hydroformylation process

专利摘要:
HYDROFORMILLATION PROCESS A multi-reaction train hydroformylation process in which a common catalyst-product separation zone is employed.
公开号:BR112016013001B1
申请号:R112016013001-4
申请日:2014-12-09
公开日:2020-12-29
发明作者:Thomas C. Eisenschmid；Morteza Mokhtarzadeh；Cloid R. Smith, Iii；Michael C. Becker；George R. Phillips；Michael A. Brammer；Glenn A. Miller；Rick B. Watson；Irvin B. Cox；Edward A. Lord；Martin Smidt
申请人:Dow Technology Investments Llc；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION
[001] The invention relates to a process for hydroformylation of olefins to produce aldehydes.
[002] It is often desirable to feed two or more olefins in the same hydroformylation plant. In some cases, the two olefins are fed to the same reactor. This process, commonly referred to as a “coalimentation” process, allows for capital savings compared to having complete, separate production trains for each olefin. The coalimentation process shares a hydroformylation reactor and catalyst-product separation equipment, and then downstream refining separates the products for further processing. Examples of such a process are disclosed in EP 0 052 999, GB 1,120,277, WO 1980/001691, US 4,262,142, Ex. 13 of US 4,400,547 and US 5,312,996.
[003] Inherent in the coalimentation operation are problems, compared to operations using 2 separate reactor trains, balancing the reactors with varying feed rates, such as when a power supply is reduced, and maintaining product isomer ratios. in the first case, a reduction in the amount of the most highly reactive olefin, for example, ethylene, greatly impacts the generation of heat, which can make the reactors unstable. Conversely, a reduction in the amount of the less reactive olefin feed will provide a first reactor enriched with highly reactive olefin and the reactor coolers may not be able to maintain steady state operation. Changes in feed composition can also impact reactor stability and catalyst performance. For example, an inhibitor in a feed will impact performance for the entire production system.
[004] Another problem with coalimentation operation, compared to operations using 2 separate reactor trains, is that the reactor volume occupied by the most reactive olefin product is not produced, and the extra time the product spends in the reactor encourages reactions secondary as heavy residue formation and ligand degradation. Sudden changes in feed quality or availability can generate very extreme concentrations of catalyst that can impact overall plant stability.
[005] It is well known that the ratio of linear and branched aldehyde isomer products, commonly referred to as the N: I ratio, depends on several factors including ligand identity and concentration, usually defined as the ratio of ligand to rhodium, temperature and partial pressures of H2 and CO. In a coalimentation system, these conditions are the same for the two reaction olefins, although the desired product N: I ratio for the two products can differ greatly, so that the conditions are a compromise rather than what is optimal for each product.
[006] Based on these concerns, it is common practice to build separate production trains for each olefin despite the additional cost of capital. It would be desirable to have a multi-reaction train hydroformylation process that could operate using a common catalyst-product separation zone, for example, a vaporizer, as this would result in capital cost savings yet still exhibit robust operational stability. SUMMARY OF THE INVENTION The invention is such a process comprising
[007] Contacting a first CO, H2 reactor train and a first feed stream comprising an olefin in the presence of a hydroformylation catalyst in a reaction fluid under hydroformylation conditions sufficient to form at least one aldehyde product,
[008] Contact in at least one additional CO, H2 reactor train and at least one additional feed stream comprising an olefin, in the presence of a hydroformylation catalyst in a reaction fluid under sufficient hydroformylation conditions to form at least one aldehyde product, in which the additional reactor train is operated in parallel to the first train, and
[009] Remove an effluent flow comprising the reaction fluid from each train and passing the effluent flows from at least 2 reactor trains to a common catalyst-product separation zone.
[0010] Surprisingly, a process in which olefins are fed to separate trains that share a common catalyst-product separation zone and downstream equipment can realize most of the desirable capital savings of a traditional coalification system while avoiding its unforeseen events. BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Figure 1 is a schematic diagram of a hydroformylation process using a common catalyst-product separation zone, for example, a thin film vaporizer.
[0012] Figure 2 is a graph of rhodium concentration and the catalyst division ratio in response to process variation.
[0013] Figure 3 is a graph of rhodium concentration and catalyst division ratio in response to process variation showing improved rhodium control by active flow control.
[0014] Figure 4 is a graph of rhodium concentration and catalyst division ratio in response to process variation, showing improved rhodium control by in-line rhodium analysis.
[0015] Figure 5 is a schematic diagram of a hydroformylation process that employs a common catalyst-product separation zone, for example, a thin film vaporizer.
[0016] Figure 6 is a schematic diagram of a hydroformylation process that employs a common catalyst-product separation zone, for example, a thin film vaporizer.
[0017] Figure 7 is a schematic diagram of a hydroformylation process that employs a common catalyst-product separation zone, for example, a thin film vaporizer.
[0018] Figure 8 is a schematic diagram of a hydroformylation process that employs a common catalyst-product separation zone, for example, a thin film vaporizer. DETAILED DESCRIPTION OF THE INVENTION
[0019] The disclosed process comprises contacting CO, H2 and at least one olefin under hydroformylation conditions sufficient to form at least one aldehyde product in the presence of a catalyst comprising, as components, a transition metal and an organophosphorous ligand.
[0020] All references to the Periodic Table of the Elements and the various groups in it are for the version published in the CRC Handbook of Chemistry and Physics, 72th Ed. (1991-1992) CRC Press, on page I-10.
[0021] Unless otherwise stated, or implied from context, all parts and percentages are based on weight and all testing methods are current as of the filing date of this order. For the purposes of US patent practice, the content of any referenced patent, patent application or publication is incorporated by reference in its entirety, or its equivalent US version is thus incorporated by reference, especially with respect to the disclosure of definitions, until the point not incompatible with any definitions specifically provided in that disclosure, and general knowledge in the art.
[0022] As used here, "one", "one", "at least one", and "one or more" are used interchangeably. The terms "comprise", "includes" and variations thereof do not have a limiting meaning where those terms appear in the description and claims. Thus, for example, an aqueous composition that includes particles of "one" hydrophobic polymer can be interpreted as meaning that the composition includes particles of "one or more" hydrophobic polymers.
[0023] Also in the present invention, the mention of numeric ranges by periods includes all numbers subsumed in that range, for example 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. For the purposes of the invention, it should be understood, consistent with what a person of ordinary skill in the art would understand, that a number range is intended to include and support all possible sub-ranges that are included in that range. For example, the range from 1 to 100 is intended to transmit from 1.01 to 100, from 1 to 99.99, from 1.01 to 99.99, from 40 to 60, from 1 to 55, etc. Also in the present invention, mentions of numerical ranges and / or numerical values, including such mentions in the claims, can be read as including the term "approximately." In such instances the term "approximately" refers to numerical ranges and / or number values that are substantially the same as those mentioned here.
[0024] As used here, the term "ppmw" means part per million by weight.
[0025] For the purposes of this invention, the term "hydrocarbon" is considered to include all permissible compounds having at least one hydrogen and one carbon atom. Such permissible compounds can also have one or more heteroatoms. In a broad sense, permissible hydrocarbons include acyclic organic compounds, with or without heteroatoms, and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic compounds, which can be substituted or unsubstituted.
[0026] As used herein, the term "substituted" is considered to include all allowable substituents on organic compounds unless otherwise indicated. In a broad sense, allowable substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, hydroxyalkyl, aminoalkyl, in which the number of carbons can vary from 1 to 20 or more, preferably from 1 to 12, as well as hydroxy, halo and amino. Permissible substituents can be one or more and the same or different for appropriate organic compounds. This invention is not intended to be limited in any way by the permissible substituents on organic compounds.
[0027] As used herein, the term "hydroformylation" is considered to include, but is not limited to, all hydroformylation processes that involve converting one or more substituted or unsubstituted olefinic compounds or a reaction mixture comprising one or more compounds substituted or unsubstituted olefins in one or more substituted or unsubstituted aldehydes or a reaction mixture comprising one or more substituted or unsubstituted aldehydes. Aldehydes can be asymmetric or non-symmetric.
[0028] The terms "reaction fluid", "reaction medium" and catalyst solution "are used interchangeably here, and may include, but are not limited to, a mixture comprising: (a) a catalyst complex metal-organophosphate ligand, (b) free organophosphorous ligand, (c) aldehyde product formed in the reaction, (d) unreacted reagents, (e) a solvent for the metal-organophosphate ligand complex catalyst and the free organophosphorous ligand , and optionally, (f) one or more phosphorous acid compounds, which can be dissolved and / or suspended, formed in the reaction. The reaction fluid may include, but is not limited to, (a) a fluid in a reactor, (b) a flow of fluid on its way to a separation zone, (c) a fluid in a separation zone, ( d) a recycling stream, (e) a fluid removed from a reaction zone or separation zone, (f) a fluid removed being treated with an acid removal system such as an extractor or other immiscible fluid in contact with the system , (g) treated or untreated fluid returned to a reaction zone or separation zone, (h) a fluid in an external cooler, and (i) ligand decomposition products and components derived therefrom, such as oxides, sulfides, salts, oligomers and the like.
[0029] Any suitable technique to separate the product from the catalyst in the effluents of the reactor train can be employed. Unit operations suitable for use in the catalyst-product separation zone are well known to those skilled in the art and may comprise, for example, solvent extraction, membrane separation, crystallization, settling or phase separation, filtration, distillation and the like , and any combination thereof. Examples of distillation include flashing, clean film evaporation, falling film evaporation, thin film evaporation, and distillation on any other type of conventional distillation equipment. Examples of membrane separation processes are disclosed in US 5,430,194 and US 5,681,473. For purposes of the invention, the term "vaporization" will be used to cover these unit operations, and the term "vaporizer" is used synonymously with "catalyst-product separation zone."
[0030] "Hydrolyzable organophosphorous ligands" are trivalent phosphorous ligands that contain at least one P-Z bond where Z is oxygen, nitrogen, chlorine, fluorine or bromine. Examples include, but are not limited to, phosphites, phosphino-phosphites, bisphosphites, phosphonites, bisphosphonites, phosphites, phosphoramidites, phosphino-phosphoramidites, bisphosphoramidites, fluorophosphites and the like. The ligands may include chelate structures and / or may contain multiple P-Z fractions such as polyphosphites, polyphosphoramidites, etc., and mixed P-Z fractions such as phosphite-phosphoramidites, fluorophosphite-phosphites and the like.
[0031] The term "free ligand" means ligand that is not complexed with, bound to or bonded with, the metal, for example, metal atom of the complex catalyst.
[0032] Hydrogen and carbon monoxide are needed for the process. These can be obtained from any suitable source, including refinery and oil cracking operations. Synthesis gas mixtures are preferred as a source of hydrogen and CO.
