WO2011028180A1 - Régénération d'un catalyseur d'hydroformylation pendant l'hydroformylation - Google Patents

Régénération d'un catalyseur d'hydroformylation pendant l'hydroformylation Download PDF

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WO2011028180A1
WO2011028180A1 PCT/SG2010/000320 SG2010000320W WO2011028180A1 WO 2011028180 A1 WO2011028180 A1 WO 2011028180A1 SG 2010000320 W SG2010000320 W SG 2010000320W WO 2011028180 A1 WO2011028180 A1 WO 2011028180A1
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hydroformylation
hydroformylation catalyst
catalyst
reaction
regeneration reagent
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PCT/SG2010/000320
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English (en)
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Chuanzhao Li
Chacko Jacob
Sa-Ei Kanichi
Marc Garland
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Agency For Science, Technology And Research
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • 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
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for hydroformylation and/or hydrocarbonylation of organic compounds.
  • Hydroformylation is one of the ten largest homogeneous catalytic processes with over 10 7 tonnes of products produced per annum. Most of the seven million tons of aldehydes produced annually by this process are hydrogenated to alcohols or oxidized to carboxylic acids. Esterification of the alcohols produces plasticizers— the largest end- use. Detergents and surfactants make up the next largest category, followed by solvents, lubricants, and chemical intermediates. Asymmetric hydroformylation is used mainly for production of agro- and pharmaceutical chemicals
  • Rhodium is frequently the metal of choice in homogeneous catalytic hydroformylations. In such systems, the nominal metal concentration is frequently in the parts-per-million range. Consequently, the presence of trace quantities of some classes of feed impurities can lead to partial or even total deactivation of the systems. These impurities are frequently referred to as poisons.
  • conjugated dienes and alkynes are known to be common poisons for homogeneous catalytic hydroformylations. It is widely accepted that conjugated dienes and alkynes act as poisons by reacting with rhodium and forming new organometallic complexes which are more-or-less stable under reaction conditions, i.e. in the presence of CO and hydrogen. Thus the amount of rhodium available for the transformation of alkene to aldehyde or alcohol is reduced.
  • the hydroformylation of conjugated dienes is known to be difficult with existing hydroformylation technology. In particular, unmodified systems show little or no activity at low temperatures. The hydroformylation of conjugated dienes has been reported, however known active systems all contain a phosphine ligand or make use of very high temperatures.
  • unsaturated aldehydes are used as starting materials in various syntheses.
  • acrolein which is a huge volume commodity, is used to make various resins and polymers.
  • More specialized unsaturated aldehydes are often used in a variety of cyclization and coupling reactions to make complex organic structures in a rapid synthetic manner.
  • Substituted furanones show considerable biological activity.
  • halogenated furanones have been reported to exhibit anti-bacterial activity and anti quorum activity.
  • Other furanones, for example cardiac glycosides have been shown to have considerable anti-cancer activity.
  • ouabain and digoxiri show Na + and K + ATPase inhibition.
  • Non-catalytic synthetic routes exist for the synthesis of unsaturated aldehydes and furanones, but they are generally not considered for more than gram-scale syntheses. Since non-catalytic syntheses are associated with a great amount of waste (large effluent loading factors), catalytic approaches are clearly the preferred way to make large amounts of these organics.
  • a method for hydroformylating or hydrocarbonylating a substrate having a carbon-carbon double or triple bond or both comprising exposing the substrate to a hydroformylation catalyst under an atmosphere comprising carbon monoxide and hydrogen in the presence of a regeneration reagent so as to form a product.
  • the regeneration reagent is such that it is capable of at least partially reversing poisoning of the hydroformylation catalyst by a diene or an alkyne or both.
  • the hydroformylation catalyst may be a metal based catalyst. It may be a metal complex, or a mixture of metal complexes. It may be a rhodium hydroformylation catalyst, a cobalt hydroformylation catalyst, an iridium hydroformylation catalyst or a ruthenium hydroformylation catalyst, or may comprise a combination of any two or more of these. It may be a rhodium complex. It may have formula H a Rh b (CO) c L d in which L is a ligand other than CO, a and d are 0 or a positive integer and b and c are non-zero integers such that H a Rh b (CO) c L d is a neutral compound. It may be Rh 4 (CO)i 2 . It may be a compound capable of being converted in situ to an active catalytic species under the conditions of the hydroformylation. It may be for example rhodium chloride.
