrogenation of the aldehyde hydroformylation products, while the catalyst, compressed near-critical petroleum gas and second organic solvent in the organic phase 26 are recycled to reaction vessel 14 via stream 16, while maintaining sufficient pressure in the settling vessel 18 to keep the petroleum gas as a liquid. Unreacted carbon monoxide and hydrogen in the gas phase 28 are meanwhile recycled in recycle stream 12c as previously indicated.
  • aqueous phase hydrogenation of the HB A and HMPA in the aqueous phase 24 (not shown) produces 1,4-butanediol and 2-methyl-l,3 propanediol, which can then be separated by a simple distillation (also not shown).
  • Suitable catalysts for the aqueous phase hydrogenation would include Raney nickel or ruthenium on carbon.
  • the second organic solvent is preferably substantially immiscible with water, preferably having, for example, a solubility of less than 10 milligrams per liter in water at 20 degrees Celsius, while being at the same time an effective solvent for the complexed, homogeneous rhodium carbonyl hydroformylation catalyst and being highly miscible with the compressed, near critical petroleum gas solvent.
  • Preferred second organic solvents include tetralin (CAS 119-64-2), methyl octanoate (CAS 67762-39-4), methyl palmitate (CAS 112-39-0), n-hexane (CAS 110-54-3), biodiesel (for example, soy methyl esters, CAS 67784-80-9), 1-octanol (CAS 11-87-5) or a combination of any of these, with tetralin and 1-octanol being preferred and 1-octanol especially preferred.
  • the extraction with methyl palmitate would likely need to be conducted at a still- elevated temperature to prevent the methyl palmitate from solidifying, but generally the extraction with water supplied in stream 22 and the subsequent equilibration/settling in vessel 18 with the other second organic solvents need not be conducted at an elevated temperature.
  • the amount used of the second organic solvent will be at least that amount that will suffice to maintain the catalyst in solution in the alternative
  • the liquefied petroleum gas solvent is removed overhead with the unreacted carbon monoxide and hydrogen by depressurization of the settling vessel 18, but preferably will not be greatly in excess of this amount.
  • an amount of the complexed rhodium carbonyl catalyst corresponding to from 10 ppm to 500 ppm by weight of rhodium in the liquid phase in the reactor 14, from 0.1 to 10 percent of the liquid phase in the reactor 14 (by volume) may be comprised of the second organic solvent.
  • a preferred amount of the second organic solvent is from 1 to 7 percent, while most preferably the second organic solvent will be from 2 to 5 percent of the liquid phase in the reactor 14.
  • FIG. 2 an alternative embodiment 30 of a process of the present invention is schematically depicted.
  • the embodiment 30 differs from the process embodiment 10 in that upon transfer of the contents of the reaction vessel 14 (following the hydroformylation therein of the allyl alcohol feed 12a) and of the volume of water supplied in stream 22, and following the formation in settling vessel 18 of the aqueous, organic and gas phases 24, 26 and 28, respectively, the liquefiable petroleum gas employed as a solvent for the allyl alcohol is recovered overhead with the unreacted carbon monoxide and hydrogen by depressurizing the settling vessel 18.
  • a much smaller recycle 16' to reaction vessel 14 of the second organic solvent and complexed, homogeneous rhodium carbonyl hydroformylation catalyst dissolved therein is employed, and the liquefiable petroleum gas is converted back into a liquid in a liquefaction step 32 for being recycled back to reaction vessel 14 with unreacted carbon monoxide and hydrogen in a mixed recycle stream 12c'.
  • the liquefaction step 32 will correspond to current commercial practice in the LPG art, and involve recompression to near-critical conditions for the petroleum gas solvent entering the reaction vessel 14, for example, from atmospheric pressure to the 26 atmosphere pressure, near-critical conditions employed for using propane as the allyl alcohol solvent in Subramaniam et al.
  • the aqueous phase was withdrawn for gas chromatographic analysis, which showed that all of the HBA and HMPA were transferred to the aqueous phase.
  • the organic phase was recycled and reused in the 100 mL Parr reactor with fresh allyl alcohol. Whereas the initial 100 mL Parr reaction gave 100% allyl alcohol conversion, the recycle conversion was still 92% and with 91% chemoselectivity to aldehydes, as compared to the initial 94% chemoselectivity to aldehydes.
  • the ratio of the more desired linear to branched aldehyde products was 8.2 in the initial reaction, and substantially unchanged at 8.13 on running the 1.3 hr recycle reaction.
  • a single solvent allyl alcohol hydroformylation was conducted as described in Subramaniam et al., using compressed, near-critical propane both as the solvent for the allyl alcohol and as the near-critical gas expansion medium for CGXL operation.
  • Two (2) gram portions of the crude hydroformylation product were then combined with five (5) milliliters of a selected, second organic solvent and ten (10) milliliters of water under ambient conditions in a glass separatory funnel.
  • the aqueous phase was withdrawn and collected.
  • the three combined aqueous phases were analyzed by gas chromatography for the

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Abstract

L'invention concerne un procédé amélioré d'hydroformylation, un liquide comprimé, dilaté par du gaz de pétrole de étant utilisé comme solvant pour une charge d'hydroformylation oléfinique dans un réacteur selon le document US 8,822,734 de Subramaniam et al, mais une petite quantité d'un deuxième solvant organique est ajoutée pour le catalyseur de type carbonyle de rhodium homogène, complexé, et le produit d'hydroformylation brut est mélangé avec une quantité d'eau pour extraire les produits de type aldéhyde de l'hydroformylation en son sein. Après la sédimentation du mélange obtenu dans un récipient de sédimentation, une phase aqueuse et une phase organique séparées sont produites. La phase aqueuse contenant des produits d'hydroformylation de type aldéhyde est séparée de la phase organique, laquelle phase organique est ensuite recyclée dans le réacteur.
PCT/US2016/058618 2015-11-04 2016-10-25 Procédé amélioré d'hydroformylation Ceased WO2017078972A1 (fr)

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