[0033] Syngas (syngas) is the name given to a gas mixture that contains varying amounts of CO and H2. Production methods are well known and include, for example: (1) steam reforming and partial oxidation of natural gas or liquid hydrocarbons and (2) the gasification of coal and / or biomass. Hydrogen and CO are typically the main components of syngas, however syngas can contain carbon dioxide and inert gases like N2 and Ar. The molar ratio of H2 to CO varies a lot but generally ranges from 1: 100 to 100: 1 and preferably between 1 : 10 and 10: 1. Syngas is commercially available and is often used as a fuel source or as an intermediary for the production of other chemicals. The most preferred H2: CO molar ratio for chemical production is between 3: 1 and 1: 3 and is normally targeted to be between approximately 1: 2 and 2: 1 for most hydroformylation applications.
[0034] Each reactor train has its own olefin feed flow. Feed flows can be the same or different. In one embodiment of the invention, the first and second feed streams comprise different olefin compositions. For example, the first feed stream may comprise ethylene and / or propylene as a first olefin, and the second feed stream may comprise at least a higher olefin. For purposes of the invention, a higher olefin is an olefin that has 3 or more carbon atoms. As a practical matter, the higher olefin may contain small amounts of ethylene. In one embodiment of the invention, the higher olefin comprises less than 40 weight percent ethylene. In another embodiment of the invention, the higher olefin comprises less than 2 weight percent ethylene.
[0035] Substituted or unsubstituted olefinic unsaturated starting material reagents that can be employed in the hydroformylation process include both optically active (proquiral and chiral) and non-optically active (achiral) unsaturated compounds containing 2 to 40, preferably 3 to 20 carbon atoms. Such olefinic unsaturated compounds can be terminally or internally unsaturated, straight chain, branched chain or cyclic. Mixtures of olefin as obtained from the oligomerization of propene, butene, isobutene, etc., as termed dimeric, trimeric or tetrameric propylene and the like, as disclosed, for example, in US 4,518,809 and 4,528,403, may be employed. In addition, such olefin compounds may further contain one or more additional ethylenic unsaturated groups, and mixtures of two or more different olefinic unsaturated compounds may be employed as the starting hydroformylation material, if desired. For example, commercial alpha olefins containing four or more carbon atoms can contain amounts of corresponding internal olefins and / or corresponding tri-substituted olefins and / or their corresponding saturated hydrocarbons and that such commercial olefins do not necessarily need to be purified from them before being hydroformed. Illustrative mixtures of olefinic starting materials that can be employed in hydroformylation reactions include, for example, mixed butenes, for example, Rafinado I and II. In addition, such olefinic 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 as described, for example, in the patents US 3,527,809, 4,769,498 and the like.
[0036] More preferably, the invention is especially useful for the production of non-optically active aldehydes by hydroformyling aquiral alpha-olefins containing 2 to 30, preferably 3 to 20, carbon atoms, and aquiral internal olefins containing 4 to 20 carbon atoms as well as mixtures of starting material from such alpha olefins and internal olefins.
[0037] Illustrative alpha olefins and internal olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 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-butene, 2-methyl propene (isobutylene), 2-methyl butene, 2 -pentene, 2-hexene, 3-hexane, 2-heptene, 2-octene, cyclohexene, propylene dimers, propylene trimers, propylene tetramers, butadiene, piperylene, isoprene, 2-ethyl-1-hexene, styrene, 4 -methyl styrene, 4-isopropyl styrene, 4-tert-butyl styrene, alpha-methyl styrene, 4-tert-butyl-alpha-methyl styrene, 1,3-diisopropenylbenzene, 3-phenyl-1-propene, 1,4- hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene as well as, 1,3-dienes, butadiene, alkyl alkenoates, for example, methyl pentenoate, alkenyl alkanoates, alkenyl alkyl ethers, alkenyls, for example, pentenois, alkenals , for example, pentenals, allyl alcohol, allyl butyrate, hex-1-en-4-ol, oct-1-en-4-ol, vinyl acetate, allyl acetate, 3-butenyl acetate, vinyl propionate, allyl propionate, methyl methacrylate, vinyl ethyl ether, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenonitrile, 5-hexenamide, eugenol, iso-eugenol, safrole, iso-safrole, anethole, 4-allyl anisol, indene, limonene, beta-pinene, dicyclopentadiene, cyclooctadiene, camfene, linalool, and the like.
[0038] Proqual and chiral olefins useful in asymmetric hydroformylation that can be used to produce enantiomeric aldehyde mixtures include those represented by the formula:
Where R1, R2, R3 and R4 are the same or different, with the proviso that R1 is different from R2 or R3 is different from R4, and are selected from hydrogen; alkyl; substituted alkyl, the substitution being selected from dialkyl amine as benzyl amino and dibenzyl amine, alkoxy as methoxy and ethoxy, acyloxy as acetoxy, halo, nitro, nitrile, thio, carbonyl, carboxamide, carboxaldehyde, carboxyl, carboxylic ester; aryl including phenyl; substituted aryl including phenyl, the substitution being selected from alkyl, amino including alkyl amino and dialkyl amino as benzyl amino and dibenzyl amino, hydroxy, alkoxy as methoxy and ethoxy, acyloxy as acetoxy, halo, nitrile, nitro, carboxyl, carboxaldehyde, carboxylic ester , carbonyl, and uncle; acyloxy as acetoxy; alkoxy such as methoxy and ethoxy; amino including amino alkyl and dialkyl amino; as amino benzyl and dibenzyl amino; acylamino and amino diacyl such as amino benzyl acetyl and amino diacetyl; nitro; carbonyl; nitrile; carboxyl; carboxamide; carboxaldehyde; carboxylic ester; and alkyl mercapto as methyl mercapto. The proquiral and chiral olefins of that definition are also understood to include molecules of the general formula above where the R groups are connected to form ring compounds, for example, 3-methyl-1-cyclohexene, and the like.
[0039] Illustrative optically active or pro-olefinic compounds useful in asymmetric hydroformylation include, for example, p-isobutylstyrene, 2-vinyl-6-methoxy-2-naphthylene, 3-ethylenylphenyl phenyl ketone, 4-ethylenephenyl-2-thienyl ketone, 4-ethenyl-2-fluorobiphenyl, 4- (1,3-dihydro-1-oxo-2H-isoindol-2-yl) styrene, 2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether, propenylbenzene, isobutyl-4 - propenylbenzene, phenyl vinyl ether and the like. Other olefinic compounds include substituted aryl ethylenes as described, for example, in US 4,329,507, 5,360,938 and 5,491,266.
[0040] A solvent is advantageously employed in the hydroformylation process. Any suitable solvent that does not unduly interfere with the hydroformylation process can be used. As an illustration, solvents suitable for rhodium catalyst hydroformylation processes include those disclosed, for example, in US patents 3,527,809, 4,148,830, 5,312,996 and 5,929,289. Non-limiting examples of suitable solvents include saturated hydrocarbons (alkanes), aromatic hydrocarbons, water, ethers, polyethers, alkylated polyethers, aldehydes, ketones, nitriles, alcohols, esters, and aldehyde condensation products. Specific examples of solvents include: tetraglime, pentanes, cyclohexane, heptanes, benzene, xylene, toluene, diethyl ether, tetrahydrofuran, butyraldehyde and benzonitrile. The organic solvent can also contain water dissolved up to the saturation limit. In general, with regard to the production of achiral aldehydes (not optically active), it is preferred to employ aldehyde compounds corresponding to the desired aldehyde products to be produced and / or condensation by-products of the highest boiling aldehyde liquid as the main organic solvents as common in the art. Such aldehyde condensation by-products can also be preformed if desired and used accordingly. Illustrative preferred solvents employed in the production of aldehydes include ketones, for example, acetone and methyl ethyl ketone, esters, for example, ethyl acetate, di-2-ethyl hexyl phthalate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, hydrocarbons, for example, toluene, nitrohydrocarbons, for example, nitrobenzene, ethers, for example, tetrahydrofuran (THF) and sulfolane. In rhodium-catalyzed hydroformylation processes, it may be preferred to employ, as the primary solvent, aldehyde compounds corresponding to the desirable aldehyde products to be produced and / or condensation by-products of higher boiling aldehyde liquid, for example, how it could be produced at the site during the hydroformylation process, as described, for example, in US 4,148,380 and US 4,247,486. Indeed, although a person may employ, if desired, any suitable solvent at the start of a continuous process, the primary solvent will normally eventually comprise both aldehyde products and condensation by-products of higher boiling aldehyde liquid ("heavy residues"), due to the nature of the ongoing process. The amount of solvent is not particularly critical and need only be sufficient to provide the reaction medium with the desired amount of transition metal concentrations. Typically, the amount of solvent ranges from approximately 5 percent to approximately 95 percent by weight, based on the total weight of the reaction fluid. Mixtures of two or more solvents can also be used.
[0041] The catalyst useful in the hydroformylation process comprises a catalytic metal. Catalytic metal can include Group 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.
[0042] The number of coordination sites available on such metals is well known in the art. Thus, the catalytic species, which may comprise a complex catalyst mixture, may comprise monomeric, dimeric or higher nuclear forms, which are preferably characterized by at least one molecule containing organophosphites complexed by a metal molecule, for example, rhodium . For example, it is considered that the catalytic species of the preferred catalyst employed in a hydroformylation reaction can be complexed with carbon monoxide and hydrogen in addition to the organophosphorous ligands in view of the carbon monoxide and hydrogen gas used by the hydroformylation reaction.
[0043] Illustrative metal-organophosphate ligand complexes employed in such hydroformylation reactions covered by that invention include metal-organophosphate ligand complex catalysts. Catalysts, as well as methods for their preparation, are well known in the art and include those disclosed in the aforementioned patents. In general, such catalysts can be preformed or formed on site as described in such references and consist essentially of metal in complex combination with an organophosphorous ligand. Carbon monoxide is also believed to be present and complexed with the metal in the active species. The active species may also contain hydrogen directly attached to the metal. The metal-organophosphate ligand complex catalyst can be optically active or non-optically active.
[0044] The permissible organophosphorous ligands that make up the metal-organophosphate ligand complexes and free organophosphorous ligands include higher triaryl phosphines, mono-, di-, tri- and polyorganophosphites. Mixtures of such ligands can be employed if desired in the metal-organophosphate ligand complex catalyst and / or free ligand and such mixtures can be the same or different. The present invention is not intended to be limited in any way by the permissible organophosphorous ligands or mixtures thereof. It should be noted that the successful practice of the present invention does not depend on and is not based on the exact structure of the metal-organophosphate ligand complex species, which may be present in its mononuclear, dinuclear and / or higher nuclear forms. Really, the exact structure is not known. Although not intended to be limited to any theory or mechanistic discourse, it appears that the catalytic species may in its simplest form consist essentially of metal in a complex combination with the organophosphorous ligand and carbon monoxide and / or hydrogen.