  • the regeneration reagent may be a metal based reagent. It may have formula H a M b L c (CO) d .
  • M is a metal ion
  • L is a ligand other than CO
  • a, c and d are each, independently, 0 or a positive integer provided that c and d are not both 0 and b is a non-zero positive integer such that the regeneration reagent is a neutral compound
  • a may be 1.
  • b may be 1.
  • c may be 0.
  • the regeneration reagent may be a rhenium complex or a manganese complex or a chromium complex or a molybdenum complex or a tungsten complex. It may be, for example, HRe(CO) 5.
  • the regeneration reagent may be generated in situ from a regeneration precursor. It may be generated from the regeneration precursor under the reaction conditions used in the hydroformylation or hydrocarbonylation reaction.
  • the precursor may be any suitable precursor capable of being converted under the reaction conditions used in the hydroformylation or hydrocarbonylation reaction into the regeneration reagent. It may be any complex that leads to the formation of a corresponding metal hydride. It may be for example RhRe(CO)9, which can be converted to HRe(CO) 5 under H 2 .
  • the ratio of hydroformylation catalyst to regeneration reagent or precursor may be between about 1 :100 and about 1:0.0001, or between about 1:3 and about 3:1, on a metal atom basis or on a mole basis.
  • the partial pressure of carbon monoxide may be about 0.1 to about 100 bar.
  • the partial pressure of hydrogen may be about 0.1 to about 100 bar.
  • the sum of the partial pressures of carbon monoxide and hydrogen may be about 1 to about 50 bar.
  • the partial pressures of carbon monoxide and hydrogen may be approximately equal.
  • the method may be conducted at a temperature of about -20 to about +150°C. It may be conducted at a temperature of about 10 to about 50°C.
  • the substrate is an olefin, whereby the product is an aldehyde.
  • the substrate may have an impurity which comprises a diene or an alkyne or both.
  • the regeneration reagent or precursor may be added to the reaction mixture after commencement of the reaction. Alternatively the regeneration reagent or precursor (if used) may be added to the reaction mixture before or at commencement of the reaction. These reactions may be conducted at about room temperature, e.g. at about 20 to about 30°C.
  • the substrate is a diene, whereby the product is an unsaturated aldehyde.
  • the diene may be a conjugated diene, whereby the product is a ⁇ , ⁇ -unsaturated aldehyde.
  • the diene may have an impurity which is an alkyne. If elevated temperatures are used, the product may in certain cases be an alcohol, or a dialcohol. Reaction at low temperatures favours production of aldehydes and/or dialdehydes over alcohols and/or dialcohols.
  • the substrate is an alkyne, whereby the product is an ⁇ , ⁇ - unsaturated aldehyde or an unsaturated furanone or a mixture of these.
  • the alkyne may have an impurity which is a diene, e.g. a conjugated diene.
  • the substrate is a mixture of any two or all of an alkene, a diene (optionally conjugated) and an alkyne, e.g. a conjugated alkene plus an alkyne.
  • alkene e.g. 1,3-butane
  • diene optionally conjugated
  • alkyne e.g. 1,3-butane
  • These groups may be in the same molecule (e.g. an enyne) or in different molecules).
  • the hydroformylation or hydrocarbonylation reaction may be conducted such that neither the regeneration reagent nor the hydroformylation catalyst has a ligand which contains phosphorus. They may contain no phosphine ligands. They may contain no phosphite ligands. They may contain neither phosphine nor phosphite ligands. It may be conducted in the absence of phosphorus containing compounds.
  • the concentration of the hydroformylation catalyst in the reaction mixture may be about 0.0001 (i:e. about lppm) to about 10wt% (or % w/v). It may be 20 to 600ppm.
  • a method for hydroformylating an olefin, optionally an unconjugated olefin, optionally in the presence of a conjugated diene or an alkyne or both comprising exposing the substrate to Rli 4 (CO)i 2 and HRe(CO) 5 under an atmosphere comprising carbon monoxide and hydrogen, each independently being at a partial pressure of about 1 to about 20 bar, in the presence of HRe(CO) 5 .
  • the HRe(CO) 5 may be added at or before the commencement of the reaction or it may be added part way through the reaction.
