Compounds, transition metal complex hydroformylation catalyst precursor compositions containing such compounds, and hydroformylation processes - Patents.com

Abstract

The present disclosure generally relates to a process for separating one or more heavies from a hydroformylation reaction product stream in a hydroformylation process comprising a compound, a transition metal complex hydroformylation catalyst precursor composition, and a metal-monophosphite ligand complex catalyst. In one aspect, the present disclosure provides a compound of formula (I): 1 -R 5 are the same or different and are H or an alkyl moiety; R 6 H, alkyl, aryl, OR 7 , -N(R 8 )2, and O(CH2CH2) y OR 8 Part, R 7 is an alkyl or aryl moiety, R 8 is H, alkyl, or aryl moiety. [Formula 1] JPEG2024545133000025.jpg50170

Description

[Technical field]

[0001] The present invention relates generally to compounds, transition metal complex hydroformylation catalyst precursor compositions, hydroformylation processes, and processes for separating one or more heavies from a hydroformylation reaction product stream in a hydroformylation process comprising a metal-monophosphite ligand catalyst.

[0002] Introduction It is known that various products and by-products can be produced by reacting one or more reactants in the presence of a metal-organophosphorus ligand complex catalyst. However, the stabilization of the catalyst and the organophosphorus ligand remains a major concern. Obviously, catalyst stability is a key issue in the use of any catalyst. Loss of catalyst or catalytic activity due to undesired reactions of very expensive metal catalysts can be detrimental to the production of desired products. Furthermore, the reduced productivity of the catalyst obviously increases the production cost of the product.

[0003] For example, in hydroformylation processes, the decomposition of organophosphorus ligands and the deactivation of metal-organophosphorus ligand complex catalysts are due in part to the vaporizer conditions present, for example, during the vaporizer step often used in the separation and recovery of aldehyde products from the reaction product mixture. When a vaporizer is used to facilitate the separation of the aldehyde products of the process, a harsh environment of higher temperatures and lower carbon monoxide partial pressures than those used during hydroformylation is created. When the organophosphorus-promoted rhodium catalyst is subjected to such vaporizer conditions, it has been found that it deactivates at an accelerated pace over time. Moreover, it is believed that this deactivation is likely caused by the formation of inactive or less active rhodium species. This is particularly evident when the carbon monoxide partial pressure is very low or absent. When the catalyst contains rhodium, it has also been observed that rhodium is prone to precipitation under prolonged exposure to such vaporizer conditions. For example, it is theorized that under harsh conditions such as those present in a vaporizer, an active catalyst, believed to comprise a complex of rhodium, an organophosphorus ligand, carbon monoxide, and hydrogen under hydroformylation conditions, loses at least a portion of its coordinated carbon monoxide, thereby providing a pathway for the formation of such catalytically inactive or less active rhodium.

[0004] These decomposition processes also increase the formation of acidic species, as discussed in U.S. Patents 4,599,206 and 5,288,918. These acids not only accelerate the decomposition of ligand hydrolysis, but also tend to catalyze aldehyde condensation reactions, which leads to increased heavies formation.

[0005] Another requirement for the vaporizer is heavies removal. Aldehyde products form condensation products (dimers, trimers, etc.), commonly referred to as heavies, as described in U.S. Patents 4,148,830 and 4,247,486. The concentration of these heavies increases and typically reaches a steady state as the molecular weight of the aldehyde decreases, where the amount of heavies volatilized and removed via the vaporizer is equal to their rate of formation. However, as the molecular weight of the product aldehyde increases, the volatility of the heavies decreases dramatically, and the vaporizer may no longer be able to remove them at the rate of formation, even under extreme conditions.

[0006] When the level of heavies rises to an undesirable level, alternative removal processes are typically used. One such method is to purge a portion of the catalyst solution and send the purged solution to a precious metal recovery (PMR) facility to recover the valuable rhodium metal. Unfortunately, any products and ligands contained are lost in this process. In addition, the rhodium in this process is unavailable for production and therefore represents idle gold.

[0007] Ultrafiltration and membrane separation techniques have been used to separate the active catalyst from the product, and typically also remove some heavies. Such membrane separation can be accomplished as described in U.S. Patents 5,430,194 and 5,681,473. However, the heavies (like the catalyst) are of high molecular weight and therefore difficult to separate if rhodium and ligand losses are to be minimized.

[0008] Organomonophosphites are well-known ligands for use in hydroformylation and often provide very active catalysts, especially with branched and higher molecular weight olefins. However, they are also known to be unstable and prone to loss of precious metals during extended operation. A balance of electronic and steric parameters in the ligand design for reactivity must be considered.

[0009] Thus, highly active hydroformylation catalysts and successful methods for preventing and / or mitigating organophosphorus ligand decomposition and catalyst deactivation, as occurs under harsh separation conditions, are highly desirable. Vaporization processes are limited due to the temperature sensitivity of the catalyst. Both phase separation and ultrafiltration processes separately suffer from unavoidable catalyst losses through the separation process, as neither is 100% effective at retaining the catalyst and / or ligand. It is desirable to minimize these losses while maintaining acceptable heavies levels in the catalyst solution over long periods of operation. Summary of the Invention

[0010] The present disclosure generally relates to compounds, transition metal complex hydroformylation catalyst precursor compositions, hydroformylation processes, and processes for separating one or more heavies from a hydroformylation reaction product stream in a hydroformylation process comprising a metal-monophosphite ligand complex catalyst. In general, it has been found that using two steps for catalyst-product separation provides better results. By using a vaporizer or other separation step to remove some or most of the product from the catalyst remaining in the catalyst-rich stream, and then performing a phase separation process on at least a portion of the resulting catalyst-rich stream to remove most of the heavies, it is possible to optimize the vaporizer for product removal while minimizing damage to the catalyst, and further, the phase separation process maintains the heavies concentration at a manageable level while minimizing rhodium loss. These and other advantages are discussed further herein.

[0011] Some embodiments of the present invention relate to a compound. In one embodiment, the compound of the present invention is a compound according to formula (I):

[0012] [ka] In the formula, R 1 -R 5are the same or different and are H or an alkyl moiety; R 6 is H, alkyl, aryl, OR 7 , -N(R 8 ) 2 , and O(CH 2 CH 2 ) y OR 8 Part, R 7 is an alkyl or aryl moiety, R 8 is H, an alkyl, or an aryl moiety. In some embodiments, R 1 and R 2 may be linked to form a cyclic moiety, such as naphthyl. In some embodiments, R 4 and R 5 may be linked to form a cyclic moiety, such as a cyclohexyl moiety.

[0013] Such compounds can be used, for example, in transition metal complex hydroformylation catalyst precursor compositions.Accordingly, some embodiments of the present invention relate to transition metal complex hydroformylation catalyst precursor compositions.In one embodiment, the transition metal complex hydroformylation catalyst precursor composition comprises a solubilized Group VIII transition metal-monophosphite complex, an organic solvent, and a free monophosphite ligand, wherein the monophosphite ligand of the metal-monophosphite complex and the free monophosphite ligand are each a compound according to formula (I).

[0014] Some embodiments of the present invention relate to a process for separating one or more heavies from a hydroformylation reaction product fluid. In one embodiment, a process for separating one or more heavies from a hydroformylation reaction product fluid comprising a metal-monophosphite ligand complex catalyst, optionally free monophosphite ligand, one or more aldehyde products, and heavies comprises: (a) in a reaction zone, a metal-monophosphite ligand complex catalyst and optionally free monophosphite ligand are reacted with C 6 ~C 40hydroformylating a mono-olefin to provide a hydroformylation reaction product stream, wherein the mono-phosphite ligand comprises a compound according to claim 1; (b) removing a portion of the hydroformylation reaction product stream from the reaction zone and transferring said portion to a product / catalyst separation zone where a portion of the aldehyde product is vaporized as an overhead stream and a devolatilized catalyst stream comprising the metal-monophosphite ligand complex catalyst is recovered as a bottoms stream; (c) mixing at least a portion of the bottoms stream obtained in step (b) in the presence of a non-polar solvent and a polar solvent to obtain, by phase separation, two phases: a first phase comprising the polar solvent, the metal-monophosphite ligand complex catalyst, and optionally free monophosphite ligand, and a second phase comprising the non-polar solvent, a portion of the heavies, and at least a portion of the remaining aldehyde products; (d) recovering the metal-monophosphite ligand complex catalyst and at least a portion of any free monophosite ligand from the first phase and returning the recovered metal-monophosphite ligand complex catalyst and any recovered free monophosphite ligand to the reaction zone.

[0015] Some embodiments of the present invention relate to a hydroformylation process. In one embodiment, a hydroformylation process for producing aldehydes comprises reacting an olefinically unsaturated compound selected from the group consisting of alpha-olefins containing from 6 to 40 carbon atoms, internal olefins containing from 6 to 40 carbon atoms, and mixtures of such alpha-olefins and internal olefins with carbon monoxide and hydrogen in a reaction zone in the presence of a rhodium-monophosphite complex catalyst consisting essentially of carbon monoxide and rhodium complexed with at least one monophosphite ligand, wherein the at least one monophosphite ligand is a compound according to formula (I).

[0016] These and other embodiments are further described in the detailed description that follows. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a ternary diagram identifying the phase behavior of all solvent systems used in the treatment of homogeneously catalyzed reaction effluent after the product / catalyst separation zone associated with the removal of heavy by-products. [Diagram 2] FIG. 1 is a schematic diagram of a system for implementing some embodiments of the process of the present invention. [Diagram 3] FIG. 1 is a schematic diagram of a system for implementing some embodiments of the process of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The disclosed process, in some embodiments, comprises reacting CO, H under hydroformylation conditions sufficient to form at least one aldehyde product in the presence of a catalyst comprising as components rhodium and a monophosphite ligand according to formula (I): 2 , and C 6 ~C 40 It may be used in combination with a hydroformylation process involving contacting an olefin. Optional process components include an amine and / or water.

[0019] All references to the Periodic Table of the Elements and the various Groups therein are to the version published in CRC Handbook of Chemistry and Physics, 72nd Ed. (1991-1992) CRC Press, page I-11.

[0020] Unless stated to the contrary or implicit from the context, all parts and percentages are by weight and all test methods are as of the filing date of this application. For purposes of United States patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the U.S. equivalent thereof is so incorporated by reference), particularly with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0021] As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably. "Comprise," "include," and variations thereof do not have a limiting meaning when these terms appear in the specification and claims. Thus, for example, an aqueous composition comprising particles of "a" hydrophobic polymer can be interpreted to mean that the composition comprises "one or more" particles of hydrophobic polymer.

[0022] Also herein, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). For purposes of the present invention, it should be understood that numerical ranges are intended to include and support all possible subranges subsumed within the range, consistent with what one of ordinary skill in the art would understand. For example, the range 1 to 100 is intended to convey 1.01 to 100, 1 to 99.99, 1.01 to 99.99, 40 to 60, 1 to 55, etc.

[0023] As used herein, the term "ppmw" means parts per million by weight.

[0024] For purposes of this invention, the term "hydrocarbon" is intended to include all permissible compounds having at least one hydrogen atom and one carbon atom. Such permissible compounds may have one or more heteroatoms. In a broad aspect, permissible hydrocarbons include acyclic (with or without heteroatoms) and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic organic compounds which may be substituted or unsubstituted.

[0025] As used herein, the term "substituted" is contemplated to include all permissible substituents of organic compounds unless otherwise indicated. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Exemplary substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxyalkyl, aminoalkyl (which can range from 1 to 20 or more carbons, preferably 1 to 12 carbons), as well as hydroxy, halo, and amino. The permissible substituents can be one or more and the same or different for appropriate organic compounds. It is not intended that this invention be limited in any manner by the permissible substituents of organic compounds.