[0045] The term "complex" as used here and in the claims means a coordinating compound formed by the union of one or more electronically rich molecules or atoms capable of independent existence with one or more electronically poor molecules or atoms, each of which also it is capable of independent existence. For example, the organophosphorous ligands employed here may have one or more phosphorus donor atoms, each having an available or unshared electron pair that are individually capable of forming a coordinate bond independently or possibly in combination, for example, through chelation , with the metal. Among the organophosphorous ligands that can serve as the ligand of the metal-organophosphate ligand complex catalyst are fluorophosphites, phospholites, phosphino-phosphoramidites, monoorganophosphite, diorganophosphite, triorganophosphite, organopolyphosphite, organophosphorphite and organophosphoramide compounds. Such organophosphorous ligands and / or methods for their preparation are well known in the art. Mixtures of the above ligands can also be used. Carbon monoxide, which is also properly classified as a ligand, can also be present and complexed with the metal. The final composition of the complex catalyst may also contain an additional ligand, for example, hydrogen or an anion that serves the coordination sites or nuclear charge of the metal. Additional illustrative ligands include, for example, halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF3, C2 F5, CN, (R) 2PO and RP (O) (OH) O, where each R is the same or different and is a substituted or unsubstituted hydrocarbon radical, for example, alkyl or aryl, acetate, acetyl acetonate, SO4, PF4, PF6, NO2, NO3, CH3, CH2 = CHCH2, CH3CH = CHCH2, C6H5CN, CH3CN, NH3, pyridine, (C2H5) 3N, mono-olefins, diolefins and triolefins, tetrahydrofuran and the like. It is to be understood that the complex species is preferably free of any additional organic ligand or anion that could poison the catalyst or have an undue adverse effect on the catalyst performance. It is preferred in hydroformylation reactions catalyzed by an organophosphite-metal ligand complex that the active catalysts are free of halogen and sulfur directly attached to the metal, although this may not be absolutely necessary.
[0046] Organophosphorous compounds that can serve as the metal organophosphorous ligand complex and / or free ligand catalyst ligand can be of the achiral (optically inactive) or chiral (optically active) type and are well known in the art. Aquiral organophosphorous ligands are preferred.
[0047] Representative monoorganophosphites may include those having the formula:
Where R10 represents a substituted or unsubstituted trivalent hydrocarbon radical containing 4 to 40 carbon atoms or more, as trivalent acyclic radicals and trivalent cyclic radicals, for example, trivalent alkylene radicals such as those derived from 1,2,2-trimethylol propane and the like, or trivalent cycloalkylene radicals such as those derived from 1,3,5-trihydroxy cyclohexane, and the like. Such monoorganophosphites can be found described in more detail, for example, in US 4,567,306.
[0048] Representative diorganophosphites may include those having the formula:
Where R20 represents a substituted or unsubstituted divalent hydrocarbon radical containing 4 to 40 carbon atoms or more and W represents a substituted or unsubstituted monovalent hydrocarbon radical containing 1 to 18 carbon atoms or more.
[0049] Representative substituted and unsubstituted monovalent hydrocarbon radicals represented by W in the formula (II) above include aryl and alkyl radicals, while representative substituted and unsubstituted hydrocarbon radicals represented by R20 include divalent acyclic radicals and divalent aromatic radicals. Illustrative divalent acyclic radicals include, for example, alkylene, alkylene-oxyalkylene, alkylene-S-alkylene, cycloalkylene radicals, and alkylene-NR24-alkylene where R24 is hydrogen or a substituted or unsubstituted monovalent hydrocarbon radical with example, an alkyl radical having 1 to 4 carbon atoms. The most preferred divalent acyclic radicals are divalent alkylene radicals as more fully disclosed, for example, in US patents 3,415,906 and 4,567,302 and the like. Illustrative divalent aromatic radicals include, for example, arylene, bisarylene, arylene-alkylene, arylene-alkylene-arylene, arylene-oxy-arylene, arylene-NR24-arylene where R24 is as defined above, arylene-S-arylene, and arylene -S-alkylene, and the like. More preferably, R20 is a divalent aromatic radical as more fully disclosed, for example, in US patents 4,599,206, 4,717,775, 4,835,299 and the like.
[0050] Representatives of a more preferred class of diorganophosphites are those of the formula:
Where W is as defined above, each Ar is the same or different and represents a substituted or unsubstituted aryl radical, each y is the same or different and is a value of 0 or 1, Q represents a divalent bond group selected from - C (R33) 2—, —O—, —S—, -NR24-, Si (R35) 2 and —CO—, where each R33 is the same or different and represents hydrogen, an alkyl radical having 1 to 12 atoms carbon, phenyl, tolyl, and anisyl, R24 is as defined above, each R35 is the same or different and represents hydrogen or a methyl radical, and has a value of 0 or 1. Such diorganophosphites are described in more detail, for example , in US patents 4,599,206, 4,717,775 and 4,835,299.
[0051] Representative triorganophosphites may include those having the formula:
Where each R46 is the same or different and is a substituted or unsubstituted monovalent hydrocarbon radical, cycloalkyl, aryl, alkaryl and aralkyl radicals that can contain 1 to 24 carbon atoms. Such triorganophosphites are described in more detail, for example, in US patents 3,527,809 and 5,277,532.
[0052] Representative organopolyphosphites contain two or more atoms of tertiary phosphorus (trivalent) and may include those having the formula:
Where X represents a substituted or unsubstituted n-valent organic bond radical containing 2 to 40 carbon atoms, each R57 is the same or different and represents a divalent organic radical containing 4 to 40 carbon atoms, each R58 is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing 1 to 24 carbon atoms, a and b can be the same or different and each has a value from 0 to 6, with the proviso that the sum of a + b is 2 to 6 and n is equal to a + b. it must be understood that when a has a value of 2 or more, each radical R57 can be the same or different. Each radical R58 can also be the same or different in any given compound.
[0053] Representative n-valent (preferably divalent) organic bonding radicals represented by X and representative divalent organic radicals represented by R57 above, include both acyclic and aromatic radicals, such as alkylene, alkylene-Qm-alkylene, cycloalkylene, arylene, bisarylene , arylene-alkylene, and arylene- (CH2) y-Qm- (CH2) y-arylene radicals, and the like, wherein each Q, yem are as defined above in Formula (III). The most preferred acyclic radicals represented by X and R57 above are divalent alkylene radicals, while the most preferred aromatic radicals represented by X and R57 above are divalent arylene and bisarylene radicals, as more fully disclosed, for example, in US patents 4,769,498, 4,774,361, 4,885,401, 5,179,055, 5,113,022, 5,202,297, 5,235,113, 5,264,616 and 5,364,950, and 5,527,950. Representative preferred monovalent hydrocarbon radicals represented by each R58 radical above include aromatic and alkyl radicals.
[0054] Illustrative preferred organopolyphosphites may include bisphosphites such as those of formulas (VI) to (VIII) below:
Where each R57, R58 and X of formulas (VI) to (VIII) are the same as defined above for formula (V). Preferably, each R57 and X represents a divalent hydrocarbon radical selected from alkylene, arylene, arylene-alkylene-arylene, and bisarylene, while each R58 represents a monovalent hydrocarbon radical selected from alkyl and aryl radicals. Organophosphite ligands of such formulas (V) to (VIII) can be found disclosed, for example, in US patents 4,668,651. 4,748,261. 4,769,498. 4,774,361. 4,885,401. 5,113,022. 5,179,055. 5,202,297. 5,235,113. 5,254,741. 5,264,616. 5,312,996. 5,364,950. and 5,391,801.
[0055] R10, R20, R46, R57, R58, Ar, Q, X, m, and y in Formulas (VI) to (VIII) are as defined above. More preferably X represents an aryl radical - (CH2) y - (Q) m - (CH2) y-divalent aryl where each y individually has a value of 0 or 1; m has a value of 0 or 1 and Q is -O-, -S- or -C (R35) 2- where each R35 is the same or different and represents hydrogen or a methyl radical. More preferably, each alkyl radical of the R8 groups defined above can contain 1 to 24 carbon atoms and each aryl radical of the above defined groups Ar, X, R57 and R58 of the formulas (VI) to (VII) above can contain 6 to 18 carbon atoms and the radicals can be the same or different, while the preferred alkylene radicals of X can contain 2 to 18 carbon atoms and the preferred alkylene radicals of R57 can contain 5 to 18 carbon atoms. Furthermore, preferably the divalent Ar radicals and X divalent aryl radicals of the above formulas are phenylene radicals in which the bonding group represented by - (CH2) y - (Q) m - (CH2) y - is attached to the radicals of phenylene in positions that are ortho to the oxygen atoms of the formulas that connect the phenylene radicals to its phosphorus atom of the formulas. It is also preferred that any substituent radical when present in such phenylene radicals is attached in the to and / or ortho position of the phenylene radicals with respect to the oxygen atom that binds the substituted phenylene radical given to its phosphorus atom.
[0056] Any of the radicals R10, R20, R57, R58, W, X, Q and Ar of such organophosphites of formulas (I) to (VIII) above can be substituted if desired, with any suitable substituent containing 1 to 30 atoms of carbon that does not unduly adversely affect the desired result of the process of the present invention. Substituents that may be on the radicals in addition to the corresponding hydrocarbon radicals as alkyl, aryl, aralkyl, alkaryl and cyclohexyl substituents, may include, for example, silyl radicals such as --Si (R35) 3; amino radicals such as -N (R15) 2; phosphine radicals such as -aryl-P (R15) 2; acyl radicals like - C (O) R15 acyloxy radicals like -OC (O) R15; starch radicals such as --CON (R15) 2 and -N (R15) COR15; sulfonyl radicals like - SO2 R15, alkoxy radicals like -OR15; sulfinyl radicals such as -SOR15, phosphonyl radicals such as -P (O) (R15) 2, as well as halo, nitro, cyano, trifluoromethyl, hydroxy, and the like, where each R15 radical individually represents the monovalent hydrocarbon radical equal or different having 1 to 18 carbon atoms, for example, alkyl, aryl, aralkyl, alkaryl and cyclohexyl radicals, as a condition that in amino substituents such as -N (R15) 2 each R15 taken together may also represent a group of divalent bond that forms a heterocyclic radical with the nitrogen atom, and in starch substituents such as -C (O) N (R15) 2 and - N (R15) COR15 each R15 attached to N can also be hydrogen. It should be understood that any of the groups of substituted or unsubstituted hydrocarbon radicals that make up a specific given organophosphite can be the same or different.
[0057] As an additional option, any organomonophosphoramidite or organopolyphosphoramidite ligand can be used as or in combination with any other organophosphorous ligand. Organophosphamidite ligands are known, and are used in the same way as organophosphite ligands. Representative organophosphoramidite ligands are of formulas IX-XI.

[0058] Organophosphoramidites are further described, for example, in US 7,615,645.