  • a method for hydroformylating or hydrocarbonylating a diene, optionally a conjugated diene, or an alkyne comprising exposing the diene or alkyne to R ⁇ CO) ⁇ and HRe(CO) 5 under an atmosphere comprising carbon monoxide and hydrogen, each independently being at a partial pressure of about 1 to about 20 bar,, or 1 to 25 bar, in the presence of HRe(CO) 5 .
  • a hydroformylation catalyst and a regeneration reagent or both in the hydroformylation or hydrocarbonylation of a substrate having a carbon-carbon double or triple bond or both, said regeneration reagent being capable of at least partially reversing poisoning of the hydroformylation catalyst by a conjugated diene or an alkyne or both.
  • a method for suppressing inhibition of a hydroformylation or hydrocarbonylation reaction catalysed by a hydroformylation catalyst by a conjugated diene or an alkyne or both comprising adding to a reaction mixture for said hydroformylation or hydrocarbonylation reaction a regeneration reagent or a precursor thereto, said regeneration reagent being capable of at least partially reversing poisoning of the hydroformylation catalyst by the conjugated diene or alkyne or both.
  • a regeneration reagent or a precursor thereto for suppressing inhibition of a hydroformylation or hydrocarbonylation reaction catalysed by a hydroformylation catalyst by a diene or an alkyne or both, said regeneration reagent being capable of at least partially reversing poisoning of the hydroformylation catalyst by the conjugated diene or alkyne or both.
  • a method of at least partially regenerating a poisoned hydroformylation catalyst said catalyst being used in a hydroformylation or hydrocarbonylation reaction, said catalyst being poisoned by a diene or an alkyne or both, said method comprising exposing said poisoned hydroformylation catalyst to a regeneration reagent or precursor thereto capable of at least partially reversing the poisoning of the hydroformylation catalyst by the conjugated diene or alkyne or both, said exposing being conducted under the conditions of the hydroformylation or hydrocarbonylation reaction.
  • the hydroformylation catalyst may be Rh 4 (CO) 12 and the regeneration reagent may be HRe(CO) 5.
  • Figure 1 is a graph showing aldehyde 4,4-dimethylpentanal formation rate in Example 1;
  • Figure 2 is a graph showing aldehyde 4 3 ⁇ 4 4-dimethylpentanal formation rate in Example 2 as a function of time and injections of alkyne or metal hydride;
  • Figure 3 is a graph showing 3-cyclohexene-l-carboxaldehyde formation rate in Example 3.
  • Figure 4 shows reaction schemes for hydrocarbonylation of alkynes of Example 4.
  • the present invention relates to improvements in hydroformylation and hydrocarbonylation reactions.
  • hydrocarbonylation and “hydroformylation refer to catalysed reactions of a substrate having a carbon-carbon double or triple bond with carbon monoxide (CO) and hydrogen (H 2 ).
  • CO carbon monoxide
  • H 2 hydrogen
  • Un-functionalized and functionalized alkenes may be hydroformylated to aldehydes, or upon further hydrogenation in the same process, to alcohols.
  • Dienes commonly unconjugated dienes, can be hydroformylated/hydrocarbonylated to mono- and di- aldehydes and alcohols.
  • the term "hydroformylation” refers in general to those reactions in which a formyl (aldehyde) group is present in the product, whereas the term “hydrocarbonylation” is used to refer generally to reactions of unsaturated compounds with hydrogen and carbon monoxide.
  • Hydrocarbonylation reactions may be hydroformylation reactions (i.e. may produce aldehydes) or may produce compounds other than aldehydes, e.g.
  • furanones In general, whether the reaction is a hydroformylation or a hydrocarbonylation (or both) will depend on the substrate. Thus olefins and dienes are generally hydroformylated to form aldehydes. Alkynes may be at least partly hydrocarbonylated to form furanones, although commonly some hydroformylation products (i.e. unsaturated aldehydes) are also formed in these reactions.
  • the reactions described in this specification may be conducted as batch reactions or may be conducted as continuous reactions. Continuous reactions may be more suitable for industrial scale reactions.
  • the invention arises from the discovery that organometallic catalysts for the hydroformylation/hydrocarbonylation reaction, which are readily poisoned by dienes and alkynes, may be regenerated, e.g. regenerated in situ, by means of suitable regeneration reagents, commonly metal complexes. Such dienes and alkynes may be introduced to the reaction as impurities in the substrate. It is thought that the poisoning is due to formation of complexes of the dienes/alkynes with the catalyst (possibly by displacement of a complexed hydrogen atom on the metal centre of the catalyst) to form relatively stable species.