[0026] As used herein, the term "hydroformylation" is intended to include, but is not limited to, all hydroformylation processes that involve the conversion of one or more substituted or unsubstituted olefinic compounds or a reaction mixture containing one or more substituted or unsubstituted olefinic compounds to one or more substituted or unsubstituted aldehydes or a reaction mixture containing one or more substituted or unsubstituted aldehydes. The aldehydes can be asymmetric or non-asymmetric.

[0027] The terms "reaction fluid," "reaction medium," and "catalyst solution" are used interchangeably herein and may include, but are not limited to, a mixture including (a) a metal-organophosphorus ligand complex catalyst, (b) free organophosphorus ligand, (c) aldehyde products formed in the reaction, (d) unreacted reactants, (e) a solvent for the metal-organophosphorus ligand complex catalyst and the free organophosphorus ligand, and, optionally, (f) one or more phosphoric acid compounds formed in the reaction, which may be dissolved and / or suspended. The reaction fluids may include, but are not limited to, (a) fluids in the reaction zone, (b) fluid streams en route to the product / catalyst separation zone, (c) fluids in the product / catalyst separation zone, (d) recycle streams, (e) fluids removed from the reaction zone or product / catalyst separation zone, (f) removed fluids being treated in an acid removal system such as a filter or extractor or other immiscible fluid contacting system, (g) treated or untreated fluids returned to the reaction zone or product / catalyst separation zone, (h) fluids in an external cooler, (i) fluids removed in the liquid-liquid separation zone (after the product / catalyst separation zone), (j) fluids separated from the liquid-liquid separation zone (fluids such as (i)) that are returned to the reaction zone or product / catalyst separation zone, (k) fluids separated from the liquid-liquid separation zone (fluids such as (i)) including heavy by-products being removed from the system (optionally further processed). A liquid-liquid separation zone is a phase separation zone where two liquid phases are present and are separated as further discussed herein.

[0028] A "hydrolyzable organophosphorus ligand" is a trivalent phosphorus ligand containing at least one PZ bond, where Z is oxygen, nitrogen, chlorine, fluorine, or bromine. Examples include, but are not limited to, phosphites, phosphino-phosphites, bisphosphites, phosphonites, bisphosphonites, phosphinites, phosphoramidites, phosphino-phosphoramidites, bisphosphoramidites, fluorophosphites, and the like. The ligands may contain chelating structures and / or may contain multiple PZ moieties, such as polyphosphites, polyphosphoramidites, and mixed PZ moieties, such as phosphite-phosphoramidites, flurophosphite-phosphites, and the like.

[0029] The term "free ligand" means a ligand that is not complexed (not associated or bonded) with a metal, e.g., a metal atom, of a complex catalyst.

[0030] As used herein, the terms "heavy by-products" and "heavies" are used interchangeably and refer to by-products having normal boiling points at least 25° C. higher than the normal boiling point of the desired product of the hydroformylation process. Such materials are known to be formed inherently in hydroformylation processes under normal operating conditions through one or more side reactions including, for example, by aldol condensation.

[0031] As mentioned above, the present disclosure generally relates to compounds, transition metal complex hydroformylation catalyst precursor compositions, hydroformylation processes, and processes for separating one or more heavies from a hydroformylation reaction product stream in a hydroformylation process comprising a metal-monophosphite ligand complex catalyst. In general, it has been found that using two steps for catalyst-product separation provides better results. By using a vaporizer or other separation step to remove some or most of the product from the catalyst remaining in the catalyst-rich stream, and then performing a phase separation process on at least a portion of the resulting catalyst-rich stream to remove most of the heavies, it is possible to optimize the vaporizer for product removal while minimizing damage to the catalyst, and further, the phase separation process maintains the heavies concentration at a manageable level while minimizing rhodium loss.

[0032] For a commercially viable process, good reaction rates and catalyst stability must also be achieved. To achieve all of these goals in the hydroformylation of mono-olefins having six or more carbons ("C6+ mono-olefins"), certain mono-phosphite ligands have been developed as described further herein. The mono-phosphite ligands, in some embodiments, may advantageously balance factors to achieve good catalyst stability, hydrolysis resistance, and high reaction rates with the correct polarity to allow for the necessary phase separation during heavies removal but not leave the hydroformylation reaction solution (particularly the vaporizer tail stream in embodiments where a vaporizer is used in the separation zone where the catalyst concentration is highest and the temperature is lowest).

[0033] Specifically, in the context of hydroformylation of C6+ monoolefins, a particular group of metal-organophosphorus ligand complex catalyzed processes have been discovered in which, according to some embodiments, heavies can be selectively extracted and separated from the catalyst-rich fluid by phase separation. According to some embodiments, it is possible to separate the desired products from the reaction product fluid using vaporization and then remove the heavies without the need to use harsh vaporization separation and the harsh conditions associated therewith. Thus, some embodiments of the present invention may provide a highly desirable separation method that uses only vaporization separation to prevent and / or mitigate organophosphorus ligand decomposition and catalyst deactivation that can occur under harsh conditions.

[0034] The invention relates, in part, to a process for separating one or more products as well as heavies from a reaction product stream, the reaction product stream including a metal-organomonophosphorus ligand complex catalyst comprising a particular group of organomonophosphorus ligands, optionally free organomonophosphorus ligand, optionally a non-polar solvent, optionally a polar solvent, one or more heavies, and the one or more products, the process comprising: (1) vaporizing the product stream from the catalyst solution; (2) separating a portion of the resulting catalyst and heavies in the presence of a polar solvent and a non-polar solvent. (3) separating the resulting mixture by phase separation to obtain a polar phase comprising the metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, and the polar solvent, and a non-polar phase comprising the one or more products, heavies, and the non-polar solvent; and (4) recovering the polar phase from the non-polar phase, wherein the organophosphorus ligand has a partition coefficient between polar and non-polar solvents of greater than about 2 and the heavies have a partition coefficient between polar and non-polar solvents of less than about 0.5.

[0035] In one embodiment, the compound of the invention is a compound according to formula (I):

[0036] [ka] In the formula, R 1 -R5 are the same or different and are H or an alkyl moiety; R 6 is H, alkyl, aryl, OR 7 , -N(R 8 ) 2 , and O(CH 2 CH 2 ) y OR 8 Part, R 7 is an alkyl or aryl moiety, R 8 is H, an alkyl, or an aryl moiety. In some embodiments, R 1 and R 2 may be linked to form a cyclic moiety, such as naphthyl. In some embodiments, R 4 and R 5 may be linked to form a cyclic moiety, such as a cyclohexyl moiety.

[0037] Such compounds can be used, for example, in transition metal complex hydroformylation catalyst precursor compositions. In one embodiment, the transition metal complex hydroformylation catalyst precursor composition comprises a solubilized Group VIII transition metal-monophosphite complex, an organic solvent, and a free monophosphite ligand, and the monophosphite ligand of the metal-monophosphite complex and the free monophosphite ligand are each a compound according to formula (I). In some embodiments, the monophosphite ligand of the metal-monophosphite complex and the free monophosphite ligand are the same compound according to formula (I). In some embodiments, when a compound according to formula (I) is used as a ligand in a hydroformylation process, the ligand can facilitate fast hydroformylation rates, thermal stability, and / or favorable partitioning into polar organic solvents.

[0038] Some embodiments of the present invention relate to a process for separating one or more heavies from a hydroformylation reaction product fluid. In one embodiment, a process for separating one or more heavies from a hydroformylation reaction product fluid comprising a metal-monophosphite ligand complex catalyst, optionally free monophosphite ligand, one or more aldehyde products, and heavies comprises: (a) in a reaction zone, a metal-monophosphite ligand complex catalyst and optionally free monophosphite ligand are reacted with C 6 ~C 40 hydroformylating a mono-olefin to provide a hydroformylation reaction product stream, wherein the mono-phosphite ligand comprises a compound according to claim 1; (b) removing a portion of the hydroformylation reaction product stream from the reaction zone and transferring said portion to a product / catalyst separation zone where a portion of the aldehyde product is vaporized as an overhead stream and a devolatilized catalyst stream comprising the metal-monophosphite ligand complex catalyst is recovered as a bottoms stream; (c) mixing at least a portion of the bottoms stream obtained in step (b) in the presence of a non-polar solvent and a polar solvent to obtain, by phase separation, two phases: a first phase comprising the polar solvent, the metal-monophosphite ligand complex catalyst, and optionally free monophosphite ligand, and a second phase comprising the non-polar solvent, a portion of the heavies, and at least a portion of the remaining aldehyde products; (d) recovering the metal-monophosphite ligand complex catalyst and at least a portion of any free monophosphite ligand from the first phase and returning the recovered metal-monophosphite ligand complex catalyst and any recovered free monophosphite ligand to the reaction zone.

[0039] In some embodiments, the recovered metal-monophosphite ligand complex catalyst and any recovered free monophosphite ligand from step (d) may be used in the reaction zone without further treatment. In some embodiments, the polar solvent present in step (d) is removed from the first phase before the recovered metal-monophosphite ligand complex catalyst and any recovered free monophosphite ligand are returned to the reaction zone. In some embodiments, the non-polar solvent is distilled from the second phase in step (d) and at least partially recycled. In some embodiments, the non-polar solvent is C 6 -C 40The non-polar solvent comprises a mono-olefin and is the same as the mono-olefin that is hydroformylated in step (a). In some embodiments, the non-polar solvent comprises unreacted mono-olefin recovered from the overhead stream in step (b).

[0040] Some embodiments of the present invention relate to a hydroformylation process. In one embodiment, the hydroformylation process for producing aldehydes comprises reacting an olefinically unsaturated compound selected from the group consisting of alpha-olefins containing 6 to 40 carbon atoms, internal olefins containing 6 to 40 carbon atoms, and mixtures of such alpha-olefins and internal olefins with carbon monoxide and hydrogen in a reaction zone in the presence of a rhodium-monophosphite complex catalyst consisting essentially of carbon monoxide and rhodium complexed with at least one monophosphite ligand, wherein the at least one monophosphite ligand is a compound according to formula (I). In some embodiments, the reaction zone further comprises at least one free monophosphite ligand, wherein the at least one free monophosphite ligand is a compound according to formula (I). In some embodiments, the hydroformylation reaction conditions include a reaction temperature of 50° C. to 120° C., a total gas pressure of hydrogen, carbon monoxide, and olefinically unsaturated organic compounds of 1 to 1500 psia, a hydrogen partial pressure of 15 to 200 psia, and a carbon monoxide partial pressure of 10 to 200 psia, and the reaction zone contains 4 to 100 moles of the monophosphite ligand per mole of rhodium. In some embodiments, the concentration of rhodium in the reaction zone is 5 to 500 ppmw. In some embodiments, the second phase comprising the non-polar solvent and heavies isolated in step (c) is further processed to recover residual aldehyde products. In some embodiments, at least a portion of the non-polar solvent and / or polar solvent used in step (c) is provided with the bottoms stream from step (b).

[0041] Turning now to the starting materials used in hydroformylation, the hydrogen and carbon monoxide may be obtained from any suitable source, including petroleum cracking and refining operations.