[0059] The triaryl phosphine employed in the process of this disclosure comprises any organic compound comprising at least one phosphorus atom covalently bonded to three aryl or aryl alkyl radicals, or combinations thereof. A mixture of triaryl phosphine ligands can also be employed. Representative organomonophosphines include those having the formula:
Each R29, R30 and R31 may be the same or different and represent a substituted or unsubstituted aryl radical containing 4 to 40 carbon atoms or more. Such triaryl phosphines can be found described in more detail, for example, in US 3,527,809, the disclosure of which is given here for reference. Illustrative triaryl phosphine ligands are triphenyl phosphine, trinaftyline, tritothyl phosphine, tri (p-biphenyl) phosphine, tri (p-methoxy phenyl) phosphine, tri (m-chlorophenyl) -phosphine, p-N, N-dimethyl aminophenyl bis- phenyl phosphine, and the like. Triphenyl phosphine, that is, the copolyte of formula I in which each R29, R30 and R31 is phenyl, is an example of a preferred organomonophosphine ligand. The hydroformylation reaction is preferably carried out in a liquid body containing excess free triaryl phosphine.
Another preferred class of ligands suitable for the present invention is polidentate ligands as described in WO 2007/078859, US 4,694,109. and US 5,332,846.
[0061] As noted above, metal-organophosphate ligand complex catalysts can be formed by methods known in the art. The metal-organophosphate ligand complex catalysts can be in homogeneous or heterogeneous form. For example, preformed rhodium-organophosphorous-carbonyl-hybrid ligand catalysts can be prepared and introduced into the reaction mixture of a hydroformylation process. More preferably, the organophosphorous-rhodium ligand complex catalysts can be derived from a rhodium catalyst precursor which can be introduced into the reaction medium for formation at the site of the active catalyst. For example, rhodium catalyst precursors such as rhodium dicarbonyl acetyl acetonate, Rh2O3, Rh4 (CO) 12, Rh6 (CO) 16, Rh (NO3) 3, and the like can be introduced into the reaction mixture together with the organophosphorous ligand for on-site formation of the active catalyst. In a preferred embodiment of the present invention, rhodium dicarbonyl acetyl acetonate is employed as a rhodium precursor and reacted in the presence of a solvent with the organophosphorous ligand to form a catalytic organophosphorous ligand complex precursor that is introduced into the reactor together with excess (free) organophosphorous ligand for formation at the site of the active catalyst. In any event, it is sufficient for the purposes of the present invention that carbon monoxide, hydrogen and organophosphorous ligand compound are all ligands that are capable of being complexed with the metal and that an active metal-organophosphate ligand catalyst is present in the reaction mixture under the conditions used in the hydroformylation reaction. Organophosphorus and carbonyl ligands, if not already complexed with the initial rhodium, can be complexed with the rhodium before or at the site during the hydroformylation process.
[0062] As an illustration, the preferred catalyst precursor composition essentially consists of a solubilized rhodium carbonyl organophosphite ligand complex precursor, a solvent and, optionally, free organophosphite ligand. The preferred catalyst precursor composition can be prepared by forming a solution of rhodium dicarbonyl acetylacetonate, an organic solvent and an organophosphite ligand. The organophosphite ligand readily replaces one of the carbonyl ligands in the rhodium acetylacetonate complex precursor at room temperature as witnessed by the evolution of carbon monoxide gas. This substitution reaction can be facilitated by heating the solution if desired. Any suitable organic solvent in which both the rhodium dicarbonyl acetyl acetonate complex precursor and rhodium organophosphite ligand complex precursor are soluble can be employed. The amounts of rhodium complex catalyst precursor, organic solvent and organophosphite ligand, as well as their preferred embodiments present in such catalyst precursor compositions can obviously correspond to those amounts employed in the hydroformylation process of the present invention. Experience has shown that the acetyl acetonate ligand in the precursor catalyst is replaced after the hydroformylation process has started with a different ligand, for example, hydrogen, carbon monoxide or organophosphite ligand, to form the active complex catalyst as explained above . The acetyl acetone that is released from the precursor catalyst under hydroformylation conditions is removed from the reaction medium with the product aldehyde and is therefore in no way detrimental to the hydroformylation process. The use of such preferred rhodium complex catalytic precursor compositions provides an economical, efficient and simple method for manipulating the rhodium precursor and starting hydroformylation.
[0063] Therefore, the organophosphite-metal ligand complex catalyst used in the process of the present invention consists essentially of the metal complexed with carbon monoxide and an organophosphite ligand, the ligand being bound (complexed) with the metal in a chelated way. and / or not chelated. In addition, the terminology "consists essentially of", is used here, does not exclude, but instead includes, hydrogen complexed with the metal, in addition to carbon monoxide and the organophosphite ligand. In addition, such terminology does not exclude the possibility of other organic ligands and / or anions that could also be complexed with the metal. Materials in quantities that unduly adversely poison or improperly deactivate the catalyst are not desirable and thus the catalyst is most desirably free of contaminants such as metal-bound halogen, for example, chlorine, and the like, although this may not be absolutely necessary. The hydrogen and / or carbonyl ligands of an active organophosphite-metal ligand complex catalyst may be present as a result of being ligands attached to a precursor catalyst and / or as a result of on-site formation, for example, due to gases of carbon monoxide and hydrogen used in hydroformylation processes.
[0064] Therefore, the organophosphite-metal ligand complex catalyst used in the process of the present invention consists essentially of the metal complexed with carbon monoxide and an organophosphite ligand, the ligand being bound (complexed) with the metal in a chelated way. and / or not chelated. In addition, the terminology “consists essentially of”, as used here, does not exclude, but instead includes, hydrogen complexed with the metal, in addition to carbon monoxide and organophosphite ligand. In addition, such terminology does not exclude the possibility of other organic ligands and / or anions that could also be complexed with the metal. Materials in quantities that unduly adversely poison or improperly deactivate the catalyst are not desirable and thus the catalyst is most desirably free of contaminants such as metal-bound halogen, for example, chlorine and the like, although this may not be absolutely necessary. The hydrogen and / or carbonyl ligands of an active organophosphite-metal ligand complex catalyst may be present as a result of being ligands attached to a precursor catalyst and / or as a result of on-site formation, for example, due to monoxide gases of carbon and hydrogen used in the hydroformylation process.
[0065] As noted, the hydroformylation process of the present invention involves the use of a metal-organophosphate ligand complex catalyst as described herein. Mixtures of such catalysts can also be employed if desired. The amount of metal-organophosphate ligand complex catalyst present in the reaction fluid of a given hydroformylation process covered by the present invention need only be that minimum amount necessary to provide the desired metal concentration desired and which will provide the basis for at least minus the catalytic amount of metal needed to catalyze the specific hydroformylation process involved as disclosed, for example, in the aforementioned patents. In general, concentrations of catalytic metal, for example, rhodium, in the range of 10 ppmw to 1000 ppmw, calculated as free metal in the reaction medium, should be sufficient for most processes, while it is generally preferred to use 10 to 500 ppmw of metal, and more preferably 25 to 350 ppmw of metal.
[0066] In addition to the metal-organophosphate ligand complex catalyst, free organophosphorous ligand, that is, ligand that is not complexed with the metal, can also be present in the reaction medium. The free organophosphorous ligand can correspond to any of the above defined organophosphorous ligands discussed above as employable here. It is preferred that the free organophosphorous ligand is the same as the organophosphorous ligand of the metal-organophosphate ligand complex catalyst employed. However, such ligands need not be the same in any given process. The hydroformylation process may involve 0.1 moles or less to 100 moles or more of free organophosphorous ligand per mole of metal in the reaction medium. Preferably, the hydroformylation process is carried out in the presence of 1 to 50 moles of organophosphorous ligand per mol of metal present in the reaction medium. More preferably, for organopolyphosphites, 1.1 to 4 moles of organopolyphosphite ligand are employed per mol of metal. The amounts of organophosphorous ligand are the sum of both the amount of organophosphorous ligand that is bound (complexed) with the metal present and the amount of free (not complexed) organophosphorous ligand present. Since it is more preferred to produce non-optically active aldehydes by hydroformylating achiral olefins, the most preferred organophosphorous ligands are achiral ligands, especially those covered by formula (V) above, and more preferably those of formulas (VI), (VII ) and (VIII) above. If desired, additional or composition organophosphorous ligand can be supplied to the reaction medium of the hydroformylation process at any time and in any suitable way, for example, to maintain a predetermined level of free ligand in the reaction medium.
[0067] As indicated above, the hydroformylation catalyst can be in heterogeneous form during the reaction and / or during product separation. such catalysts are particularly advantageous in hydroformylating olefins to produce highly boiling or thermally sensitive aldehydes, so that the catalyst can be separated from the products by filtration or decantation at low temperatures. For example, the rhodium catalyst can be attached to a support so that the catalyst retains a solid form during the stages of both hydroformylation and separation, that is, it is soluble in a liquid reaction medium at elevated temperatures and then precipitates on cooling.
[0068] The use of an aqueous extraction system, preferably employing a buffer solution, to prevent and / or decrease hydrolytic degradation of an organophosphite ligand and inactivation of an organophosphite-metal ligand complex is well known and is disclosed by for example, in US 5,741,942 and US 5,741,944. Such buffer systems and / or methods for their preparation are well known in the art. Buffer mixes can be used.
Illustrative metal-organophosphate ligand complex-catalyzed hydroformylation processes that may experience hydrolytic degradation include those processes as described, for example, in US patents 4,148,830. 4,593,127. 4,769,498. 4,717,775. 4,774,361. 4,885,401. 5,264,616. 5,288,918. 5,360,938. 5,364,950. 5,491,266 and 7,196,230. Species containing P-Z that are likely to undergo hydrolytic degradation include organophosphonites, phosphoramidites, fluorophosphonites, and the like as described in WO 2008/071508, WO 2005/042458, and US Patents 5,710,344. 6,265,620. 6,440,891. 7,009,068. 7,145,042. 7,586,010. 7,674,937. and 7,872,156. These species will generate a variety of acidic and / or polar degradation products that can be removed using technology disclosed in US patents 5,744,649 and 5,741,944. Therefore, the hydroformylation processing techniques that are advantageously employed with the invention disclosed herein can correspond to any known processing techniques. Preferred hydroformylation processes are those involving recycling of catalyst liquid.
[0070] Extraction contact conditions can vary widely and any suitable combination of such conditions can be used here. For example, a decrease in one of these conditions can be offset by an increase in one or more of the other conditions, while the corollary is also true. In general, liquid temperatures ranging from 10 ° C to 120 ° C, preferably from 20 ° C to 80 ° C and more preferably from 25 ° C to 60 ° C, should be suitable in most cases, although lower temperatures or higher can be employed, if desired. Advantageously, the treatment is carried out at pressures varying from environment to reaction pressure, and the contact time can vary from a matter of seconds or minutes to a few hours or more.