  • hydroformylation catalyst refers to a substance added to the hydroformylation or hydrocarbonylation reaction mixture in order to catalyse the hydroformylation or hydrocarbonylation reaction. It may be, for example, a rhodium carbonyl complex. It is thought that this converts under the reaction conditions to an active catalytic species, which, in the case of a rhodium complex hydroformylation catalyst, is thought to be a hydridorhodium complex, e.g. a hydridorhodium carbonyl complex.
  • This may be HRh(CO) 4 or, more generally, H a Rh b (CO) c L d where L is a ligand other than CO and a, b, c and d are non-negative integers such that the complex is a neutral species, a may be 1. It may be 0. b may be 1. c may be 4. d may be 0.
  • “Poisoning” of a catalyst refers to the reduction in the effectiveness of a catalyst due to the presence of a compound, referred to as a "poison". This may be due to the catalyst (or the active catalytic species) reacting with the poison so that the poison bonds chemically but does not release (or releases only slowly), or chemically alters the catalyst. This effectively reduces the usefulness of the catalyst by reducing (in the extreme to zero) the number of active sites on the catalyst (or the active catalytic species) which are capable of participating in the reaction with which it was to catalyze.
  • a method for hydroformylating or hydrocarbonylating a substrate having a carbon-carbon double or triple bond optionally in the presence of a diene or an alkyne or both.
  • the substrate is exposed to a hydroformylation catalyst, e.g. a rhodium complex, under an atmosphere comprising carbon monoxide and hydrogen in the presence of a regeneration reagent so as to form a product.
  • the reaction may be conducted as a continuous reaction, or it may be conducted as a semi-continuous reaction or it may be conducted as a batch reaction.
  • the hydroformylation catalyst may be an active catalyst for the hydroformylation or hydrocarbonylation reaction, or it may be converted under the conditions of the reaction to an active catalytic species.
  • the hydroformylation catalyst which is added to the reaction may be a precursor to the active catalytic species.
  • the active catalytic species may be formed in situ.
  • the regeneration reagent is capable of at least partially reversing poisoning of the hydroformylation catalyst or of the active catalytic species by one or more conjugated dienes or one or more alkynes or both. It may in at least some cases do so by replacing the conjugated diene or alkyne as ligands in a complex derived from the hydroformylation catalyst by a hydrogen atom.
  • the regeneration reagent may be generated from a regeneration precursor which actually regenerates the hydroformylation catalyst or active catalytic species. It may be converted to said regeneration reagent under the conditions of the hydroformylation or hydrocarbonylation reaction. It may be converted thereto in situ.
  • the invention relates to conversion of alkenes to aldehydes by addition of hydrogen and carbon monoxide.
  • the regeneration reagent serves to reverse and/or inhibit and/or guard against poisoning of the catalyst. It may therefore be added at the start of the reaction, or it may be added part way through the reaction, for example at a time when the reaction has slowed unacceptably.
  • the invention in another form, relates to conversion of dienes and alkynes, which would normally poison the catalyst, to aldehydes, dialdehydes, furanones and other related products.
  • the addition of the regeneration reagent prevents or inhibits poisoning of the catalyst by the substrate, allowing the reaction to proceed.
  • Substrates these have one or more (e.g. 1, 2, 3, 4 or 5) carbon-carbon double bonds and/or one or more (e.g. 1, 2, 3, 4 or 5) carbon-carbon triple bonds. In the event that there are more than one carbon-carbon double or triple bonds, these may be conjugated or unconjugated, or some may be conjugated and others unconjugated.
  • the substrates which may be used in the present invention include alkenes (which may be for example monoalkenes, unconjugated di- or polyalkenes, unconjugated alkenynes etc.), conjugated dienes and alkynes (which may be for example monoalkynes, conjugated or unconjugated di- or polyalkynes, conjugated or unconjugated alkenynes etc.).
  • the alkenes, dienes and alkynes may have the saturation at a terminal carbon (e.g. 1-butene, 1,3 -butadiene) or may have saturated terminal carbons (e.g. 2-butene, 2-butyne). They may be linear, branched, cyclic or any combination of the above.
  • the substrate may comprise one or more dienes and/or alkynes as an impurity.