[0042] Syngas (derived from synthesis gas) contains varying amounts of CO and H 2 Syngas is the name given to a gas mixture containing hydrogen, argon, and nitrous oxide. Methods of production are well known and include, for example, (1) steam reforming and partial oxidation of natural gas or liquid hydrocarbons, and (2) gasification of coal and / or biomass. Hydrogen and CO are typically the primary components of syngas, although syngas can also contain carbon dioxide, as well as CH 4 , N 2 , and inert gases such as Ar. 2 The molar ratio of H to CO can vary widely, but is generally in the range of 1:100 to 100:1, preferably 1:10 to 10:1. Syngas is commercially available and is often used as a fuel source or as an intermediate for producing other chemicals. The most preferred H for chemical production is 2 The hydrogen and CO molar ratio is from 3:1 to 1:3, typically targeted to be about 1:2 to 2:1 for most hydroformylation applications. Syngas mixtures are preferred as sources of hydrogen and CO.

[0043] In some embodiments, the olefin starting material reactant is one or more C 6 ~C 40In some embodiments, the olefin starting reactants that may be used in the hydroformylation process of the present invention include both optically active (prochiral and chiral) and non-optically active (achiral) olefinically unsaturated compounds containing from 6 to 40, preferably from 8 to 20, carbon atoms. Such olefinically unsaturated compounds may be substituted or unsubstituted, terminally or internally unsaturated, linear, branched, or cyclic. Olefin mixtures such as those obtained from the oligomerization of ethylene, propene, butene, isobutene, and the like (e.g., so-called dimeric, trimeric, or tetrameric propylene, as disclosed in U.S. Pat. Nos. 4,518,809 and 4,528,403) may be used. Moreover, such olefinic compounds may further contain one or more additional ethylenically unsaturated groups, and mixtures of two or more different olefinically unsaturated compounds may be used as the starting hydroformylation material, if desired. For example, commercially available alpha olefins containing 6 or more carbon atoms may contain small amounts of corresponding internal olefins and / or their corresponding saturated hydrocarbons, and such commercially available olefins do not necessarily need to be purified therefrom before being hydroformylated. Furthermore, such olefinically unsaturated compounds and the corresponding aldehyde products derived therefrom may also contain one or more groups or substituents that do not unduly adversely affect the hydroformylation process or the process of the present invention, for example, as described in U.S. Patents 3,527,809, 4,769,498, and the like.

[0044] Some embodiments of the present invention are particularly useful for the production of non-optically active aldehydes by hydroformylating achiral alpha-olefins containing from 6 to 40, preferably from 8 to 20, carbon atoms, and achiral internal olefins containing from 6 to 20 carbon atoms, as well as starting material mixtures of such alpha-olefins and internal olefins.

[0045] Exemplary alpha and internal olefins that may be hydroformylated according to some embodiments of the present invention include, for example, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 2-octene, propylene dimer, propylene trimer, propylene tetramer, 2-ethyl-1-hexene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, and the like.

[0046] Prochiral and chiral olefins useful in asymmetric hydroformylation that can be used to generate enantiomeric aldehyde mixtures include those represented by the formula:

[0047] [ka] In the formula, R 11 , R 12 , R 3 , and R 14 are the same or different (except for R 11 is R 12 or R 13 is R 14 (different from), hydrogen; alkyl; substituted alkyl. Prochiral and chiral olefins of this definition also include molecules of the general formula above where the R groups are joined to form a ring compound, such as, for example, 3-methyl-1-cyclohexene.

[0048] As mentioned above, the process of the present invention is carried out in the presence of one or more non-polar solvents and one or more polar solvents, or in the presence of one or more non-polar solvents followed by mixing with one or more polar solvents, or in the presence of one or more polar solvents followed by mixing with one or more non-polar solvents. Depending on the particular catalyst and reactants used, suitable non-polar reaction and extraction solvents include, for example, alkanes, cycloalkanes, alkenes, alkadienes, aldehydes, ketones, ethers, esters, amines, aromatic compounds, silanes, silicones, carbon dioxide, and the like. Examples of inappropriate non-polar solvents include fluorocarbons and fluorinated hydrocarbons. These are undesirable due to their high cost, risk of environmental pollution, and potential for the formation of multiple phases. In some embodiments, one or more reactants, the metal-organophosphorus ligand complex catalyst, and optionally the free organophosphorus ligand, exhibit sufficient solubility in the non-polar or polar solvent so that no phase transfer agent or surfactant is required.

[0049] Mixtures of one or more different non-polar solvents may be used if desired. The amount of polar and / or non-polar solvent used in the reaction zone, if any, is not critical to the invention, and need only be an amount sufficient to provide the reaction medium with the particular metal concentration desired for a given process. The amount of non-polar solvent used in the extraction and phase separation zone is not critical to the invention, and need only be an amount sufficient to extract one or more heavy by-products from the reaction product stream in the liquid-liquid separation zone for any given process, and not result in precipitation of catalyst components. To illustrate the considerations in determining the amount of non-polar solvent to use, reference is now made to FIG. 1, which is a ternary diagram identifying the phase behavior of the total solvent system used to treat the homogeneously catalyzed reaction effluent after the product / catalyst separation zone associated with the removal of heavy by-products. The amount of non-polar solvent used in the liquid-liquid separation zone should be sufficiently controlled to obtain two immiscible liquid phases, including a polar phase and a non-polar phase, as indicated by regions 2, 4, and 6 in Figure 1, and to prevent or minimize the formation of three immiscible liquid phases, as indicated by region 5 in Figure 1, and one homogenous liquid phase, as indicated by regions 1, 3, and 7 in Figure 1. Generally, the amount of non-polar solvent used can range from about 5 weight percent or less to about 95 weight percent or more, based on the total weight of the reaction mixture.

[0050] Exemplary non-polar reaction and extraction solvents useful in some embodiments of the present invention include, for example, propane, 2,2-dimethylpropane, butane, 2,2-dimethylbutane, pentane, isopropyl ether, hexane, triethylamine, heptane, octane, nonane, decane, isobutyl isobutyrate, tributylamine, undecane, 2,2,4-trimethylpentyl acetate, isobutyl heptyl ketone, diisobutyl ketone, cyclopentane, cyclohexane, isobutylbenzene, n-nonylbenzene, n-octylbenzene, n-butylbenzene, p-xylene, ethylbenzene, 1,3,5-trimethylbenzene, m-xylene, toluene, o-xylene, decene, dodecene, tetradecene, and heptadecanal. In some embodiments of the present invention, one or more by-products or unreacted olefins (fresh or recycled) may serve as the non-polar reaction solvent. Some embodiments of the present invention may involve recovering and recycling unconverted olefins as part of the non-polar solvent (optionally along with hydrocarbons from the feedstock or from inadvertent hydrogenation during the hydroformylation process). Solubility parameters of exemplary non-polar solvents that may be used in some embodiments are shown in Table 1 below.

[0051] [Table 1]

[0052] As known to those skilled in the art, the hydroformylation process may result in the production of undesired heavies or heavy by-products. In an embodiment of the present invention, the undesired heavies may be selectively removed by extraction and phase separation in a non-polar extraction solvent. As described above, the process of the present invention is carried out in the presence of one or more non-polar solvents and one or more polar solvents, or in the presence of one or more non-polar solvents followed by mixing with one or more polar solvents, or in the presence of one or more polar solvents followed by mixing with one or more non-polar solvents. The undesired heavies are preferably extracted from the reaction product fluid by using a suitable non-polar extraction solvent, so that the extraction of any of the one or more reactants, the metal-organophosphorus ligand complex catalyst, and optionally the free organophosphorus ligand from the reaction product fluid is minimized or eliminated. The one or more reactants, the metal-organophosphorus ligand complex catalyst, and optionally the free organophosphorus ligand are preferably retained in the reaction product fluid by using a suitable polar extraction solvent, so that the extraction of the undesired heavies products from the reaction product fluid is maximized. In some embodiments, the polar solvent is an aqueous mixture preferably containing up to about 30-40 weight percent water. In other embodiments, the polar solvent is an aqueous mixture containing up to about 10 weight percent water. Depending on the particular undesired heavies, suitable polar reaction and extraction solvents include, for example, lactones, nitriles, alkanols, cyclic acetals, pyrrolidones, formamides, sulfoxides, water, and the like. In some embodiments, the polar solvent is not a combination of primary alkanols and water, since primary alkanols are undesirable in this process.

[0053] Mixtures of one or more different polar solvents may be used if desired. In some embodiments, the Hildebrand solubility parameter for the polar solvent or mixture of one or more different polar solvents is about 13.5 (cal / cm 3 ) 1 / 2 or 873 (kJ / m 3 ) 1 / 2 less than about 13.0 (cal / cm 3 ) 1 / 2 or 841 (kJ / m 3 )1 / 2 and more preferably less than about 12.5 (cal / cm 3 ) 1 / 2 or 809 (kJ / m 3 ) 1 / 2 The amount of polar and / or non-polar solvent used in the reaction zone, if any, is not critical to the invention and need only be an amount sufficient to provide the reaction medium with the particular metal concentration desired for a given process. The amount of polar solvent used in the liquid-liquid separation zone is not critical to the invention and need only be an amount sufficient to facilitate extraction of one or more heavy by-products from the reaction product stream for any given process while minimizing loss of ligand and rhodium. The amount of polar solvent used in the liquid-liquid separation zone should be sufficiently controlled to obtain two immiscible liquid phases, including a polar phase and a non-polar phase, by phase separation, as shown by regions 2, 4, and 6 in FIG. 1, and to prevent or minimize the formation of three immiscible liquid phases, as shown by region 5 in FIG. 1, and one immiscible liquid phase, as shown by regions 1, 3, and 7 in FIG. 1. In general, the amount of polar solvent used can range from about 5 weight percent or up to about 50 weight percent based on the total weight of the reaction product stream.

[0054] Exemplary polar reaction and extraction solvents useful in embodiments of the present invention may include, for example, propionitrile, 1,3-dioxolane, 3-methoxypropionitrile, N-methylpyrrolidone, N,N-dimethylformamide, 2-methyl-2-oxazoline, adiponitrile, acetonitrile, epsilon caprolactone, glutaronitrile, 3-methyl-2-oxazolidinone, water, dimethyl sulfoxide, and sulfolane. In some embodiments, one or more hydroformylation reaction products may serve as the polar solvent. Solubility parameters of exemplary polar solvents are shown in Table 2.

[0055] [Table 2]

[0056] The extraction to obtain one phase containing one or more reactants, the metal-monophosphite ligand complex catalyst, optionally free monophosphite ligand, and a non-polar or polar solvent, and at least one other phase containing one or more heavy by-products and a polar or non-polar solvent, is an equilibrium process. The relative volumes of polar and non-polar solvents or reaction product fluids in this extraction operation are determined in part by the solubility of the one or more reactants, the metal-monophosphite ligand complex catalyst, optionally free monophosphite ligand, and one or more products in the solvent used, and the amount of undesired heavy ends extracted. For example, if the heavy ends to be extracted exhibit high solubility in a polar or non-polar solvent and are present in a relatively low concentration in the reaction product fluid, it is possible to extract the heavy ends by using a polar or non-polar solvent in a relatively small volume ratio to the reaction product fluid. The above polar and non-polar solvents can be used as extraction solvents. As described herein, both polar and non-polar solvents are present in the liquid-liquid separation zone.