[0071] The success in removing phosphorous acid compounds from the reaction fluid can be determined by measuring the rate of degradation (consumption) of the organophosphorous ligand present in the hydroformylation reaction medium. The consumption rate can vary over a wide range, for example from <0.6 to 5 grams per liter per day, and will be governed by the best compromise between ligand cost and treatment frequency to keep hydrolysis below autocatalytic levels. Preferably, the treatment of aqueous buffer solution is carried out in such a way that the consumption of the desired organophosphorous ligand present in the hydroformylation reaction medium is maintained at an acceptable rate, for example, <0.5 grams of ligand per liter per day, and more preferably <0.1 gram of ligand per liter per day, and more preferably <0.06 gram of ligand per liter per day. As the neutralization and extraction of phosphorous acid compounds in the aqueous buffer solution proceeds, the pH of the buffer solution will slowly decrease.
[0072] The removal of at least a certain amount of phosphorous acid compounds, for example, H3PO3, H3PO4, aldehyde acids such as hydroxy alkyl phosphonic acids, such as hydroxyl butyl phosphonic acid and hydroxyl pentyl phosphonic acid, and the like, from The hydroformylation system allows a person to control the acidity of the hydroformylation reaction medium, thereby stabilizing the useful organophosphorous ligand by preventing or decreasing its hydrolytic decomposition.
[0073] A slow loss in catalytic activity has been observed when metal catalysts promoted by organopolyphosphite ligand are employed in processes involving harsh conditions such as recovery of the aldehyde through vaporization.
[0074] Optionally, an organic nitrogen compound can be added to the hydroformylation reaction fluid to clean the acid hydrolysis by-products formed after hydrolysis of the organophosphorous ligand, as taught, for example, in US 4,567,306. Such organic nitrogen compounds can be used to react with and neutralize acid compounds by forming conversion product salts with them, thereby preventing the catalytic metal from complexing with acid hydrolysis by-products and thereby helping to protect the activity of the catalyst while present in the reaction zone under reaction conditions.
Preferred organic nitrogen compounds useful for cleaning phosphorous acid compounds are heterocyclic compounds selected from the group consisting of diazoles, triazoles, diazines and triazines, and the like, as disclosed in US 5,731,472. Benzimidazole and benzitriazole are preferred. The amount of organic nitrogen compound that can be present in the reaction fluid is typically sufficient to provide a concentration of at least 0.0001 moles of free organic nitrogen compound per liter of reaction fluid. In general, the ratio of organic nitrogen compound to total organophosphorous ligand, whether bound or present as free organophosphorous ligand, is at least 0.1: 1 and even more preferably at least 0.5: 1. Molar ratios of organic nitrogen compound: 1: 1 to 5: 1 organophosphorous ligand should be sufficient for most purposes.
[0076] The treatment of aqueous buffer solution will not only remove free phosphoric acid compounds from the reaction fluids containing metal-organophosphate ligand complex catalyst, but also remove the phosphorous acid material from the salt of the conversion product formed using the cleaner. organic nitrogen compound when used, that is, the phosphorous acid of the conversion product salt remains behind in the aqueous buffer solution, while the treated reaction fluid, together with the reactivated (free) organic nitrogen compound is returned to the reaction.
[0077] When using hydrolyzable ligands, it is preferred to employ medium to remove ligand degradation products from the process to avoid acid catalyzed autocatalytic ligand degradation. The use of extractors, amine additives, epoxies and other means is known to control and / or remove these degradation products. See, for example, US 5,741,942. US 5,741,944. JP 3864668. US 5,648,554. US 5,731,473. US 5,744,649. US 5,789,625. US 6,846,960. and US 6,995,292. These degradation product control means are advantageously implemented in the catalyst recycling stream, and can be located before or after the recycling stream is split after the vaporizer.
[0078] The process of the invention employs at least 2 reactor trains, each of which has its own olefin feed flow for the first reaction zone of the train, and each feed flow can be identical to or different from the other. For purposes of the invention, the term "reactor train" means an equipment system comprising at least one reactor that feeds at least a portion of the liquid effluent into a catalyst-product separation zone. a reactor train can have multiple reactors arranged in parallel, series or both. In one embodiment of the invention, the process employs 2 reactor trains. Preferably, trains are operated in parallel, although other modes of operation are possible. For the sake of brevity, the process as described below will refer to a system with two reactor trains. The term “first reactor” refers to the first reactor in the first reactor train. The term "in parallel" is intended to include configurations such as those shown in figures 5, 6 and 8.
[0079] Each reactor vessel can comprise a single reaction zone or multiple reaction zones, as, for example, described in US 5,728,893. In various embodiments of the invention, two or three reaction zones are present in a single reactor vessel.
[0080] Each olefin feed flow is subjected to hydroformylation on its respective train. The first reactor train is characterized by having an olefin feed of higher reactivity per structure, for example, ethylene> propylene> 1-olefins> 2-olefins, or concentration, inert providing lower reactivity. “Reactivity” can be defined as kg-moles of product / h / kg-mol of rhodium or kJ / h / liter of reactor volume. Highly reactive feeds that generate substantial reaction heat must be controlled more closely than less reactive feeds.
[0081] In a reactor or reactor train, reaction zones can be arranged in series or in parallel. The hydroformylation process can be conducted in an elongated tubular zone or series of such zones.
[0082] Examples of single train hydroformylation designs are disclosed in EP 1 008 580, US 5,105,018. US 7,615,645. US 7,329,783, and CN 101293818. In one embodiment, the hydroformylation process can be carried out in a multi-zone or multistage reactor as described, for example, in US 5,728,893. Such multistage reactors can be designed with internal physical barriers that create more than one reaction zone or theoretical reactive stage per container. In reality, a number of reactor zones are contained within a single continuous agitated tank reactor container. Placing multiple reaction zones in a single vessel is a cost-effective way of using reactor vessel volume, and significantly reduces the number of vessels that would otherwise be required to achieve the same results. Having fewer containers reduces the overall capital required and reduces maintenance concerns associated with having separate agitators and containers.
[0083] The hydroformylation process can be carried out using one or more suitable types of reactor such as, for example, a tubular reactor, a bubble column reactor, or a continuous agitated tank reactor (CSTR). A reaction zone can be adapted with one or more internal and / or external heat exchanger (s) to control temperature fluctuations, and to avoid any possible “leak” reaction temperatures.
[0084] The choice of suitable construction materials for process equipment can be readily made by those skilled in the art. The materials used must be substantially inert to the starting materials and the reaction mixture, and the process equipment must be able to withstand reaction pressures and temperatures. For example, the hydroformylation process can be conducted in reaction equipment coated with glass, stainless steel or similar type.
[0085] Means for introducing and / or adjusting the quantity of starting materials or ingredients introduced in batch, semi-continuously or continuously in the reaction zone during the course of the reaction can be conveniently used in the process, and such means are useful to maintain the ratio desired molar content of the starting materials. The reaction steps can be carried out by incrementally adding one of the starting materials to the other.
[0086] The hydroformylation process of the invention can be conducted in one or more zones or stages on each train. As known to those skilled in the art, the exact configuration of reaction trains, including the number of reaction zones or stages, will be governed by the best compromise between capital costs and achieving high selectivity of catalyst, activity, life span and ease of operability, as well as the intrinsic reactivity of the starting materials in question, the stability of the starting materials and the desired reaction product (s) to the reaction conditions on each train.
[0087] In one embodiment, one or more effluent flows from one train are fed to the other reactor train. For example, an effluent flow from the additional reactor train can be added to the second reaction zone of the first reactor train so that the majority of the reaction on both trains has already occurred. The need for strict control of reaction temperature and N: I ratio after the first reaction zone is less critical, and improved conversion of the small amount of remaining olefin (s) is of primary interest. In reality, this configuration employs a reaction zone after the first reaction zone as a “polishing” reaction zone for the other reactor train. In this flow scheme, the common catalyst-product separation zone is processing the output of the two trains, although the effluent from the trains merges to some extent in one of the trains upstream of the catalyst-product separation zone. the modalities of this configuration are shown in figures 5, 6 and 8.
[0088] In one embodiment of the invention, the concentration of catalytic metal in the first reactor is determined indirectly according to methods well known to those skilled in the art. For example, the relative concentration of heavy aldehyde residues, ligands, ligand decomposition products (oxides, etc.) or other markers, which correlate with rhodium, can be analyzed by gas chromatography, high pressure liquid chromatography (HPLC) ), UV-Vis or IR spectroscopy and other well-known techniques. If the catalytic metal concentration is too high or too low, the fraction of the total catalyst recycling mass from the vaporizer can be lowered or raised, respectively, to effect the desired change in the catalytic metal concentration in the first reactor train.
[0089] The catalytic metal concentration in the first reactor can be correlated with the mass ratio of (a) new olefin fed to the first reactor to (b) the total amount of new olefin fed to all reactor trains. Based on this ratio, the metal concentration in the first reactor is controlled by altering the mass ratio of fed catalyst recycling streams to the reactor trains. The relevant flow rates can be measured using mass flow meters. Alternatively, the mass ratio of the catalyst recycling streams can be measured directly.
[0090] Ethylene and propylene hydroformylation reaction kinetics are more responsive to changes in kinetic variables than kinetics for higher olefins. In this way, a preferred control scheme will control the catalytic metal concentration in the first reactor train and allow the catalytic metal concentration in the second reaction train to vary or "fluctuate". The temperature of the second reactor train, which can be controlled by means known to those skilled in the art, can be reduced to compensate for any effects of higher catalytic metal concentrations than design on the second reactor train, if desired.
[0091] The catalytic metal concentration in a reactor can be controlled by monitoring the partial pressure of olefin in the reactor. For a given temperature and partial pressure of CO, the partial pressure of olefin is generally a function of catalytic metal content; therefore, if olefin partial pressure is outside the desired range, then the catalyst recycle flow can be adjusted to maintain the olefin partial pressure within the desired range based on known kinetics for the catalyst. This “inferential control” can employ commercially available monitoring systems.
[0092] In one mode, for added temperature control, especially in the first reactor, it is preferred to keep the partial pressure of H2 considerably lower than stoichiometric requirements, as described in US 4,593,127. This will act as an inherent brake to stop a “leak” reaction since the supply of H2 would be quickly depleted and the reaction would stop. The required H2 can be added to downstream reactors where the potential for leak reactions is lower since there is less olefin available to react.
[0093] Hydroformylation products can be asymmetric, non-asymmetric or a combination thereof, with preferred products being non-asymmetric. The process can be conducted in any batch, continuous or semi-continuous mode and can involve any desired catalyst liquid recycling operation. It is generally preferred to carry out the hydroformylation process in a continuous manner. Continuous hydroformylation processes are well known in the art.