  • the initial concentration of the substrate in the reaction mixture may be about 0.1 to 99.9% w/v, or about 0.1 to 50, 0.1 to 20, 0.1 to 10, 0.1 to 5, 0.1 to 1, 0.1 to 0.5, 0.5 to 99.9, 1 to 99.9, 5 to 99.9, 10 to 99.9, 59 to 99.9, 1 to 50, 1 to 20, 1 to 10, 10 to 50, 20 to 50 or 5 to 10%, e.g. about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2,-3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 95, 99, 99.5 or 99.9% w/v.
  • the substrate may be used neat, particularly in the case where it is a liquid at the temperature used in the hydroformylation or hydrocarbonylation reaction.
  • Products these are the products of the hydroformylation or hydrocarbonylation. They may be aldehydes (which may be saturated other than the aldehyde functionality, or may be unsaturated, e.g. ⁇ , ⁇ -unsaturated, ⁇ , ⁇ -ubsaturated or otherwise), dialdehydes, alcohols, dialcohols and furanones. They may be hydroformylation products. They may be hydrocarbonylation products.
  • Catalyst poisons may be impurities in the starting material. They may be difficult to completely remove from the starting material, or to remove sufficiently so as to not substantially, or unacceptably, affect the reaction rate. They are commonly dienes, e.g. conjugated dienes, and/or alkynes. It is thought that they poison the catalyst by binding strongly to a central metal atom or ion of the hydroformylation catalyst (or active catalytic species) so as to occupy a binding site that might otherwise be occupied by a hydrogen atom or a substrate molecule. Thus they may be compounds that bind to the metal atom or ion more strongly than hydrogen, or more strongly than the desired substrate, or both. They may effectively not release from the metal atom or ion under the reaction conditions in the absence of the regeneration reagent (see below).
  • Hydroformylation catalyst this is a catalyst which is capable of catalysing a hydrocarbonylation or hydroformylation reaction. It may be a precursor to the active catalytic species, or it may be the active catalytic species. It may be a precursor that is converted under the conditions of the reaction to the active catalytic species. It may be a rhodium complex, or it may be a complex of some other catalytically active metal, e.g. cobalt, iridium or ruthenium, or it may be a mixture of such complexes (or a mixed complex of two or more of said metals). It may be a rhodium carbonyl complex. It may be for example R ⁇ CO) ⁇ .
  • the hydroformylation catalyst may have no phosphorus containing ligands (e.g. phosphines, phosphites etc.). It may be present in the reaction mixture at a concentration of about 0.0001 to about 10%, or about 0.0001 to 1, 0.0001 to 0.1, 0.0001 to 0.01. 0.0001 to 0.001, 0.001 to 10, 0.01 to 10, 0.1 to 10. 1 to 10, 0.001 to 1, 0.10 to 0, 0.001 to 0.1 or 0.01 to 0.1%, e.g.
  • the ratio of substrate to hydroformylation catalyst to substrate may be about 1:10 to about 1:100000, or about 1:10 to 1:10000, 1:10 to 1:1000, 1:10 to 1:100, 1 :10 to 1:50, 1:100 to 1 :100000, 1 :1000 to 1 :100000, 1 :10000 to 1 :100000, 1:100 to 1:10000, 1 :100 to 1 :1000 or 1:1000 o 1 :10000.
  • the ratio of substrate to catalyst may be in the above ranges, or may be down to about 1 : 10 7 ,
  • Regeneration reagent this may be a complex capable of allowing the hydroformylation catalyst (or an active catalytic species derived in situ therefrom) to catalyse a hydroformylation or hydrocarbonylation reaction, e.g. of an olefin in the presence of a conjugated diene, or an alkyne or both, or of a diene, or of an alkyne. It may be a co-catalyst or a co-reagent. It may be a metal carbonyl complex. It may be a hydridometal carbonyl complex.
  • the metal complex may be present at a concentration of about 0.5 to 2mM, or about 0.5 to 1, 1 to 1.5, 1 to 2 or 1.5 to 2mM, e.g. about 0.5, 0.6, 0.7, 0 r 8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2mM.