[0057] Generally, there is little advantage to using temperatures higher than the hydroformylation reaction temperature in the extraction and phase separation process (liquid-liquid separation), and desirable results can be obtained by using extraction temperatures lower than the hydroformylation reaction temperature. Extraction is when both polar and non-polar solvents are mixed and the components of the hydroformylation reaction product fluid separate into different phases, and phase separation is when the polar phase separates from the non-polar phase. Depending on the particular process, the phase separation temperature can range from about -80°C or lower to about 200°C or higher, preferably 0°C to 70°C, and most preferably 25 to 50°C. With regard to pressure, there is generally little advantage to performing extraction and phase separation at high pressure, other than to avoid degassing the fluid. However, extraction can be performed at high pressure if it is desired to keep gas dissolved. The temperatures and pressures used in the separation zone should be sufficiently controlled to obtain, by phase separation, two immiscible liquid phases including a polar phase and a non-polar phase, as indicated by regions 2, 4, and 6 in FIG. 1, and to prevent or minimize the formation of three immiscible liquid phases, as indicated by region 5 in FIG. 1, and one immiscible liquid phase, as indicated by regions 1, 3, and 7 in FIG. 1.

[0058] The time for mixing the reaction product fluid with the polar or non-polar solvent (i.e., the time before phase separation) depends on the rate at which the two phases reach equilibrium. Generally, such times can vary from less than a minute to longer times, such as an hour or more, depending, for example, on the particular components in the reaction product fluid and the solvent used.

[0059] Some embodiments of the present invention relate to a compound. In one embodiment, the compound of the present invention is a compound according to formula (I):

[0060] [ka] In the formula, R 1 -R 5 are the same or different and are H or an alkyl moiety; R 6 is H, alkyl, aryl, OR7 , -N(R 8 ) 2 , and O(CH 2 CH 2 ) y OR 8 Part, R 7 is an alkyl or aryl moiety, R 8 is H, an alkyl, or an aryl moiety, and y is 1 to 20. In some embodiments, R 1 and R 2 may be linked to form a cyclic moiety, such as naphthyl. In some embodiments, R 4 and R 5 may be linked to form a cyclic moiety, such as a cyclohexyl moiety. Such compounds may be advantageously used as monophosphite ligands in transition metal complex hydroformylation catalyst precursor compositions according to some embodiments of the invention, as well as in metal-monophosphite ligand complex catalysts in processes according to some embodiments of the invention (e.g., processes for separating one or more heavies from a hydroformylation reaction product stream and hydroformylation processes). Additional information regarding compounds according to formula (I) is provided below in the discussion regarding their use as ligands, which may be referred to as monophosphite ligands according to formula (I).

[0061] Some embodiments of the present invention relate to a transition metal complex hydroformylation catalyst precursor composition comprising a solubilized Group VIII transition metal-monophosphite complex, an organic solvent, and free monophosphite ligand, wherein the monophosphite ligand of the metal-monophosphite complex and the free monophosphite ligand are each a compound according to formula (I). In some embodiments, the monophosphite ligand of the metal-monophosphite complex and the free monophosphite ligand are the same compound according to formula (I).

[0062] The metal-monophosphite ligand complex catalysts useful in the process of the present invention include a catalytic metal, which may include Groups 8, 9, and 10 metals selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os), and mixtures thereof, with preferred metals being rhodium, cobalt, iridium, and ruthenium, more preferably rhodium, cobalt, and ruthenium, especially rhodium.

[0063] The number of available coordination sites on such metals is well known in the art. Thus, the catalytic species that may comprise the complex catalyst mixture may include monomeric, dimeric, or higher nuclear forms, and is preferably characterized as at least one complexed monophosphite-containing molecule (e.g., a compound according to formula (I)) per metal, e.g., rhodium, molecule. For example, it is believed that the catalytic species of the preferred catalyst used in the hydroformylation reaction may be complexed with carbon monoxide and hydrogen in addition to the monophosphite ligand according to formula (I) in view of the carbon monoxide and hydrogen gases used by the hydroformylation reaction.

[0064] Exemplary metal-monophosphite ligand complex catalysts that can be used in such hydroformylation reactions encompassed by the present invention include metal-monophosphite ligand complex catalysts using compounds according to formula (I). Such catalysts can be prepared using techniques known to those skilled in the art based on the teachings herein. In general, such catalysts can be preformed or formed in situ and consist essentially of a metal in combination with a monophosphite ligand according to formula (I) in complex. Carbon monoxide is also present and is believed to be complexed with the metal in the active species. The active species can also contain hydrogen bonded directly to the metal.

[0065] The term "complex" as used herein means a coordination compound formed by the binding of one or more independently capable electronically rich molecules or atoms with one or more independently capable electronically poor molecules or atoms, each of which can exist independently. For example, a monophosphite ligand according to formula (I) bears a phosphorus donor atom and has one available or unshareable pair of electrons that can form a coordinate bond independently or possibly in concert with the metal (e.g., via chelation). Carbon monoxide is also properly classified as a ligand, but may be present and coordinated to the metal. The final composition of the complex catalyst may also contain additional ligands, such as hydrogen or anions that fill the coordination sites or nuclear charge of the metal. Exemplary additional ligands include, for example, halogens (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF 3 , C 2 F 5 , C.N., (R) 2 PO, and RP(O)(OH)O, where each R is the same or different and is a substituted or unsubstituted hydrocarbon radical, e.g., alkyl or aryl, acetate, acetylacetonate, SO 4 , P.F. 4 , P.F. 6 , NO 2 , NO 3 , C.H. 3 , C.H. 2 =CHCH 2 , C.H. 3 CH=CHCH 2 , C 6 H 5 CN, CH 3 CN, NH 3 , pyridine, (C 2 H 5 ) 3 N, mono-, di- and triolefins, tetrahydrofuran, etc. The complex species preferably does not contain any additional organic ligands or anions that may poison the catalyst or unduly adversely affect catalyst performance. In metal-monophosphite ligand complex catalyzed hydroformylation reactions, it is preferred, although not absolutely necessary, that the active catalyst does not contain halogens and sulfur directly bonded to the metal.

[0066] As noted above, triorganophosphites that may serve as the monophosphite ligand and / or the free ligand of the metal-monophosphite ligand complex catalyst include those according to the following formula (I):

[0067] [ka] In the formula, R 1 -R 5 are the same or different and are H or an alkyl moiety; R 6 is H, alkyl, aryl, OR 7 , -N(R 8 ) 2 , and O(CH 2 CH 2 ) y OR 8 Part, R 7 is an alkyl or aryl moiety, R 8 is H, an alkyl, or an aryl moiety. In some embodiments, R 1 and R 2 may be linked to form a cyclic moiety, such as naphthyl. In some embodiments, R 4 and R 5 may be linked to form a cyclic moiety, such as a cyclohexyl moiety. R of such monophosphites according to formula (I) above 1-6 Any of the radicals may be substituted, if desired, with any suitable substituent containing from 1 to 30 carbon atoms which does not unduly adversely affect the desired outcome of the process of the invention. Substituents which may be present on the radicals, in addition to the corresponding hydrocarbon radicals such as alkyl, aryl, aralkyl, alkaryl, and cyclohexyl substituents, include, for example, -C(O)R 15 Acyl radicals such as -OC(O)R 15 acyloxy radicals such as --CON(R 15 ) 2 and -N(R 15 )COR 15 Amide radicals such as -SO 2 R 15Sulfonyl radicals such as -OR 15 Alkoxy radicals such as -SOR 15 Sulfinyl radicals such as -P(O)(R 15 ) 2 and the like; as well as halo, nitro, cyano, trifluoromethyl, hydroxyl radicals, and the like, where each R 15 The radicals independently represent the same or different monovalent hydrocarbon radicals having 1 to 18 carbon atoms (e.g., alkyl, aryl, aralkyl, alkaryl, and cyclohexyl radicals), provided that -C(O)N(R 15 ) 2 and -N(R 15 )COR 15 In an amide substituent such as 15 can also be hydrogen. Any of the substituted or unsubstituted hydrocarbon radicals that make up a particular given monophosphite can be the same or different.

[0068] More specifically, exemplary substituents include primary, secondary, and tertiary alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, t-butyl, neo-pentyl, n-hexyl, amyl, sec-amyl, t-amyl, isooctyl, decyl, octadecyl, and the like; aryl radicals, such as phenyl, naphthyl, and the like; aralkyl radicals, such as benzyl, phenylethyl, and triphenylmethyl, and the like; alkaryl radicals, such as tolyl and xylyl, and the like; alicyclic radicals, such as cyclopentyl, cyclohexyl, 1-methylcyclohexyl, cyclooctyl, and cyclohexylethyl, and the like; methoxy, ethoxy, propoxy, t-butoxy, -OCH 2 CH 2 OCH 3 , -O(CH 2 CH 2 ) 2 OCH 3 , -O(CH 2 CH 2 ) 3 OCH 3 alkoxy radicals such as phenoxy; aryloxy radicals such as -NH2 , -N(CH 3 ) 2 , -NHCH 3 , -NH(C 2 H 5 ) and amino radicals such as -C(O)CH 3 , -C(O)C 2 H 5 , -C(O)C 6 H 5 Acyl radicals such as -C(O)OCH 3 Carbonyloxy radicals such as -O(CO)C 6 H 5 Oxycarbonyl radicals such as -CONH 2 , -CON(CH 3 ) 2 , -NHC(O)CH 3 Amide radicals such as; -S(O) 2 C 2 H 5 Sulfonyl radicals such as -S(O)CH 3 Sulfinyl radicals such as -SCH 3 , -SC 2 H 5 , -SC 6 H 5 Sulfidyl radicals such as -P(O)(C 6 H 5 ) 2 , -P(O)(CH 3 ) 2 , -P(O)(C 2 H 5 ) 2 , -P(O)(C 3 H 7 ) 2 , -P(O)(C 4 H 9 ) 2 , -P(O)(C 6 H 13 ) 2 , -P(O)CH 3 (C 6 H 5 ), -P(O)(H)(C 6 H 5 ) and other phosphonyl radicals.

[0069] Some typical examples of monophospite ligands according to formula (I) according to some embodiments of the present invention include:

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] As noted above, the metal-monophosphite ligand complex catalyst may be formed by methods known in the art based on the teachings herein. The metal-monophosphite ligand complex catalyst may be in homogeneous or heterogeneous form. For example, a preformed rhodium hydride-carbonyl-monophosphite ligand catalyst may be prepared and introduced into the reaction mixture of the hydroformylation process. More preferably, the rhodium-monophosphite ligand complex catalyst may be derived from a rhodium catalyst precursor that may be introduced into the reaction medium for in situ formation of the active catalyst. For example, rhodium dicarbonyl acetylacetonate, Rh 2 O 3 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Rh(NO 3 ) 3A rhodium catalyst precursor such as may be introduced into the reaction mixture together with the monophosphite ligand according to formula (I) for the formation of an active catalyst in situ. In some embodiments, rhodium dicarbonyl acetylacetonate may be used as the rhodium precursor and reacted with the monophosphite ligand according to formula (I) in the presence of a solvent to form a catalytic rhodium-monophosphite ligand complex precursor, which is introduced into the reactor together with an excess (free) monophosphite ligand for the formation of an active catalyst in situ. In either case, carbon monoxide, hydrogen, and the monophosphite ligand according to formula (I) are all ligands capable of complexing with the metal, and are sufficient for the purposes of the present invention that an active metal-monophosphite ligand catalyst complex is present in the reaction mixture under the conditions used for the hydroformylation reaction. The carbonyl and monophosphite ligands may be complexed with the rhodium prior to the hydroformylation process or in situ during the hydroformylation process if they are not already complexed with the initial rhodium.