[0094] The reaction conditions of the hydroformylation process in each reactor train can include any hydroformylation conditions of the appropriate type to the present day to produce optically active and / or non-optically active aldehydes. For example, the total pressure of hydrogen gas, carbon monoxide and olefin starting compound in the hydroformylation process can vary from 100 to 69,000 kPa. In general, however, it is preferred that the process be operated at a total pressure of hydrogen gas, carbon monoxide and olefin starting compound less than 14,000 kPa and more preferably less than 3,400 kPa. The minimum total pressure is predominantly limited by the amount of reagents needed to obtain a desired rate of reaction. More specifically, the partial pressure of carbon monoxide in the hydroformylation process is preferably from 1 to 6,900 kPa, and more preferably from 21 to 5,500 kPa, while the partial pressure of hydrogen is preferably from 34 to 3,400 kPa and more preferably from 69 to 2,100 kPa. In general, the molar ratio of H2: CO gas hydrogen to carbon monoxide in a reaction zone can range from 1:10 to 100: 1 or higher, the most preferred molar ratio of hydrogen to carbon monoxide being 1 : 10 to 10: 1.
[0095] In general, the hydroformylation process can be conducted at any operable reaction temperature. Advantageously, the hydroformylation process is carried out at a reaction temperature of -25 ° C to 200 ° C. In general, hydroformylation reaction temperatures of 50 ° C to 120 ° C are preferred for all types of olefinic starting materials. As known to those skilled in the art, the hydroformylation reaction conditions employed are governed by the type of aldehyde product desired.
[0096] It is well known that the N: I ratio of product of linear and branched aldehyde isomers depends on several factors including ligand identity and concentration, normally defined as the ratio of ligand to rhodium, temperature and partial pressures of CO and H2. Known methods for controlling the N: I ratio can be employed in the process of the invention. For example, each train can have Rh concentrations, partial pressures CO and H2 and different temperatures. In the event that the two trains use the same olefin, or two olefins with almost equal reactivity, variation in these parameters may also allow N: I of variable product.
[0097] In one modality, the temperature and partial pressures of CO and H2 in the two trains can be the same or different to optimize conversion and N: I ratio for each olefin in each train. In addition, temperatures and partial pressures in different reactors on each train can be optimized separately depending on the optimal conditions for each olefin. In each reactor train, CO and H2 partial pressures can be optimized and changed independently to adjust for changes in rhodium concentrations and residence times that can result in changes in the catalyst recycling rate and rhodium concentration. This allows for increased reactor stability and N: I product ratio control.
[0098] In one embodiment, a train can be operated under "isomerization conditions" as taught in US 7,615,645. These conditions may be desirable for one olefin feed and not for the other, depending on the desired product mixture.
[0099] In yet another modality, as the feed rates for the separate trains change, the residence time on each train will change and so the reactor temperature (s) on each train can be changed. additionally optimized without impacting the other train. For example, if the supply of power to the first train is reduced, the residence time on the first reactor train will increase. If the conversion is already close to 100%, this longer residence time is not contributing to production, but it only contributes to higher degradation of ligand and formation of heavy residues. Therefore, reaction temperatures can be reduced to reduce these losses without losing significant conversion of olefin.
[00100] It is well known that the reaction rate is a function of temperature and catalyst concentration, among other factors. The conversion rate is mainly controlled by controlling the temperature of the reaction mass and the concentration of the catalyst in each reactor train. In one embodiment, the flow rate of at least one of the catalyst recycling streams is controlled to control the catalyst concentration in the first reactor train. In one embodiment of the invention, control is performed by adjusting the desired concentration of catalytic metal for the first reactor train. In one embodiment of the invention, the concentration of catalytic metal in the first reactor is determined directly by analytical methods, which can be carried out online or offline. Examples of direct analytical methods include inductively coupled plasma mass spectroscopy, atomic absorption spectroscopy, HPLC and X-ray fluorescence.
[00101] At a given temperature, all being equal, the rate of hydroformylation reaction is directly proportional to the catalytic metal concentration. The catalytic metal concentration in each reactor train is related to the mass flow rate and catalytic metal concentration in each recycling stream. Thus, the rate of hydroformylation reaction is a function of the recycling mass flow rate and the catalytic metal catalyst concentration in the recycling flow.
[00102] The process of the invention employs a common catalyst-product separation zone, that is, at least a portion of the effluent from each reactor train is sent, directly or indirectly, to a catalyst-product separation zone shared in which the effluent is separated into a flow comprising mainly product and a flow comprising the relative majority of the catalyst in solution, that is, the catalyst recycling flow. The product stream is advantageously sent for further processing, for example, refinement. The catalyst recycling stream is recycled directly or indirectly back to the reactor trains. In one embodiment of the invention, the catalyst recycling stream leaves the separation zone and is divided directly between the reactor trains. For purposes of the invention, the term "catalyst-product separation zone" means any means for separating a substantial portion of the aldehyde product from a mixture of product and catalyst solution. Advantageously, more than 90% and more preferably more than 95% of the total product that is removed from the process is separated from the catalyst in the catalyst-product separation zone, although relatively small portions of the product can also be collected by other equipment, as sigh knockout containers and the like.
[00103] A preferred and conventional method of catalyst-product separation is distillation, preferably in a falling film evaporator, in one or more stages under normal, reduced or elevated pressure, as appropriate, with the residue containing non-metal catalyst volatilized being recycled to the reactor trains. For example, catalyst separation and recycling for a single train is shown in US 5,288,918, and the separation techniques employed therein can be employed in the process of the invention.
[00104] Preferably, the effluent from the first reactor train is fed directly or indirectly to a vaporizer. Similarly, in an embodiment of the invention, the effluent from the second reactor train is fed directly, for example, as shown in figures 1, 5 and 7, or indirectly, for example, as shown in figures 6 and 8, for the same vaporizer. The unvaporized liquid effluent from the common vaporizer is advantageously divided and recycled for the first and second reactor trains. The product flow of steam effluent from the vaporizer can be manipulated by conventional means, for example, sending it to a refining stage.
[00105] The common vaporizer may comprise multiple vaporization units in series, such as high pressure and low pressure vaporizers, as shown, for example, in CN102826969. For example, each train can have its own high-pressure vaporizer, and each non-volatilized flow from the high-pressure vaporizers is fed to the common low-pressure vaporizer. This allows recycling of light pressurized waste, such as propylene or butene, for each train from the high pressure vaporizer and the separation of catalyst-final product is carried out in the common low pressure vaporizer. In any case, the common final catalyst recycling stream is divided, on or after the vaporizer, and sent back to the reactor trains.
[00106] As indicated above, the desired aldehydes can be recovered from the reaction mixture. For example, the recovery techniques disclosed in US patents 4,166,773, 4,148,830 and 4,247,486 can be employed. In a continuous liquid catalyst recycling process, the portion of the liquid reaction mixture, containing aldehyde product, catalyst, etc., that is, reaction fluid, removed from the reactor trains can be passed to a separation zone of catalyst-product, eg vaporizer / separator, in which the desired aldehyde product can be separated by distillation, in one or more stages, under normal, reduced or elevated pressure, from the liquid reaction fluid, then condensed and collected in a product receiver, and further refined or purified if desired. The remaining liquid reaction mixture containing non-volatilized catalyst can be recycled back to the reactor trains, as can any other volatile materials, for example, unreacted olefin, together with any hydrogen and carbon monoxide after separation from them. condensed aldehyde product. In general, it is preferred to separate the desired aldehydes from the reaction mixture containing catalyst under reduced pressure and at low temperatures in order to avoid possible degradation of the organophosphorous ligand and reaction products.
[00107] More particularly, distillation of the desired aldehyde product from the reaction fluid containing metal-organophosphate complex catalyst can take place at any suitable temperature desired. In general, it is preferred that such distillation occurs at relatively low temperatures, such as below 150 ° C, and more preferably at a temperature in the range of 50 ° C to 140 ° C. It is generally preferred that such aldehyde distillation occurs under a total gas pressure that is lower than the total gas pressure employed during hydroformylation when low boiling aldehydes, for example, C3 to C6 are involved, or under vacuum when boiling aldehydes high, for example, C7 or greater, are involved. In general, distillation pressures ranging from vacuum pressures to a total gas pressure of 340 kPa (49.3 psia) are sufficient for most purposes.
[00108] A common practice is to degas the liquid reaction product medium removed from the hydroformylation reaction before the catalyst-product separation zone in order to volatilize a substantial portion of the unreacted gases dissolved in the liquid medium. These unreacted gases can be recycled, if desired.
[00109] An amazing benefit of using a common vaporizer, compared to separate vaporizers, is that in the case where the olefin in the first reactor train is lighter than the olefin in the other reactor trains, the presence of a high flow of the components lighter (from the first reactor train) will act to help “extract” the higher molecular weight components generated in the second train out of the vaporizer, particularly the heavy aldol residues formed as a natural side reaction. This allows vaporization to be carried out at a lower average temperature, thereby reducing the potential formation of heavy residues and degradation of ligands. These heavy residues, which are described in US 4,148,830, can accumulate over time and limit the life of the catalyst. The vaporizer operating conditions, particularly temperature, are preferably controlled to prevent or minimize degradation of ligand. Ligand degradation is discussed in detail in WO 2010/003073.
[00110] In one embodiment, the catalyst recycling flow sent to each reaction train can be divided between two or more different reactors on each train to control the N: I ratio on each train as taught in WO 2010/087690. This also reduces the average residence time of the catalyst at high temperature, thereby reducing the formation of heavy residues and decomposition of ligand.
[00111] The recycling procedure generally involves removing a portion of the liquid reaction medium containing the catalyst and aldehyde product from at least one of the hydroformylation reactor trains, continuously or intermittently, and recovering the aldehyde product at thereafter by the use of a catalyst-product separation zone. the collection of the removed aldehyde product, typically by condensation of the volatilized materials, and further separation and refining thereof, for example, by distillation, can be carried out in any conventional way, and the crude aldehyde product can be passed on for further purification isomer separation, if desired, and any recovered reagents, for example, olefinic starting material and synthesis gas, can be recycled in any desired way to the hydroformylation zone (reactor). Aldehyde products can be refined by distillation, including multistage distillation, to remove unreacted material and recover a purified product. Unreacted recovered reagents can optionally be concentrated to recycle to the reaction system with or without subsequent processing. The residue containing non-volatilized metal catalyst recovered from such separation can be recycled to one or more of the hydroformylation reactor trains in any desired conventional manner.
[00112] Various types of recycling procedures are known in the art and may involve recycling liquid from the separate metal-organophosphate complex catalyst fluid from the desired aldehyde reaction product (s), such as disclosed, for example, in US 4,148,830. a continuous liquid catalyst recycling process is preferred. Examples of suitable liquid catalyst recycling procedures are disclosed in US patents 4,668,651. 4,774,361. 5,102,505 and 5,110,990.
[00113] The resulting product flow can be processed by conventional means. For example, aldehyde products can be separated and separately processed by hydrogenation or aldolization / hydrogenation in alcohols. Alternatively, the aldehyde products can be hydrogenated and the individual alcohols can be separated after hydrogenation. Another possibility involves aldolization / hydrogenation in a mixture of alcohols and higher alcohols followed by distillation to isolate the individual alcohols. An example of such multiple processing schemes is given in WO 2012/008717.