  • hydroformylation catalyst i.e. [regeneration reagent]: [hydroformylation catalyst]
  • hydroformylation catalyst i.e. [regeneration reagent]: [hydroformylation catalyst]
  • hydroformylation catalyst i.e. [regeneration reagent]: [hydroformylation catalyst]
  • mole (or metal atom) basis or about 100:1 to 0.001:1, 100:1 to 0.01:1, 100:1 to 0.1 :1, 100:1 to 1:1, 100:1 to 10:1, 10:1 to 0.0001:1, 1:1 to 0.0001:1, 0.1:1 to 0.0001 :1, 0.01:1 to 0.0001:1, 0.001 :1 to 0.0001:1, 10:1 to 1 :1, 1 :1 to 0.001 :1, 1:1 to 0.01 :1 or 10:1 to 0.01:1, e.g.
  • the reaction may be conducted in a solvent.
  • the solvent may be capable of dissolving the substrate. It may be capable of dissolving the regeneration reagent and/or precursor thereto. It may be capable of dissolving the hydroformylation catalyst and/or an active catalytic species derived in situ therefrom. It may be capable of dissolving any two or all of these.
  • It may be a hydrocarbon solvent. It may be a saturated hydrocarbon. It may be for example pentane, hexane, heptane, octane, cyclohexane, cycloheptane, isooctane etc. or may be a mixture of suitable solvents.
  • the reaction may be conducted with no solvent other than the substrate.
  • the reaction may be conducted at room temperature. It may be conducted at a temperature of about -20 to about +150°C, or about -20 to +20, -20 to 0, 0 to 20, 0 to 150, 20 to 150, 50 to 150, 100 to 150, 0 to 100, 0 to 50, 10 to 50 or 50 to 100°C, e.g. about -20, -10, 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150°C.
  • the partial pressures of carbon monoxide and of hydrogen in the method may, independently, be about 0.1 to about 100 bar, or about 0.1 to 50, 0.1 to 20, 0.1 to 10, 0.1 to 5, 0.1 to 2, 0.1 to 1, 0.1 to 0.5, 0.5 to 1, 1 to 100, 10 to 100, 50 to 100, 1 to 50, 1 to 20, 1 to 10, 10 to 50 or 20 to 50 bar, e.g. about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45 or 50 bar.
  • the partial pressures of carbon monoxide and hydrogen may be approximately equal, or they may be different.
  • the total pressure may be about 1 to about 100 bar, or about 1 to 50, 1 to 20, 20 to 100k, 50 to 100 or 20 to 50 bar, e.g. about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90 or 100 bar.
  • the total pressure is commonly above atmospheric pressure. It is therefore common to conduct the reaction in a vessel capable of withstanding the pressure used. It may for example be conducted in a pressure vessel.
  • the vessel may be equipped with a pressure release valve in case of excessive pressure buildup. It may comprise a pressure gauge for determining the pressure inside the vessel.
  • the vessel may be fitted with an addition port for adding species to the vessel. The addition port may be designed so that species may be added without releasing pressure within the vessel.
  • the atmosphere used in the reaction may consist essentially of carbon monoxide and hydrogen, although minor impurities may also be present.
  • the pressure, temperature and solvent are preferably such that the solvent is a liquid.
  • the reaction may be conducted for sufficient time to obtain the desired conversion.
  • the actual time may depend on the nature of the reagents, the conditions (e.g. temperature, pressure) used, the concentration and nature of the metal complex and rhodium complex etc.
  • the reaction time may be from about 1 to about 1000 minutes, but may be more or less than this in some circumstances. It may be about 1 to 500, 1 to 100, 1 to 50, 1 to 20, 1 to 10, 10 to 100, 10 to 500, 10 to 50, 50 to 500, 50 to 100, 100 to 500, 100 to 200, 200 to 1000, 500 to 1000, 200 to 800, 200 to 500 or 500 to 800 minutes, e.g. about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70,. 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000 minutes.
  • Reaction rate the above conditions may result in a reaction rate for conversion of alkenes of about 0.5 to about 5mM/min, or about 0.5 to 2, 0.5 to 1, 1 to 5, 2 to 5, 1 to 2 or 1 to 3 mM/min, e.g. about 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5 mM/min.
  • the rate may be somewhat slower, e.g. about 0.1 to about ImM/min, or about 0.1 to 0.5, 0.5 to 1, 0.2 to 1, 0.2 to 0.8 or 0.5 to 0.8mM/min, e.g.
  • reaction rate may be about 1.5 to about 10 fold, or about 2 to 10, 5 to 10, 1.5 to 5, 1.5 to 2 or 2 to 5 fold, e.g. about 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9 or 10 fold.