[0074] As an example, a transition metal complex hydroformylation catalyst precursor composition consists essentially of a solubilized rhodium carbonyl monophosphite ligand complex precursor, a solvent, and optionally free monophosphite ligand, where the monophosphite ligand is a compound according to formula (I). The catalyst precursor composition can be prepared by forming a solution of rhodium dicarbonyl acetylacetonate, an organic solvent, and the monophosphite ligand according to formula (I). The monophosphite ligand easily replaces one of the carbonyl ligands of the rhodium acetylacetonate complex precursor at room temperature, as evidenced by the evolution of carbon monoxide gas. This replacement reaction can be facilitated by heating the solution, if necessary. Any suitable organic solvent in which both the rhodium dicarbonyl acetylacetonate complex precursor and the rhodium monophosphite ligand complex precursor are soluble can be used. The amount of the rhodium complex catalyst precursor, organic solvent, and monophosphite ligand present in such catalyst precursor composition, as well as the preferred embodiments thereof, can correspond to the amounts thereof that can be used in the hydroformylation process of the present invention. Experience has shown that after the hydroformylation process is initiated, the acetylacetonate ligand of the precursor catalyst is replaced with a different ligand, such as hydrogen, carbon monoxide, or monophosphite ligand, to form an active complex catalyst as described above. The acetylacetone liberated from the precursor catalyst under hydroformylation conditions is removed from the reaction medium together with the product aldehyde, and is therefore in no way detrimental to the hydroformylation process. The use of such a preferred rhodium complex catalyst precursor composition provides a simple, economical and efficient method for handling the rhodium precursor and initiation of hydroformylation.

[0075] Thus, the metal-organophosphite ligand complex catalyst used in the process of the present invention consists essentially of a metal (e.g., rhodium) complexed with carbon monoxide and a monophosphite ligand according to formula (I), the ligand being bound (complexed) to the metal in a chelating and / or non-chelating manner. Furthermore, the term "consisting essentially of," as used herein, does not exclude, but rather includes, hydrogen complexed with the metal in addition to carbon monoxide and the monophosphite ligand. Furthermore, such terms do not exclude the possibility of other organic ligands and / or anions that may also be complexed with the metal. An amount of material that excessively poisons or deactivates the catalyst is undesirable, and thus the catalyst is most desirably free of contaminants such as metal-bound halogens (e.g., chlorine), although this may not be absolutely necessary. The hydrogen and / or carbonyl ligands of the active metal-monophosphite ligand complex catalyst may be present, for example, as a result of the ligands being attached to a precursor catalyst and / or as a result of being formed in situ due to the hydrogen and carbon monoxide gases used in the hydroformylation process.

[0076] As noted above, hydroformylation processes according to embodiments of the invention involve the use of a metal-monophosphite ligand complex catalyst as described herein. Mixtures of such ligands may also be used if desired. The amount of metal-monophosphite ligand complex catalyst present in the reaction fluid of a given hydroformylation process encompassed by the present invention need only be the minimum amount necessary to provide the given metal concentration desired to be used, and the minimum amount that provides a reference for at least the catalytic amount of metal required to catalyze the particular hydroformylation process involved. Generally, catalytic metal (e.g., rhodium) concentrations in the range of 5 ppmw to 1000 ppmw calculated as free metal in the reaction medium should be sufficient for most processes, although it is generally preferred to use 10 to 500 ppmw of metal, and more preferably 25 to 350 ppmw of metal. Analytical techniques for measuring catalytic metal concentrations are well known to those skilled in the art and include atomic absorption (AA), inductively coupled plasma (ICP), and X-ray fluorescence (XRF). AA is typically preferred.

[0077] In addition to the metal-monophosphite ligand complex catalyst, free monophosphite ligand according to formula (I) (i.e., ligand not complexed with a metal) may also be present in the reaction medium. The free monophosphite ligand may correspond to any of the above-defined monophosphite ligands according to formula (I) discussed above as possible for use herein. It is preferred that the free monophosphite ligand is the same as the monophosphite ligand of the metal-monophosphite ligand complex catalyst used. However, such ligands need not be the same in any given process. The hydroformylation process may involve up to 0.1 moles to 200 moles or more of free monophosphite ligand of formula (I) per mole of metal in the reaction medium. Preferably, the hydroformylation process is carried out in the presence of 1 to 100 moles of free monophosphite ligand of formula (I) per mole of metal present in the reaction medium. The amount of monophosphite ligand is the sum of both the amount of monophosphite ligand bound to the metal (complexed) present and the amount of free (uncomplexed) monophosphite ligand present. If necessary, make-up or additional monophosphite ligand according to formula (I) can be provided to the reaction medium of the hydroformylation process at any time and in any suitable manner, for example to maintain a predetermined level of free ligand in the reaction medium.

[0078] The use of optional aqueous buffers to prevent and / or reduce hydrolysis of organophosphite ligands and deactivation of metal-organophosphite ligand complexes is disclosed in U.S. Pat. Nos. 5,741,942 and 5,741,944, which employ aqueous buffers that are generally Group 1 or Group 2 metal (Na, K, Ca, etc.) salts of weak acids.

[0079] Some embodiments of the present invention relate to hydroformylation processes utilizing a monophosphite ligand according to formula (I).

[0080] In one embodiment, a process for separating one or more heavies from a hydroformylation reaction product stream comprising a metal-monophosphite ligand complex catalyst, optionally free monophosphite ligand, one or more aldehyde products, and heavies comprises: (a) in a reaction zone, a metal-monophosphite ligand complex catalyst and optionally free monophosphite ligand are reacted with C 6 ~C 40 hydroformylating a mono-olefin to provide a hydroformylation reaction product stream, wherein the mono-phosphite ligand comprises a compound according to claim 1; (b) removing a portion of the hydroformylation reaction product stream from the reaction zone and transferring said portion to a product / catalyst separation zone where a portion of the aldehyde product is vaporized as an overhead stream and a devolatilized catalyst stream comprising the metal-monophosphite ligand complex catalyst is recovered as a bottoms stream; (c) mixing at least a portion of the bottoms stream obtained in step (b) in the presence of a non-polar solvent and a polar solvent to obtain, by phase separation, two phases: a first phase comprising the polar solvent, the metal-monophosphite ligand complex catalyst, and optionally free monophosphite ligand, and a second phase comprising the non-polar solvent, a portion of the heavies, and at least a portion of the remaining aldehyde products; (d) recovering the metal-monophosphite ligand complex catalyst and at least a portion of any free monophosphite ligand from the first phase and returning the recovered metal-monophosphite ligand complex catalyst and any recovered free monophosphite ligand to the reaction zone.

[0081] In some embodiments, a hydroformylation process for producing aldehydes comprises reacting an olefinically unsaturated compound selected from the group consisting of alpha-olefins containing from 6 to 40 carbon atoms, internal olefins containing from 6 to 20 carbon atoms, and mixtures of such alpha-olefins and internal olefins, with carbon monoxide and hydrogen in a reaction zone in the presence of a rhodium-monophosphite complex catalyst consisting essentially of carbon monoxide and rhodium complexed with at least one monophosphite ligand, wherein the at least one monophosphite ligand is a compound according to formula (I).

[0082] The hydroformylation products may be asymmetric, non-asymmetric, or a combination thereof, with the preferred products being non-asymmetric. The process may be carried out in any batch, continuous, or semi-continuous mode, with any desired catalyst liquid and / or gas recycle operation.

[0083] The recycle procedure generally involves continuously or intermittently removing a portion of the liquid reaction medium (reaction product fluid) containing catalyst and aldehyde product from the hydroformylation reactor, i.e., reaction zone, and recovering the aldehyde product therefrom using composite membranes as disclosed in U.S. Pat. Nos. 5,430,194 and 5,681,473, or, as appropriate, by the more conventional and preferred method of distilling the aldehyde product in a separate distillation zone in one or more stages at normal, reduced, or elevated pressures, i.e., vaporization separation, with the non-volatilized metal catalyst-containing residue being recycled to the reaction zone, e.g., as disclosed in U.S. Pat. No. 5,288,918. In one embodiment, vaporizers and membrane separation processes can be used in series or parallel to effect the product / catalyst separation. Condensation of the volatilized material and its separation and further recovery, for example by further distillation, can be carried out in any conventional manner, the crude aldehyde product can be passed for further purification and isomer separation, if necessary, and any recovered reactants (e.g., olefinic starting material and syngas) can be recycled to the hydroformylation zone (reactor) in any desired conventional manner. The recovered metal catalyst-containing raffinate of such membrane separation or the recovered non-volatilized metal catalyst-containing residue of such vaporization separation can be recycled to the hydroformylation zone (reactor) in any desired conventional manner. For the purposes of this disclosure, the product / catalyst separation zone, including the vaporizer and / or membrane separation process, can also be referred to as the "vaporization zone", since vaporization is the more common method. The majority of the products from the hydroformylation process are recovered by use of this product / catalyst separation zone. Other product recoveries, such as from the reactor vent condenser and downstream heavies recovery or cracking operations, are considered separately.

[0084] In some embodiments, the hydroformylation reaction product fluids that may be used herein include any fluid derived from any corresponding hydroformylation process that contains at least some amount of five different major components or constituents, namely, aldehyde product, metal-monophosphite ligand (according to formula (I)) complex catalyst, free monophosphite ligand according to formula (I), organic solubilizing agent for the catalyst and the free ligand, and heavies (which may contribute to or ultimately include most (or all) of the organic solubilizing agent), which components correspond to those used and / or produced by the hydroformylation process from which the hydroformylation reaction product fluids may be derived. The hydroformylation reaction product fluids that may be used herein may, and usually will, contain small amounts of additional components, such as those purposely used in the hydroformylation process or formed in situ during the process. Examples of such components which may also be present include unreacted olefin starting material, carbon monoxide and hydrogen gas, and products of the type formed in situ, such as unreacted isomerized olefins corresponding to the saturated hydrocarbon and / or olefin starting material, ligand decomposition compounds, and high boiling liquid aldehyde condensation by-products, as well as other inert co-solvent type materials or hydrocarbon additives, if used.

[0085] The reaction conditions of the hydroformylation process encompassed by the embodiments of the present invention may include any suitable hydroformylation conditions that have been used to produce optically active and / or non-optically active aldehydes. For example, the total gas pressure of hydrogen, carbon monoxide, and olefin starting compounds of the hydroformylation process may range from 1 to 69,000 kPa. However, in general, it is preferred that the process be operated at a total gas pressure of hydrogen, carbon monoxide, and olefin starting compounds of less than 14,000 kPa, and more preferably less than 3,400 kPa. The minimum total pressure is primarily limited by the amount of reactants required to obtain the desired reaction rate. More specifically, the carbon monoxide partial pressure of the hydroformylation process of the present invention is preferably 1 to 6,900 kPa, and more preferably 21 to 5,500 kPa, and the hydrogen partial pressure is preferably 34 to 3,400 kPa, and more preferably 69 to 2,100 kPa.

[0086] In general, the hydroformylation process may be carried out at any operable reaction temperature. Advantageously, the hydroformylation process may be carried out at a reaction temperature between -25°C and 200°C. In general, a hydroformylation reaction temperature between 50°C and 120°C is preferred for all types of olefinic starting materials. It is understood that when a non-optically active aldehyde product is desired, an achiral type of olefinic starting material and an organophosphorus ligand are used, and when an optically active aldehyde product is desired, a prochiral or chiral type of olefinic starting material and an organophosphorus ligand are used. The hydroformylation reaction conditions used depend on the type of aldehyde product desired.