[00114] The use of an extractor, mentioned above, can introduce various levels of water in the catalyst recycling flows and thus, in the reactor trains. As taught in WO 2012/064586 and JP 2006/306815, the presence of water in hydroformylation reactors can be important to decrease reactor fouling. A main source of this water is from the extractor, and a primary means of removing water is through a vaporizer. Changes in the catalyst recycling rate will necessarily change the amount of water being supplied to each train and it may be desirable to have auxiliary means to add water to each train independently. Alternatively, it may be desirable to maintain a "dry" train to decrease ligand hydrolysis, as taught in US 7,262,330. thus, only treating a catalyst recycling stream may be desirable to remove the degradation acids from the most tolerant train. The extraction process, if employed, may comprise a single container or may comprise two or more distinct containers.
[00115] The hydroformylation process of the invention can be conducted with recycling of unconsumed catalytic and non-catalytic starting materials, if desired. When complete conversion is not desired or not obtainable, the starting materials can be separated from the product, for example, by distillation, and the starting materials then recycled back to a reaction zone.
[00116] Illustrative non-optically active aldehyde products include, for example, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-methyl 1-butyraldehyde, hexanal, hydroxyhexanal, 2-methyl valeraldehyde, heptanal, 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-methylglutaraldehyde, 2-methyladipaldehyde, 3-methyladipaldehyde , 3-hydroxypropionaldehyde, 6-hydroxyhexanal, alkenals, for example 2-, 3- and 4-pentenal, alkyl 5-formylvalerate, 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, heptadecanal, 2-methyl-1-hexadecanal, octadecanal, 2-methyl-1-heptadecanal, nonodecanal, 2-methyl-1-octadecanal, 2-ethyl 1-heptadecanal, 3-propyl-1-hexadecanal, eicosanal, 2-methyl -1- nonadecanal, heneicosanal, 2-methyl-1- eicosanal, tricosanal, cyclohexane-dialdehyde, 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, 2-methyl-1-triacontanal, and the like.
[00117] Illustrative optically active aldehyde products include aldehyde (enantiomeric) compounds prepared by the asymmetric hydroformylation process of the present invention such as, for example, S-2- (p-isobutylphenyl) -propionaldehyde, S-2- (6-methoxy -2-naphthyl) propionaldehyde, S-2- (3-benzoylphenyl) - propionaldehyde, S-2- (p-thienylphenyl) propionaldehyde, S-2- (3-fluoro-4-phenyl) phenylpropionaldehyde, S-2- [ 4- (1,3-dihydro-1-oxo-2H-isoindol-2-yl) phenyl] propionaldehyde, and S-2- (2-methylacetaldehyde) -5-benzoylthiophene.
[00118] Various modalities of the process are shown in figures 1 and 5-8.
[00119] In figure 1, propylene (1) and synthesis gas (2) are fed to the first train represented by the reactor (3). Rafinate C4 (4) and synthesis gas (5) are fed to the second train represented by the reactor (6). The effluent from reactors (3) and (4) are fed into the catalyst-product separation zone (7) in which a product (flow (8)) is separated from the catalyst recycling (flow (9)). (Flow (8)) is condensed by the condenser (10) to obtain mixed aldehydes (11) which are then separated by conventional means, such as distillation. Light residues (12) can be purged or recycled as appropriate. Each reactor train can have optional sighs (13) and portions of each sigh can be recycled as desired. Recycling (flow (9)) comprising catalyst, over-linking, solvent (usually heavy aldehyde residues), residual aldehyde products, and unreacted reagents is returned to the two reactor trains via (flows (14) and (15) ).
[00120] With reference to figure 5, at least a portion of the sigh (flow (13a)) from one or more reactors on one train can be fed to one or more of the reactors on the other train via line (18) preferably , the sigh (flow (18)) from the last reactor in the second train is sent to the first reactor train and, more preferably, to the last reactor (3b) of the first train. Sigh line (13a) can have a knockout container to collect condensable compounds, such as aldehyde products, and the non-condensed olefin and synthesis gas are sent via line 18 to the other train.
[00121] With reference to figure 6, at least a portion of the liquid outlet (flow (17)) from one or more reactors from one train can be fed to one or more of the reactors on the other train via the line (19). Preferably, the output from the last reactor (6) on the second train is sent to the first reactor train via line (19) and more preferably, to the last reactor on the first train. The resulting combined product (16) from the final reactor on the first train, which comprises product from the two trains, is then sent to the common product-catalyst separation zone (7). Line (20) can be used to balance flows or can be used if the first train is not available or if any train is operating at reduced speeds.
[00122] With reference to figure 7, a portion of the catalyst recycling (flow (14)) is divided between reactors in a train. A portion (flow (14)) is diverted through the line (21) to a subsequent reactor (3b). in one embodiment of the invention, the rhodium concentration in any of the first (3a) or subsequent (3b) reactors is controlled. Preferably, the rhodium concentration in the first reactor (3a) on the first train is controlled and is allowed to float in the downstream reactor (3b) on the first train. Preferably, the overall rhodium concentration in the final reactor (3b) on the first train is also monitored, for example in (flow (16)), to determine the ratio of (flow (14)) to (flow (15)) , this is the catalyst division ratio. The flow rate of (flow (21)) can be used to control rhodium concentration in the reactors in the first train to control the N: I ratio as taught in WO 2011/087690.
[00123] In figure 8, two trains are operated in a substantially parallel mode. The supply of catalyst for the first train is at least partially supplied by a portion of the product from the second train (flow (19)) rather than exclusively from the separation zone. The catalyst recycling is substantially entirely sent to the second train via line (9). This scheme can be used when the rhodium requirement for the first train is substantially lower than that for the second train. For example, if the second train operates at 300 ppm Rh and the first train runs at 100 ppm, the output concentration at (flow (17)) is more than sufficient to provide the catalyst needed for the first train. The rhodium concentration in the first train is controlled by the ratio of (flows (19) to (22)) instead of the ratio of (flows (14) to (15)) as in figure 1. The combined products of the two trains (flows (16) and (22)) are then fed to the same separation zone (7). Optionally, line (23) can be used to allow operation if the second train is reduced or if any train is operating at reduced production rates.
[00124] In one embodiment of the invention, the flow rate of (flow 19)) is higher than the corresponding (flow (14)) in figure 1. Therefore, small variations in valve performance will result in a minor percentage change in rhodium concentration on the first train. SPECIFIC MODALITIES OF THE INVENTION
[00125] All parts and percentages in the following examples are by weight unless otherwise indicated. Pressures are given as absolute pressure unless otherwise indicated. Example 1
[00126] ASPEN Plus Dynamics ™ process simulation software is used to develop an Oxo reaction system process control model for the process in Figure 1. The catalyst is a typical Rh bisphosphite-catalyst as described in US 4,668,651 and the reaction conditions are essentially those of example 5 of that patent for butene-1 and Example 9 of that patent for propylene except for the following: a stream of raffinate is used instead of butene-1, the initial target rhodium concentration for the train propylene is 72 ppm Rh, and for the raffinate train the rhodium concentration design target is 260 ppm rhodium, with a Ligand: Rh ratio of> 1 for both trains. These are efficient levels that would be used in conventional plants having two completely separate trains, providing high reaction rates, high conversions, and low ligand consumption at design rates for each train.
[00127] The basis for modeling the reactor control system is as follows: 1) The Oxo reaction rate is directly proportional to the rhodium concentration at constant temperature. 2) Rhodium concentration in each reactor train is a function of the mass flow rate of recycling catalyst and concentration of recycling rhodium fed to each reaction train. The net volume in each reactor is constant. 3) The recycling rhodium concentration is a function of the olefin feed rates of the two catalyst trains and the rhodium concentration in each train and thus the ratio of the outputs of each train being fed to the common vaporizer. 4) The effects of items 1 and 2 combine so that the oxo reaction rate is a function of the recycling catalyst feed rate and recycling catalyst rhodium concentration. 5) Since ethylene and propylene hydroformylation reaction kinetics are more responsive to changes in kinetic variables than raffinate kinetics, the control scheme is designed to control the rhodium concentration of the propylene reactor, and maintain the temperature of the reactor (3) constant, and let the rhodium concentration in the rafinate reaction train vary as needed. The temperature of the raffinate reactor can be reduced to compensate for any rhodium concentrations higher than design.
[00128] The results demonstrate conversion and efficiency that are comparable to those for a process running 2 parallel trains that each have their own catalyst-product separation zones. temperature variations due to changes in rhodium concentration caused by changes in the recycling flow are slow, on the order of hours. Therefore, reactor temperature control is done using conventional cooling techniques such as internal cooling coils, external heat exchangers, or both.
[00129] The process of the invention allows good control of the rhodium concentration profile. This results in good raw material efficiencies, good reactor temperature control and low cost / use of ligand. Example 2
[00130] A series of ASPEN Plus Dynamics ™ process simulations is performed using the process of example 1 to demonstrate the effect of process disturbances on the reactor behavior typically seen in commercial operation. These involve reductions in one feed or the other.
[00131] The sequence of process power disturbances is as follows:. initially, feed flow rates for raffinate and propylene are at design flow rates. . at 4 hours, the raffinate feed flow rate starts to halve the design flow over a 6 hour ramp period. . over 10 hours, the rafinate feed flow is maintained at 50% design rates. . over 40 hours, the raffinate feed flow rate starts to increase by 6 hours returning to design rates. At 46 hours, the raffinate is maintained at design flow rates. . at 75 hours, the propylene feed flow rate starts a 50% reduction ramp that takes 10 hours. . over 85 hours, the propylene supply is maintained at 50% of the design flow rate. . at 103 hours, the propylene feed flow rate starts a 10 hour ramp returning to design flow rates. . at 113 hours, the propylene feed rate is maintained at the design flow rate until the end of the simulation course.
[00132] Figure 2 shows the variation over time of the rhodium concentration and the catalyst division ratio, which is the mass flow rate of (flow (14)) divided by the mass flow rate of the flow of vaporizer tail (flow (9)). Figure 2 shows the rhodium concentration profiles that result from the process disturbances described above. The catalyst mass flow rates for reactors 3 and 6 are initially adjusted to design values. Throughout the disturbance sequence, the catalyst flow to reactor 3 is maintained at the design rate and the flow to reactor 6 is allowed to vary as determined by the material balance. No process control is in place to adjust the catalyst recycling flow rates to respond to process variations that occur in the reaction system, such as the feed flow rate changes illustrated here.