  • This increase may require a regeneration reagent to hydroformylation catalyst as described above, more commonly about 100 to 200% of the hydroformylation catalyst on a mole basis, e.g. about 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200%.
  • the actual reaction rate in an industrial scale process is dependent on reactor size and reaction conditions used. The experimental data presented herein are from laboratory scale reactions and may not translate directly to industrial conditions.
  • reaction conditions do not exclusively provide hydroformylation or hydrocarbonylation products, and may for example provide partial or complete hydrogenation products. Conversion to products may be high under the reaction conditions described herein. They may for example be greater than about 75%, or greater than about 80, 85, 90 or 95%. They may be for example about 75, 80, 85, 90, 95 or 100%. In the event that more than one product is formed, this conversion is of course the total of all of the products formed.
  • Described herein is a method for the re-activation of catalysed, e.g. rhodium catalysed, hydroformylation and hydrocarbonylations poisoned by conjugated dienes and/or alkynes.
  • catalysed e.g. rhodium catalysed
  • the problem of poisoning is usually approached in a preventative manner by cleaning up the feed stock. There seems to have been little or no attention given to the re-activing a poisoned system. Sometimes, the feed is not entirely cleaned up and trace impurities remain. In such cases, the preventative measures fail and a way of regenerating the deactivated system is needed.
  • the present invention disclosure provides an in situ reactivation procedure.
  • the present invention addresses the problem of poisoning of catalyzed hydroformylations and hydrocarbonylations by conjugated dienes and/or alkynes.
  • the basis for this invention is the observation that some metal hydride complexes react with rhodium-diene or rhodium-alkyne complexes. This results in re-activation of the system, in particular of rhodium organometallic species present in the active hydroformylations and hydrocarbonylations, and leads to renewed hydroformylation/hydrocarbonylation activity.
  • the invention therefore relates to the use of metal hydride complexes for preferential reaction with rhodium-diene or rhodium-alkyne complexes, resulting in renewed hydroformylation/hydrocarbonylation activity.
  • suitable metal containing precursors may be used that, under hydroformylation/hydrocarbonylation conditions, generate the metal hydride complexes.
  • the hydroformylation rate was circa ⁇ . ⁇ ⁇ ⁇ "4 mole/(L-min) before 0.1ml (0.02mole/L) conjugated diene isoprene was added.
  • the addition of isoprene resulted in the system deactivation and the hydroformylation rate decreased to circa 7 10° mole/(L-min).
  • alkyne Upon addition of 25 micro-liter (0.0042 mole/L) 1-heptyne, the rate of hydroformylation decreased to 4x10 "3 mole/(L-min). Upon addition of another 25 microliter (0.0042 mole/L) 1-heptyne, the rate of hydroformylation decreased further to 2.2x10 " 6 mole/(L-min).
  • alkyne clearly causes significant deactivation of the system. On a mole-to-mole basis, the first injection of alkyne corresponds to a 3: 1 ratio of alkyne to rhodium. Alkyne is a strong poison.
  • a metal e.g. rhenium
  • Another option which may in some cases be preferable, involves the deliberate addition of the metal (e.g. rhenium) hydride complex, or precursor thereto, during startup of the reaction or shortly thereafter.
  • a suitable level of the rhenium hydride complex or precursor would be such that the Rh:Re ratio is about 1 :0.01 or about 1:0.001. In this manner, the rhenium hydride complex can continuously attack any rhodium-alkyne or rhodium-diene complexes that are generated.
  • feed purification may not need to be as stringent as it might otherwise have been, and hence purification costs may be reduced.
  • purification costs may be reduced.
  • a very small amount of rhenium hydride complex allows the process to be more robust toward continuous feed impurities as well as upsets.
  • Described herein is also a method for hydroformylation of conjugated dienes at low temperature without use of phosphine ligands, by means of a combination of a rhodium complex and a complex of a selected second metal.
  • This reaction may be conducted at low temperatures to yield mono- and di-aldehydes. At higher temperatures the reaction results in the formation of mono- and di-alcohols.
  • the inventors have found that a mixed metal catalyst containing rhodium may be used in place of the combination of metal complexes in this reaction, again resulting in the hydroformylation of conjugated dienes at low temperatures to form mono- and di- aldehydes and at higher temperatures results to form mono- and di-alcohols.
  • the invention also provides a method for hydroformylation of internal and terminal alkynes at low temperature and low pressure without use of phosphine ligands, to form unsaturated aldehydes and substituted furanones.