[0087] The hydroformylation process of the present invention may be carried out using one or more suitable reactors, such as, for example, a fixed bed reactor, a fluidized bed reactor, a tubular reactor, a Venturi reactor, a bubble column reactor, a continuous stirred tank reactor (CSTR), or a slurry reactor. The optimal size and shape of the reactor will depend on the type of reactor used. The at least one reaction zone used in the present invention may be a single vessel or may comprise two or more separate vessels. The at least one liquid-liquid separation zone used in the present invention may be a single vessel or may comprise two or more separate vessels. The optional at least one buffer treatment zone that may be used in some embodiments of the present invention as taught in U.S. Pat. No. 5,741,944 may be a single vessel or may comprise two or more separate vessels. The reaction zone, product / catalyst separation zone, and liquid-liquid separation zone used herein may be in the same vessel or in different vessels. For example, reactive separation techniques such as reactive distillation, reactive membrane separation, etc. may occur in the reaction zone.

[0088] The hydroformylation process of the present invention may be carried out in a batch or continuous mode, with recycle of unconsumed starting materials as necessary. The reaction may be carried out in a single reaction zone or in multiple reaction zones, in series or parallel, or in an elongated tubular zone or series of such zones, batch or continuous. The materials of construction used should be substantially inert to the starting materials during the reaction, and the fabrication of the equipment should be able to withstand the reaction temperatures and pressures. Means for introducing and / or regulating the amounts of starting materials or components introduced batchwise or continuously into the reaction zone during the reaction may be conveniently utilized in the process, particularly to maintain the desired molar ratio of starting materials. The reaction steps may be carried out by incrementally adding one of the starting materials to the other. The reaction steps may also be combined by simultaneous addition of the starting materials. The starting materials may be added to each or all of the reaction zones in series. If complete conversion is not desired or cannot be obtained, the starting materials may be separated from the product, for example by distillation, and the starting materials may then be recycled back to the reaction zone. Such types of recycle procedures are well known in the art and may involve liquid recycle of the metal-organophosphorus complex catalyst fluid separated from the desired aldehyde reaction product, as disclosed, for example, in U.S. Pat. No. 4,148,830, or gas recycle procedures, as disclosed, for example, in U.S. Pat. No. 4,247,486, and combinations of both liquid and gas recycle procedures, if desired. A particularly desirable hydroformylation process of the present invention involves a continuous liquid catalyst recycle process. Suitable liquid catalyst recycle procedures are disclosed, for example, in U.S. Pat. Nos. 4,668,651, 4,774,361, 5,102,505, and 5,110,990.

[0089] Such hydroformylation processes may be carried out in either glass-lined, stainless steel or similar type reactors. The reaction zone may be fitted with one or more internal and / or external heat exchangers to control excessive temperature fluctuations or to prevent any possible "runaway" reaction temperatures.

[0090] The hydroformylation process of the present invention may be carried out in one or more steps, zones, or stages. The exact number of reaction steps, zones, or stages will depend on the inherent reactivity of the starting materials and the stability of the starting materials and the desired reaction products to the reaction conditions, as well as the best compromise between capital costs and the high catalyst selectivity, activity, life, and ease of operation achieved.

[0091] In some embodiments, the hydroformylation process of the present invention can be carried out in a multi-stage reactor, such as described in U.S. Pat. No. 5,728,893. Such a multi-stage reactor can be designed with internal physical barriers that create two or more theoretical reaction stages per vessel. In effect, it is like having multiple reactors in a single continuous stirred tank reaction vessel. Multiple reaction stages in a single vessel can be a cost-effective way of using the volume of the reaction vessel. This can greatly reduce the number of vessels that would be required to achieve the same result. The reduction in the number of vessels reduces the overall capital and maintenance concerns required for separate vessels and agitators.

[0092] As mentioned above, it is generally preferred to carry out the hydroformylation process of the present invention in a continuous manner.In general, continuous hydroformylation processes are well known in the art and may involve (a) hydroformylating an olefinic starting material with carbon monoxide and hydrogen in a liquid homogeneous reaction mixture containing a solvent, a metal-organophosphorus ligand complex catalyst, and free organophosphorus ligand, (b) maintaining reaction temperature and pressure conditions suitable for hydroformylating the olefinic starting material, (c) feeding make-up amounts of the olefinic starting material, carbon monoxide, and hydrogen to the reaction medium as the reactants are exhausted, and (d) recovering the desired aldehyde hydroformylation product in any manner desired.According to an embodiment of the present invention, the organophosphorus ligand is a monophosphite ligand according to formula (I). The continuous process may be run in a single pass mode, i.e., the vapor mixture containing unreacted olefinic starting material and vaporized aldehyde product is removed from the liquid reaction mixture, the aldehyde product is recovered from the liquid reaction mixture, and make-up olefinic starting material, carbon monoxide, and hydrogen are fed to the liquid reaction medium for a next single pass through without recycle of unreacted olefinic starting material.

[0093] In some embodiments of the present invention, the aldehyde product mixture is separated from other components of the hydroformylation reaction product fluid in which the aldehyde mixture is produced in a product / catalyst separation zone. Suitable product / catalyst separation methods include, for example, distillation, vaporization, wiped film evaporation, falling film evaporation, membrane, or the like, or any combination thereof.

[0094] As mentioned above, at the end of (or during) the process of the present invention, the desired aldehyde can be recovered from the hydroformylation reaction product stream used in the process of the present invention. For example, the recovery techniques disclosed in U.S. Patent Nos. 4,148,830 and 4,247,486 can be used. For example, in a continuous liquid catalyst recycle process, the hydroformylation reaction product stream (containing aldehyde product, catalyst, etc.), i.e., a portion of the reaction stream, removed from the reaction zone can be passed to a product / catalyst separation zone (e.g., vaporizer / separator), and the desired aldehyde product can be separated from the reaction product stream via distillation under normal, reduced, or elevated pressure in one or more stages, condensed, collected in a product receiver, and further purified as necessary. The liquid reaction mixture (bottoms stream) containing the remaining non-volatilized catalyst may then be recycled to the reactor, optionally along with any hydrogen and carbon monoxide dissolved in the bottoms stream, after separating any other volatile materials (e.g., unreacted olefins) from the condensed aldehyde products, for example by distillation in any conventional manner. Generally, it is preferred to separate the desired aldehyde from the catalyst-containing reaction mixture under reduced pressure and at low temperature to avoid possible decomposition of the monophosphite ligand and reaction products. When an alpha-mono-olefin reactant is also used, its aldehyde derivative may also be separated by the above methods.

[0095] More specifically, the distillation and separation of the desired aldehyde products from the metal-organophosphorus complex catalyst containing reaction fluid can occur at any suitable temperature desired. Generally, it is preferred that such distillation be carried out at relatively low temperatures, e.g., below 150° C., and more preferably at temperatures in the range of 50° C. to 140° C. Such aldehyde distillation can be carried out, for example, at low boiling point aldehydes (e.g., C 6 ), under reduced pressure at a total gas pressure substantially lower than the total gas pressure used during hydroformylation, or with high boiling aldehydes (e.g., C 7It is also generally preferred to conduct the reaction under vacuum when the reaction involves a pressure of about 1000 psi (or more). For example, it is common practice to subject the reaction product stream removed from the hydroformylation reactor to reduced pressure to volatilize a significant portion of the unreacted gases dissolved in the reaction product stream and then provide the reaction product stream to a product / catalyst separation zone, such as a vaporizer / separator, where the desired aldehyde product is distilled. In general, distillation pressures ranging from vacuum pressure up to 340 kPa total gas pressure should be sufficient for most purposes.

[0096] Recent improvements for phosphite-catalyzed hydroformylation processes use stripping gas vaporizers such as those disclosed in WO1997007086, WO2010003073, WO2016089602, and WO2020240194. These processes may increase the amount of heavies removed during the vaporization process while also reducing catalyst losses. However, the desired aldehyde product in embodiments of the present invention is C 6 Beyond aldehydes, the ability of such strip gas vaporizers to remove heavies at the rate they form may be limited.

[0097] In a process separate from the product / catalyst separation process described above, in some embodiments of the invention, a portion of the catalyst-containing residue (e.g., bottoms stream from the vaporizer) or membrane residue may be subjected to a phase separation process in which catalyst and catalyst components are separated from at least a portion of the heavies. By inducing phase separation, a partitioning of materials can be obtained where the partition coefficients of the catalyst and heavies are sufficiently different to provide suitable removal of the heavies with minimal catalyst loss.

[0098] Phase separation processes for hydroformylation fluids are known and are generally carried out in suitable equipment, such as glass-lined stainless steel or similar types of equipment, preferably under an inert atmosphere. The extraction and phase separation steps (liquid-liquid separation) of some embodiments of the present invention can be carried out in one or more stages. The extraction system preferably has two or more theoretical extraction stages, both above and below the entry point of the residue from the product / catalyst separation zone. The exact number of stages is governed by the best compromise between capital costs, equipment footprint, and the desire for high extraction efficiency and ease of operation. The extraction process can be carried out continuously or in batch mode. If carried out continuously, the process can be cocurrent, countercurrent, or fractional countercurrent.

[0099] Once the aldehyde product stream is separated from the residual catalyst solution (bottoms stream from the product / catalyst separation zone), the bottoms stream may be phase separated in the presence of a non-polar solvent and a polar solvent to provide two phases: a first phase comprising the polar solvent, the metal-monophosphite ligand complex catalyst, optionally free monophosphite ligand, and a portion of the aldehyde product, and a second phase comprising the non-polar solvent, a portion of the aldehyde product, and a portion of the heavies. The choice of polar and non-polar solvent depends on the polarity of the catalyst and catalyst components and the polarity of the heavies. In general, with high molecular weight monofunctional aldehydes, the resulting heavies tend to be non-polar, in which case it is preferred that the ligand and catalyst have a higher polarity. The polarity (described as the solubility parameter) of the heavy trimers from the ligand and C9 linear aldehydes may be predicted by using the group contribution approach theory as described in U.S. Pat. No. 5,932,772. To effect an efficient separation of these two compounds, a difference in calculated polarity of at least 0.5, preferably 1, and even more preferably 1.5 is believed to be necessary. Using this approach, the following calculated polarities can be determined:

[0100] [Table 3]

[0101] As can be seen, the model C9 heavy nonanal trimer has virtually the same solubility parameter as the control ligand (tris(2,4-ditertbutylphenyl)phosphite) and therefore a phase separation process would not be effective in separating these heavies from the corresponding ligand or the corresponding rhodium catalyst. However, ligands A-J of the present invention (compounds according to formula (I) (monophosphite ligands)) exhibit a difference between their solubility parameter and that of the heavy by-products well above 1.0, so good phase separation is expected.

[0102] One approach to determining suitable polar and non-polar solvents for removing heavies using phase separation is to select a solvent that provides a desired partition coefficient for the heavies while minimizing catalyst and catalyst component (e.g., monophosphite ligand) loss. For example, a polar and non-polar solvent can be selected and then the concentration of the heavies in each phase can be measured by gas chromatography using techniques known to those skilled in the art. The partition coefficient for the heavies after extraction can be defined as follows: K p1 :

[0103]

number

[0104] In some embodiments, the polar solvent and the non-polar solvent have a partition coefficient (K p1 In some embodiments, the polar and non-polar solvents are selected to provide a partition coefficient (K) of 0.2 or less. p1 In some embodiments, the polar and non-polar solvents are selected to provide a partition coefficient (K) of 0.1 or less. p1 ) is chosen to provide a low K p1 The value causes the heavies to distribute preferentially into the non-polar phase.