[00133] The dotted line is the initial target for rhodium concentration (72 ppm), the solid line is the effective rhodium concentration in the reactor (3) and the dotted line is the catalyst division ratio. With a constant design recycle catalyst flow rate (flow (14)) to reactor 3, the catalyst split ratio changes with vaporizer tail flow rate variations. A constant fraction of the combined reactor effluent is removed from the vaporizer (7) as a product and, as such, a constant fraction of the effluent goes into (flow (9)). With changes in the reagent feed rate, the effluent flow rate will change and correspondingly, the flow of (flow (9)) will change. The rhodium concentration will also change as the fraction of the vaporizer supply for each reactor train changes and the two trains operate at significantly different rhodium concentrations. Given these changes, the concentration of reactor rhodium (3) varies correspondingly over a wide range. As Figure 2 shows, the rhodium concentration of the reactor (3) varies between -12 ppm to +30 ppm from the design setpoint, resulting in poor reactor performance. In particular, for the time period between 20 and 40 hours when the propylene supply does not change, the rhodium concentration drops by 17%, which reduces the efficiency of the reactor by a comparable amount. A disturbance in the raffinate train has a dramatic impact on the propylene train, which is surprising. So, between 75 and 113 hours when the propylene feed rate is the lowest, the rhodium concentration in the propylene train is the highest, when it is not needed compared to the rafinate train, effectively the rhodium concentration is reduced in the raffinate flow. Example 3
[00134] Example 2 is repeated except that a different inspection scheme is used, as follows:
[00135] Maintain the propylene reactors, reactor (3), at constant temperature and vary the catalyst recycling mass flow rate (14) to obtain the desired rhodium concentration. The purpose of the control scheme is to keep the propylene reactors, reactor (3), in constant reactivity and vary the catalyst recycling mass flow rate (14) to obtain the desired rhodium concentration. The approach is to "infer" the rhodium concentration of the reactor (3) based on the balance of general material and physical volume and geometry of the Oxo reaction system from which the change in control is determined. Once the total rhodium inventory is known and fixed, the effect of changes in the operation of each reactor train can be used to predict performance. The main variable for each reaction train is the supply of olefin, propylene and raffinate for reactors (3) and (6), respectively.
[00136] The contrast scheme consists of the integration of two advanced feed controllers to adjust the recycled catalyst feed to the reactor (3) (flow (14). The first controller takes the propylene feed measurement, multiplies it by a gain factor, and adds an adjustment propensity to calculate the required recycled catalyst feed flow rate. This causes the catalyst recycle feed flow rate to be reduced by a predetermined proportional amount when the propylene feed a measured quantity is reduced. The second controller takes the rafinate feed flow measurement, multiplies it by a second gain factor, and adds a trend to calculate a coefficient that is multiplied to the result of the first controller. the flow portion of the recycling reactor going to the propylene reactors during a reduction of rafinat feed The. The product of this algorithm is sent to the set point of a conventional feedback flow controller to regulate the recycling catalyst supply to the first propylene reactor (3).
[00137] The performance of the scheme is shown in figure 3. It shows a 50% reduction in the raffinate feed followed by the return to design flow rates. After that is a 50% reduction in the propylene supply followed by its return to design fees. The controller coefficients were calculated based on the main effects of feed rates on the rhodium concentration of the process due to the dilution effect of product formation. if interaction / side effects were included, the variation of reactor rhodium would have been less. However, the effect of reduced propylene for falling rhodium concentration is seen as advantageous since less rhodium is required in the decreased production rate.
[00138] The rhodium concentration of the reactor (3) is controlled at ± 4 ppm in the first half of the simulation. After hour 80, a drop in rhodium concentration with a decrease in propylene feed rate is advantageous because less rhodium is needed to achieve the same conversion. This is in contrast to example 2, where the rhodium level increases to a high level in the reactor (3) and the high rhodium level has no benefit. Specifically, the longer contact time in the reactor (3) negates the need for higher rhodium levels, since after ca. At 100% conversion, no benefit is obtained from the added rhodium. At hour 103, the propylene supply starts to return to the original value and the rhodium concentration in the reactor (3) increases proportionally back to the original rhodium concentration setpoint. Controlling the catalyst split ratio is the key to maintaining the proper reactor rhodium (3) concentration in relation to the propylene feed. This provides the best performance on the most sensitive reactor train. Example 4
[00139] Example 2 is repeated except that a different control scheme is employed. The control scheme employs an in-line rhodium analyzer that samples the liquid output from the reactor (3) (flow (16)). The analyzer provides a rhodium concentration value that is used to adjust the catalyst recycling flow (flow (14)) to maintain the desired rhodium concentration in the reactor (3). The results are shown in figure 4.
[00140] Figure 4 above shows the required catalyst split Ratio versus time for a range of propylene and raffinate feed rates. The rhodium analyzer is a reliable flow analyzer that is calibrated and periodically updated with manual laboratory analysis according to methods known to those skilled in the art. Figure 4 shows that the rhodium concentration can be controlled to ± 2 ppm in the reactor (3). Since rhodium concentrations are maintained at design levels, the two trains have the optimal rhodium concentrations. Since the rhodium concentration is constant in the reactor (3), a lower reaction temperature can be used in the propylene train to reduce ligand decomposition and formation rates of heavy aldehyde residues if desired without loss of conversion one the residence time is longer when the propylene feed rate is reduced. Similarly, reactor operating temperatures on the raffinate reaction train (reactor 6) can be lowered to maintain the required reaction rate, based on effective olefin feed rates.
[00141] These examples show that compared to a conventional process using separate trains, the invention can be operated stably at comparable performance while being able to respond to typical process disturbances.
[00142] The invention offers the following advantages: 1) Rhodium can be moved from one reactor to another (in a few hours) to match the olefin feed rates so that the rhodium concentration is optimized in each reaction train. This aspect is also an advantage when starting or whenever a new rhodium catalyst charge is required because only a rhodium catalyst concentration is required for the catalyst charge. Any desired rhodium concentration for a reactor train can be achieved by simply adjusting the recycling catalyst division (between flows 14 and 15) while circulating the catalyst through reactors and vaporizer for a few hours. 2) The process allows good control of rhodium concentration and operating temperatures, resulting in minimized consumption of ligand and formation of heavy residues. 3) The partial pressures of CO and H2 in each train can be independently controlled to optimize N: I and avoid side reactions, for example, olefin hydrogenation, ligand decomposition, in which the optimal conditions may be different for each olefin. 4) The combined catalyst recycling stream will contain residual components from the two trains which can help to reduce fouling that would occur on separate but parallel trains. For example, the lighter residual components of the first train may exhibit better solubilities for materials that tend to encrust on the second train, thereby avoiding operational difficulties that would occur on totally separate trains.

权利要求:
Claims (15)
[0001]
1. Hydroformylation process, characterized by the fact that it comprises: - contacting a first CO, H2 reactor train and a first feed stream comprising an olefin in the presence of a hydroformylation catalyst in a reaction fluid under sufficient hydroformylation conditions to form at least one aldehyde product, - contact at least one additional CO, H2 reactor train and at least one additional feed stream comprising an olefin, in the presence of a hydroformylation catalyst in a reaction fluid under conditions of sufficient hydroformylation to form at least one aldehyde product, in which the additional reactor train is operated in parallel to the first train, and - remove an effluent flow comprising the reaction fluid from each train and pass the effluent flows from at least 2 reactor trains for a common catalyst-product separation zone, - the olefin composition of the first feed stream is different from olefin composition of at least one additional feed stream, and - the hydroformylation conditions in the first reactor train being different from the hydroformylation conditions in at least one additional reactor train.
[0002]
2. Process, according to claim 1, characterized by the fact that it also comprises conducting the separation in the separation zone to produce a product flow and a recycling flow of liquid containing catalyst; dividing the recycling stream into a first recycling stream and a second recycling stream; and returning the first recycling stream at least partially to a reaction train and returning the second recycling stream at least partially to another reaction train.
[0003]
3. Process according to claim 2, characterized in that at least a portion of the liquid recycling flow is sent to the second train and the liquid effluent flow from the second train is at least partially sent to the first train and at least partially sent to the catalyst-product separation zone.
[0004]
4. Process according to claim 1, characterized in that the separation in the catalyst-product separation zone comprises vaporization, in which the term vaporization refers to unit operations that are selected from the group consisting of solvent extraction , membrane separation, crystallization, phase separation or decantation, filtration, distillation and any combination thereof.
[0005]
5. Process according to claim 1, characterized in that at least one train produces at least one process or flow of effluent, and at least part of the process or flow of effluent is added to at least one reactor on the other train.
[0006]
6. Process according to claim 1, characterized in that the second train produces at least one stream of steam, at least part of which is sent to at least one reactor in the first train.
[0007]
7. Process, according to claim 1, characterized by the fact that the effluent flow from the second train is sent to a reaction zone on the first train that is downstream of the first reaction zone on the first train.
[0008]
8. Process according to claim 1, characterized in that the olefin from the first feed stream is selected from the group consisting of propylene, ethylene and mixtures thereof.
[0009]
Process according to claim 1, characterized in that the olefin in the first feed stream comprises propylene and the olefin in the second feed stream comprises butene.
[0010]
10. Process according to claim 1, characterized in that the reaction temperature of at least one reaction zone of each train is controlled in response to a combination of the olefin feed rate, olefin concentration and metal concentration catalytic for each relevant zone.
[0011]
11. Process according to claim 1, characterized by the fact that the concentration of the catalyst in each train is changed to changes in the olefin feed rate for any train.
[0012]
12. Process according to claim 1, characterized in that the catalyst comprises a catalyst metal chosen from Rh, Co, Ir, Ru, Fe, Ni, Os, Pt or Pd and an organophosphorous ligand, and the concentration of catalytic metal in the first reactor train is controlled by measuring the catalytic metal concentration in at least one reactor and / or at least one of the recycling streams and controlling the flow rate of at least one recycling stream.
[0013]
13. Process according to claim 12, characterized in that the concentration of the catalytic metal is measured by atomic absorption, X-ray fluorescence, or inductively coupled plasma mass spectroscopy and / or measured at least in a flow of recycling catalyst components that correlate with rhodium metal concentration by GC, UV-vis and / or HPLC.
[0014]
14. Process according to claim 2, characterized by the fact that the amount of the first recycling stream, in relation to the second recycling stream, is determined by inferential means based on an observed reactor temperature, partial pressures of olefin and CO, and total pressure to control the partial pressure of olefin within a desired range.
[0015]
Process according to claim 4, characterized in that the olefin in the first reactor train is lighter than the olefin in at least one additional reactor train.

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EP3083542A1|2016-10-26|

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US20160257635A1|2016-09-08|

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TW201529551A|2015-08-01|

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JP2020002161A|2020-01-09|

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US9688598B2|2017-06-27|

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法律状态:
2020-01-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-10-27| B09A| Decision: intention to grant|

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2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361918353P| true| 2013-12-19|2013-12-19|

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US61/918,353|2013-12-19|

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PCT/US2014/069190|WO2015094781A1|2013-12-19|2014-12-09|Hydroformylation process|

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