  • low temperature and low pressure metal mediated catalytic syntheses of unsaturated aldehydes and substituted furanones, using rhodium and rhenium carbonyls are described.
  • the reactions go to completion in about 2-9 hours using both internal and terminal alkynes, where the substrate to metal ratios are about 100 : 1 to 1000 : 1.
  • a list of alkyne substrates and reaction conditions used are provided in Table 1 and Figure 4 shows reaction schemes for hydroformylation/hydrocarbonylation of alkynes.
  • Table 1 A list of alkyne substrates and reaction conditions used are provided in Table 1 and Figure 4 shows reaction schemes for hydroformylation/hydrocarbonylation of alkynes.
  • the results in Table 1 indicate that the use of a rhodium catalyst and a selected second metal complex results in the conversions of alkynes at low temperatures and low pressures to form unsaturated aldehydes and substituted furanones.
  • the syntheses avoid the use of phosphines or phosphites.
  • Fig. 4 shows the reactions for various hydroformylation/hydrocarbonylation reactions according to the present invention. Details are set out below, showing the selectivity of the rhodium-rheniumcarbonyl catalytic systems, in which A represents substituted unsaturated aldehyde products and B represents furanone products (except in the case of hydroformulation of diphenylacetylene, in which case these are B and C respectively). All numbers are base on ⁇ -NMR ratio.
  • the invention also provides a method for transforming dienes/alkynes to unsaturated aldehydes and furanones:
  • a rhodium precursor and a selected second metal complex H a M b L c (CO) d or any complex that leads to the formation of a corresponding metal hydride
  • the Rh-Re systems are particularly good in the absence of phosphorus containing Iigands.

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Abstract

L'invention concerne un procédé d'hydroformylation ou d'hydrocarbonylation d'un substrat ayant une double ou triple liaison carbone-carbone ou les deux. Le procédé comprend l'exposition du substrat à un catalyseur d'hydroformylation sous une atmosphère comprenant du monoxyde de carbone et de l'hydrogène en présence d'un réactif de régénération de façon à former un produit. Le réactif de régénération est tel qu'il est capable d'au moins partiellement inverser l'empoisonnement du catalyseur d'hydroformylation par un diène ou un alcyne ou les deux.
PCT/SG2010/000320 2009-09-04 2010-09-03 Régénération d'un catalyseur d'hydroformylation pendant l'hydroformylation WO2011028180A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013176346A1 (fr) * 2012-05-25 2013-11-28 (주)엘지화학 Procédé de régénération d'un catalyseur d'hydrogénation
US9492813B2 (en) 2012-05-25 2016-11-15 Lg Chem, Ltd. Method for regenerating hydrogenation catalyst
US9493725B2 (en) 2014-09-08 2016-11-15 The Procter & Gamble Company Detergent compositions containing a predominantly C15 alkyl branched surfactant
US9493726B2 (en) 2014-09-08 2016-11-15 The Procter & Gamble Company Detergent compositions containing a predominantly C15 branched alkyl alkoxylated surfactant
CN112892601A (zh) * 2019-12-03 2021-06-04 中国科学院大连化学物理研究所 一种由3-环己烯-1-甲醛制备1,4-环己烷二甲醛的方法

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US5520722A (en) * 1995-01-18 1996-05-28 Exxon Research And Engineering Company Multiunsaturates removal process
WO2005049537A1 (fr) * 2003-11-18 2005-06-02 Sasol Technology (Proprietary) Limited Production de produits oxygenes

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013176346A1 (fr) * 2012-05-25 2013-11-28 (주)엘지화학 Procédé de régénération d'un catalyseur d'hydrogénation
US9492813B2 (en) 2012-05-25 2016-11-15 Lg Chem, Ltd. Method for regenerating hydrogenation catalyst
US9493725B2 (en) 2014-09-08 2016-11-15 The Procter & Gamble Company Detergent compositions containing a predominantly C15 alkyl branched surfactant
US9493726B2 (en) 2014-09-08 2016-11-15 The Procter & Gamble Company Detergent compositions containing a predominantly C15 branched alkyl alkoxylated surfactant
CN112892601A (zh) * 2019-12-03 2021-06-04 中国科学院大连化学物理研究所 一种由3-环己烯-1-甲醛制备1,4-环己烷二甲醛的方法

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