[0105] As alluded to above, another important factor in selecting polar and non-polar solvents for phase separation is that rhodium phase separates into the polar phase (away from the heavies). In other words, some embodiments of the present invention aim to remove the heavies without losing rhodium. Thus, the partition coefficient of the heavies (K p1 ) should be low for a given combination of polar and non-polar solvents, while the distribution coefficient of rhodium (K p2 , defined below) should be as large as possible for the same combination in order to effectively separate rhodium from the heavies. p2 When calculating the distribution coefficient (K), the concentrations of rhodium in the polar and non-polar phases may be measured by atomic absorption, inductively coupled plasma, and other techniques known to those skilled in the art, but the same measurement technique should be used to measure the concentration in both phases. p2 ) is defined as follows:

[0106]

number

[0107] K p2 When K is high, the rhodium is retained in the polar phase and is recycled back to the reaction zone rather than being lost with the heavies reject stream (the non-polar phase). When the phases are equal in volume, K p2 should be at least 2.5, preferably greater than 5, and most preferably greater than 10.

[0108] K p2 can be estimated by the partition coefficient of the monophosphite ligand, since the rhodium-ligand complex exhibits similar solubility behavior as the ligand itself. The concentration of the monophosphite ligand is generally much easier to measure than the concentration of rhodium. The partition coefficient of the monophosphite (K p2’ ) is defined as follows:

[0109]

number

[0110] K p2’ When K is high, the rhodium is retained in the polar phase and is recycled back to the reaction zone rather than being lost with the heavies reject stream (the non-polar phase). When the phases are equal in volume, K p2’ should be at least 2.5, preferably greater than 5, and most preferably greater than 10.

[0111] The efficiency factor (Ef) is also a function of the distribution coefficient of rhodium (K p2 ) to the distribution coefficient of the heavy substance (K p1 ) can be calculated by dividing it by

[0112]

number

[0113] In some embodiments of the present invention, the polar and non-polar solvents are selected to maximize the efficiency factor, as it indicates that most of the heavies have partitioned into the non-polar phase and most of the ligand / rhodium has partitioned into the polar phase. In some embodiments, the polar and non-polar solvents are selected to provide an efficiency factor (Ef) of 25 or greater. In some embodiments, the polar and non-polar solvents are selected to provide an efficiency factor (Ef) of 30 or greater. In some embodiments, the polar and non-polar solvents are selected to provide an efficiency factor (Ef) of 100 or greater.

[0114] 2 and 3 are schematic diagrams of systems for implementing some embodiments of the process of the present invention.

[0115] In FIG. 2, syngas (1) and olefins (2) are added to one or more hydroformylation reaction zones (3). A portion of the hydroformylation reaction product fluid is removed via line (4) to one or more product / catalyst separation zones (e.g., vaporizers) (5), where an overhead stream (6) containing most of the aldehyde products is removed and a non-volatilized stream (9) containing catalyst and heavies is recovered. A portion of stream (9) is sent back to the reaction zone (3) via line (10) and a portion is sent to a liquid-liquid separation zone (8) via line (10a). A polar solvent (fresh from line (11) or optionally including recycled solvent via line (14)) and a non-polar solvent (fresh from line (12) or optionally including recycled solvent via line (17)) are added and phase separation occurs. The top (non-polar) layer containing heavies (15) is removed and the bottoms stream (10b) is recovered and returned to the reaction zone (3) or to the product / catalyst separation zone (5). Stream (15) is optionally sent to a distillation system (18) to recover and recycle the non-polar solvent and the desired aldehyde product. Similarly, stream (6) can be sent to an optional distillation system (7) to recover the polar solvent and unreacted olefins and recycle them back via line (14). Both stills (7) and (18) may recover both the polar and non-polar solvent as well as some of the desired aldehyde, depending on the composition of the feed streams and the distillation conditions, but all are recovered and recycled in unit (8). The desired aldehyde product is removed via line (13) (if unit (7) is used) or simply via line (6) for further processing. Undesirable heavies are removed via line (16) (if unit (18) is used) or simply via line (15). Because there is minimal catalyst in stream (15), the distillation in (18) can be more severe in order to effectively recover as much of the solvent and desired aldehyde product as possible without concern about catalyst losses. Stream (14) can be distilled before recycling to unit (8), but is typically used as produced since this stream may contain unreacted olefins, thus providing some olefins recycle.A purge (not shown) may be present above (14) to accommodate buildup of hydrocarbons or other inerts as well as purging of syngas and inert gases, if desired.

[0116] Figure 3 shows a system similar to that of Figure 2, where a portion, preferably a majority, of the bottoms stream from the liquid-liquid separation zone (8) is sent to a distillation system (19) to recover the polar solvent and optionally any remaining non-polar solvent (via line 10d) before sending the catalyst stream back to the reaction zone or product / catalyst separation zone via line (10c). This optional process may reduce the concentration of inerts in the reaction zone and is useful when the polar solvent may contribute to side reactions (e.g., water or alcohol).

[0117] In addition, some solvent combinations may form azeotropes that enhance the vaporization and distillation process. For example, small amounts of water in the product / catalyst separation zone (e.g., vaporizer) (5) or stills (7), (18), and / or (19) can azeotrope acetonitrile and cyclohexane, enhancing their recovery and recycle.

[0118] Exemplary non-optically active aldehyde products that may be produced using the hydroformylation process of the present invention include, for example, 2-methyl-1-hexanal, octanal, 2-methyl-1-heptanal, nonanal, 2-methyl-1-octanal, 2-ethyl-1-heptanal, 3-propyl-1-hexanal, decanal, adipaldehyde, 2-methyladipaldehyde, 3-methyladipaldehyde, 2-methyl-1-nonanal, undecanal, 2-methyl-1-decanal, dodecanal, 2-methyl-1-undecanal, tridecanal, 2-methyl-1-tridecanal, 2-ethyl, 1-dodecanal, 3-propyl-1-undecanal, pentadecanal, 2-methyl-1-tetradecanal, hexadecanal, 2-methyl-1-pentadecanal, hexadecanal, hex ... Putadecanal, 2-methyl-1-hexadecanal, octadecanal, 2-methyl-1-heptadecanal, nonodecanal, 2-methyl-1-octadecanal, 2-ethyl-1-heptadecanal, 3-propyl-1-hexadecanal, 2-methyl-1-nonadecanal, heneicosanal, 2-methyl-1-eicosanal, tricosanal, 2-methyl-1-docosanal tetracosanal, 2-methyl-1-tricosanal, pentacosanal, 2-methyl-1-tetracosanal, 2-ethyl-1-tricosanal, 3-propyl-1-docosanal, heptacosanal, 2-methyl-1-octacosanal, nonacosanal, 2-methyl-1-octacosanal, hentriacontanal, and 2-methyl-1-triacontanal.

[0119] Some embodiments of the invention are described in more detail in the following examples. EXAMPLES

[0120] All parts and percentages in the following examples are by weight unless otherwise indicated. Pressures are listed as absolute pressures unless otherwise indicated.

[0121] General Procedure for a Continuous Hydroformylation Process The hydroformylation process is carried out in a glass pressure reactor operated in a continuous mode. The reactor consists of a 3 ounce pressure bottle with the glass front partially immersed in an oil bath for observation. After purging the system with nitrogen, approximately 20-30 mL of freshly prepared rhodium catalyst precursor solution is loaded into the reactor via syringe. The catalyst precursor solution contains approximately 50 ppmw rhodium (introduced as rhodium dicarbonyl acetylacetonate), specific ligands, and tetraglyme as a solvent. After sealing the reactor, the system is purged with nitrogen and the oil bath is heated to provide the desired hydroformylation reaction temperature. The hydroformylation reaction is carried out at a total pressure of 150-160 psig (1034-1103 kPa) and a temperature of approximately 70°C. Feeds containing nitrogen, syngas, and propylene are started. Feed gas (H 2 , CO, Propylene, N 2 The flow rates of the two gases are controlled separately by mass flow meters, and the combined feed gases are dispersed into the catalyst precursor solution through a fritted sparger. 2 , H 2 The partial pressures of the aldehyde, CO, propylene and aldehyde products are determined by GC analysis and by analyzing the vent stream by Dalton's Law. The unreacted portion of the feed gas is continuously vented to allow stripping of the butyraldehyde product and to maintain a substantially constant liquid level. The flow rate and feed gas partial pressure are set to obtain a hydroformylation reaction rate of up to 4 grams moles of aldehyde per liter of reaction fluid per hour. The outlet gas is continuously analyzed by GC. Samples of the reaction fluid are removed (via syringe) for rhodium analysis by atomic absorption and / or HPLC analysis to confirm catalyst composition and feed purity. In practice, it has been frequently observed that it takes about a day for the system to reach steady state as traces of air are removed from the feed lines and thermal equilibrium is reached with the oil bath. The apparatus also provides a continuous flow of gases for the reaction temperature, CO and H. 2 It is possible to generate hydroformylation rates as a function of olefin partial pressure, as well as rhodium content. Reaction rates are converted to constant olefin partial pressure to allow comparison (assuming first order olefin kinetics).

[0122] General Procedure for a Batch Hydroformylation Process Into an autoclave Parr reactor, add 30 mL of 1-octene. Pressurize / depressurize the reactor from 200 psi to 50 psi five times at room temperature to flush the reactor with CO / H 2 The reactor is then filled with a 1:1 mixture of CO / H 2 The mixture is stirred at 70° C. under a mixture of atmosphere (1:1).

[0123] A solution of the ligand to be tested (1 mL, 10 equivalents, 112 μmol) is added, followed by a solution of rhodium dicarbonyl acetylacetonate (1 mL, 1 equivalent, 11.2 μmol) in acetonitrile solvent. The control ligand was provided as a toluene solution, and the ligand of the invention was provided in acetonitrile.

[0124] CO / H fed to reactor 2 The reaction is followed by continuously monitoring the volume of the (1:1) mixture and the reactor pressure is maintained using a Brooks totalizer.

[0125] Example 1: Synthesis of Ligand A Ligand A (shown above) is an example of a compound of the invention according to formula (I) and can be synthesized as follows: To a stirred solution of 2-tert-butylhydroquinone (2 g, 12 mmol) and potassium carbonate (2.484 g, 18 mmol, 1.5 equiv.) in acetonitrile (10 mL), chloroacetone (1.448 mL, 18 mmol, 1.5 equiv.) is added dropwise at room temperature under an inert atmosphere. After stirring overnight, the solution is diluted with water and extracted with diethyl ether (3×15 mL). The combined organic extracts are washed with brine and dried over sodium sulfate. After filtration, the solvent is removed under vacuum to give 1-(3-(tert-butyl)-4-hydroxyphenoxy)propan-2-one in 96% yield (2.557 g, 11.5 mmol), which is purified by recrystallization. The structure of Ligand A precursor is: 1 H NMR analysis and 13 C NMR analysis confirms the following: 1H NMR (400 MHz, chloroform-d) δ 6.89 (d, 1H), 6.60 (d, 1H), 6.52 (dd, 1H), 4.48 (s, 2H), 2.29 (s, 3H), 1.39 (s, 9H). 13 C NMR (101 MHz, CDCl 3 )δ206.64,151.60,149.03,137.93,116.83,114.93,111.35,73.88,34.71,29.40,26.62.

[0126] To a stirred solution of 1-(3-(tert-butyl)-4-hydroxyphenoxy)propan-2-one (1 g, 4.5 mmol) and imidazole (1.224 g, 18 mmol, 4 equiv.) in dichloromethane (10 mL) is added phosphorus trichloride (0.129 mL, 1.5 mmol, 0.33 equiv.) dropwise at room temperature. The solution is stirred overnight, filtered, and the solvent is removed under vacuum to give the product tris(4-hydroxyacetone-2-tert-butylphenyl)phosphite in 90% yield (0.937 g, 1.35 mmol), which is used without further purification. The structure of ligand A is: 1 H NMR analysis, 13 C NMR analysis, and 31 P NMR analysis confirms the following: 1 H NMR (400 MHz, chloroform-d) δ 7.18 (dd, 1H), 6.93 (d, 1H), 6.53 (dd, 1H), 4.47 (s, 2H), 2.26 (s, 3H), 1.32 (s, 9H). 13 C NMR (101 MHz, CDCl 3 )δ205.70,153.39,145.90,141.85,120.12,115.30,110.84,73.49,34.94,29.83,26.57. 31 P NMR (162MHz, CDCl 3 )δ129.78.

[0127] Example 2 and Control Example 1 Hydroformylation experiments are carried out (continuous reactor mode) to compare the reaction rate of tris-(2-tertbutyl-4-(propoxy-2-one)phenyl)phosphite (ligand A) against the control ligand tris-(2,4-ditertbutylphenyl)phosphite (control), a well-known prior art ligand. Ligand A and the control were run at equal ligand / Rh ratios.

[0128] [ka]

[0129] The test conditions are as follows.

[0130] [Table 4] The reaction is continuously monitored by GC to obtain the reaction rate and product selectivity from normal aldehydes to isoaldehydes (i.e., N / I ratio). The results are presented in Table 5.

[0131] [Table 5] The data in Table 5 show that Ligand A and the control exhibit similar activity at steady state conditions as well as similar N / I ratios of 1.2. The above data confirm that the monophosphite ligands of the present invention (compounds according to formula (I)) are effective ligands for the preparation of effective and stable hydroformylation catalysts.

[0132] Example 3: General procedure for ligand distribution (K p2’ )experiment: The partitioning of monophosphite ligands (compounds according to formula (I)) according to some embodiments of the present invention in a biphasic acetonitrile (polar) and hexane (non-polar) mixture is then studied as follows: In a nitrogen-filled glove box, a mixture of acetonitrile (5 mL), hexane (5 mL), and 100 mg of the ligand to be tested is mixed for 30 min. Stirring is stopped and the two phases are left for another 30 min to allow phase separation. Using a 1 mL syringe, 0.2 mL of the top phase (hexane phase (non-polar)) and the bottom phase (acetonitrile phase (polar)) are sampled and diluted to 1 mL with a 1 wt% solution of cyclohexyldiphenyl phosphine (CHDPP, an oxygen scavenger) in tetraglyme. The samples are analyzed by HPLC analysis with a pre-calibrated method to determine the ligand content in each phase, and the partition coefficients (K) are calculated using the above equation. p2’ The results are shown in Table 6.

[0133] [Table 6] The data show how Ligand A partitions favorably in the polar phase compared to prior art ligands.

[0134] Examples 4-8 and Comparative Examples 3-8: Determination of Ef for optimal heavies removal with minimal catalyst losses. A series of partitioning experiments similar to those in Example 3 are carried out using a number of models of aldehydes and heavy aldehydes. Texanol (isobutyraldehyde trimer) was used to 4 Model the heavy products and use isopropyl palmitate to obtain C 8 The trimer was modeled using 2-ethyl-hexenal and octanal, respectively, as the less polar C 3 Dimer and C 4 The dimer was modeled. Nonanal is a nonpolar mixed C 4 / C 5To model dimers (e.g., ene-alts after mixed aldol condensation or mixed ether by-products), a sample of the monophosphite catalyst solution used for branched octene hydroformylation was concentrated under vacuum to give C 9 Most of the aldehyde product is removed and then C 9 This sample containing trimer ("INA trimer") is tested. The concentration of each phase is determined by GC (C 9 (The trimers were multiple peaks that were summed together). As shown in Table 7, the Kp 1 is less than or equal to 1.0, the phase separation process is governed by the partition coefficient of ligand A from Table 6 above (K for ligand A p2’ =21.9) provides optimal heavies removal with minimal rhodium loss as indicated by Ef values ​​of over 25 and some well above 100. Heavies such as C4 trimers with ester and alcohol moieties that are polar (e.g., texanol) do not partition well (Ef<10), but 8 Or C 9 Low polarity, high molecular weight heavies such as the heavies are effectively removed via this process. In Table 7, "a" represents the top (non-polar) layer and "b" represents the bottom (polar) layer.

[0135] [Table 7]

[0136] To test the performance of the monophosphite ligands of the present invention according to formula (I) on higher olefins, 1-octene is used as the olefin in a batch reactor. The heavies produced by this system will be the same as the isononyl alcohol trimer tested in Example 6 above (and therefore the associated Kp given in Table 7 above). 1 is used to calculate the Ef value below. The results are shown in Table 8.

[0137] [Table 8]

[0138] The conversion, selectivity, and rate of Ligand A are comparable to the control ligand. The important next step is to demonstrate that the catalyst using Ligand A can be effectively removed from the catalyst mixture while minimizing rhodium loss (Ef) and removing heavies.

[0139] Example 8 and Comparative Example 8: Reactor samples from Comparative Example 7 and Example 7 are measured for rhodium content, then 1 g of each reactor crude mixture (1-octene hydroformylation reaction product fluid with control ligand or Ligand A) is mixed with 4 grams of acetonitrile and 4 grams of hexane. After the phases are allowed to separate, the rhodium content of each phase is measured. The results are compared to the Kp values ​​from Table 7 for INA trimer (Example 3). 1 Based on this, the following is shown:

[0140] [Table 9]

[0141] Ligand A has a clearly superior Ef value compared to the control ligand, and it is clear that the phase separation of the system effectively recovers most of the rhodium while very effectively removing heavies from the catalyst solution. This result also indicates that the Kp 2’ and Kp 2 Correlation with the former is confirmed, and predictions based on the former are verified by actual catalyst tests.

Claims

1. A compound of formula (I): 【Chemistry 1】 In formula (I), R １ -R ５ are the same or different and are H or alkyl moieties, and R ６ is H, alkyl, aryl, O-R ７ , -N(R ８ ) ２ , and O(CH ２ CH ２ ) ｙ OR ８ part, R ７ is an alkyl or aryl moiety, and R ８ is a H, alkyl, or aryl moiety.

2. A transition metal complex hydroformylation catalyst precursor composition comprising a solubilized Group VIII transition metal-monophosphite complex, an organic solvent, and free monophosphite ligand, wherein the monophosphite ligand of the metal-monophosphite complex and the free monophosphite ligand are each compounds of formula (I): 【Chemistry 1】 In formula (I), R 1 -R 5 are the same or different and are H or alkyl moieties; R 6 is H, alkyl, aryl, O-R 7 , -N(R 8 ) 2 , and O(CH 2 CH 2 ) y OR 8 moieties; R 7 is an alkyl or aryl moiety; and R 8 is H, alkyl, or aryl moiety.

3. 3. The transition metal complex hydroformylation catalyst precursor composition of claim 2, wherein the monophosphite ligand of the metal-monophosphite complex and the free monophosphite ligand are the same compound.

4. 1. A process for separating one or more heavies from a hydroformylation reaction product stream comprising a metal-monophosphite ligand complex catalyst, optionally free monophosphite ligand, one or more aldehyde products, and heavies, said process comprising: (a) in a reaction zone, said metal-monophosphite ligand complex catalyst and optionally free monophosphite ligand, ６ ~C ４０ a method for producing a hydroformylation reaction product stream by hydroformylating a monoolefin, wherein the monophosphite ligand in the metal-monophosphite ligand complex catalyst comprises a compound of formula (I): 【Chemistry 1】 In formula (I), R 1 -R 5 are the same or different and are H or alkyl moieties; R 6 is H, alkyl, aryl, O-R 7 , -N(R 8 ) 2 , and O(CH 2 CH 2 ) y OR 8 moieties; R 7 is an alkyl or aryl moiety; and R 8 is H, alkyl, or aryl moiety; (b) removing a portion of said hydroformylation reaction product stream from said reaction zone and transferring said portion to a product / catalyst separation zone, wherein said aldehyde product portion is vaporized as an overhead stream and a devolatilized catalyst stream comprising said metal-monophosphite ligand complex catalyst is recovered as a bottoms stream; (c) mixing at least a portion of the bottoms stream obtained in step (b) in the presence of a non-polar solvent and a polar solvent to obtain, by phase separation, two phases: a first phase comprising the polar solvent, the metal-monophosphite ligand complex catalyst, and optionally free monophosphite ligand, and a second phase comprising the non-polar solvent, a portion of the heavies, and at least a portion of any remaining aldehyde products; (d) recovering said metal-monophosphite ligand complex catalyst and at least a portion of any free monophosphite ligand from said first phase and returning the recovered metal-monophosphite ligand complex catalyst and any recovered free monophosphite ligand to said reaction zone.

5. 5. The process of claim 4, wherein the recovered metal-monophosphite ligand complex catalyst and any recovered free monophosphite ligand from step (d) can be used in the reaction zone without further treatment.

6. 5. The process of claim 4, wherein the polar solvent present in step (d) is removed from the first phase before the recovered metal-monophosphite ligand complex catalyst and any recovered free monophosphite ligand are returned to the reaction zone.

7. 7. The process of any one of claims 4 to 6, wherein the non-polar solvent is distilled from the second phase in step (d) and at least partially recycled.

8. The non-polar solvent is C ６ -C ４０ 7. The process of any one of claims 4 to 6, comprising a mono-olefin, the mono-olefin being the same as that hydroformylated in step (a).

9. The process of any one of claims 4 to 6, wherein the non-polar solvent comprises unreacted mono-olefin recovered from the overhead stream in step (b).

10. 1. A hydroformylation process for producing an aldehyde, said process comprising:

1. A process comprising reacting an olefinically unsaturated compound selected from the group consisting of alpha-olefins containing from 6 to 40 carbon atoms, internal olefins containing from 6 to 40 carbon atoms, and mixtures of such alpha and internal olefins with carbon monoxide and hydrogen in a reaction zone in the presence of a rhodium-monophosphite complex catalyst consisting essentially of carbon monoxide and rhodium complexed with at least one monophosphite ligand, wherein said at least one monophosphite ligand is a compound of formula (I): 【Chemistry 1】 In formula (I), R 1 -R 5 are the same or different and are H or alkyl moieties; R 6 is H, alkyl, aryl, O-R 7 , -N(R 8 ) 2 , and O(CH 2 CH 2 ) y OR 8 moieties; R 7 is an alkyl or aryl moiety; and R 8 is H, alkyl, or aryl moiety.

11. 11. The process of claim 10, wherein the reaction zone further comprises at least one free monophosphite ligand, the at least one free monophosphite ligand being the compound of formula (I).

12. 11. The process of claim 10, wherein the hydroformylation reaction conditions comprise a reaction temperature of 50°C to 120°C, a total gas pressure of hydrogen, carbon monoxide, and olefinically unsaturated organic compound of 1 to 1500 psia, a hydrogen partial pressure of 15 to 200 psia, and a carbon monoxide partial pressure of 10 to 200 psia, and the reaction zone contains 4 to 200 moles of the monophosphite ligand per mole of rhodium.

13. 11. The process of claim 10, wherein the concentration of rhodium in the reaction zone is from 5 to 500 ppmw.

14. 14. The process of any one of claims 4 to 6 and claims 10 to 13, wherein the second phase comprising the non-polar solvent and heavies isolated in step (c) is further processed to recover residual aldehyde products.

15. 14. The process of any one of claims 4 to 6 and claims 10 to 13, wherein at least a portion of the non-polar solvent and / or polar solvent used in step (c) is provided with the bottoms stream from step (b).

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