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WO2001051441A1 - Procedes d'hydroformylation, pour la production d'aldehydes a partir d'olefines a encombrement sterique - Google Patents

Procedes d'hydroformylation, pour la production d'aldehydes a partir d'olefines a encombrement sterique Download PDF

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Publication number
WO2001051441A1
WO2001051441A1 PCT/US2001/000135 US0100135W WO0151441A1 WO 2001051441 A1 WO2001051441 A1 WO 2001051441A1 US 0100135 W US0100135 W US 0100135W WO 0151441 A1 WO0151441 A1 WO 0151441A1
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olefins
catalyst
ligand
rhodium
tert
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English (en)
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William Anthony Slegeir
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Eastman Chemical Co
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Eastman Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions

Definitions

  • the present invention relates to hydroformylation of certain sterically hindered olefins to produce aldehydes.
  • the present invention relates to solubilized rhodium phosphite complex catalyzed hydroformylation of specific sterically hindered olefins to produce aldehydes.
  • the present invention relates to a hydroformylation process for preparing aldehydes from C 6 -C ⁇ sterically hindered olefins using a rhodium containing catalyst and a triorganophosphite ligand and particularly triarylphosphite ligands.
  • the hydroformylation process also known as the oxo process, involves the oxygenating an olefinic feedstock to produce an aldehyde having one carbon atom greater than the mono-olefin feedstock.
  • the process typically includes contacting the olefinic feedstock with carbon monoxide and hydrogen in the presence of a catalyst, typically at an operating pressure greater than about 400 psi and a temperature greater than about 120°C.
  • a catalyst typically at an operating pressure greater than about 400 psi and a temperature greater than about 120°C.
  • the most extensive use of the oxo process is for preparing normal- and iso-butyraldehyde from propylene.
  • the ratio of normal aldehyde product to the iso aldehyde product typically is referred to as the normal to iso (N:I) or the normal to branched (N:B) ratio.
  • N:I normal to iso
  • N:B normal to branched
  • the normal- and iso-butyraldehydes obtained from propylene are in turn converted into many commercially-valuable chemical products such as, for example, n-butanol, 2-ethyl- hexanol, n-butyric acid, isobutanol, neopentyl glycol, 2,2,4-trimethyl-l,3-pentanediol, the mono-isobutyrate and di-isobutyrate esters of 2,2,4-trimethyl-l,3-pentanediol.
  • the process involves conducting an oxo reaction with a hexene mixture composed mainly of methyl pentenes, as produced by dimerization of propylene, and a cobalt catalyst to obtain a heptanal product in which carbonylation has occurred primarily on the terminal carbon and then conducting an aldol reaction of the heptanal product to obtain C ⁇ alcohols.
  • the patent further discloses that the cobalt catalyst produces a relatively high ratio of aldehydes without 2-branching, as is necessary for aldol reactions to give a good yield of aldol product.
  • the oxo reaction is operated under pressures of from 500 psig to 5000 psig.
  • 4,263,449 discloses a process for producing an alcohol by hydroformylation of an olefin in a substantially water immiscible solvent and in the presence of a hydroformylation catalyst which is soluble in the solvent. Water is added to the reaction mixture at a ratio of from 0.5 to 30 times the amount, by weight, of the resulting aldehyde. The product is then hydrogenated in the presence of a hydrogenation catalyst. The resulting product is separated by phase separation. The intermediate aldehyde is not separated prior to hydrogenation.
  • the hydroformylation catalyst used is HRh(CO)(PR 3 ) 3 or HRh(CO) 2 (PR 3 ) 2 where the PR 3 moiety is an organic tertiary phosphine and R is a C 2 -C 2 o alkyl group or C 6 -C 20 aryl group.
  • U.S. Patent No. 4,599,206 discloses the use of diorganophosphite ligands in Group VIII transition metal complex catalyzed carbonylation processes.
  • U.S. Patent No. 4,426,542 discloses a process for converting butenes to Cio plasticizer alcohols having at least 80-90 % 2-propylheptanol using an oxo reaction of the butenes to obtain amyl aldehydes followed by an aldol reaction of the aldehydes under conditions to cause the n-pentanal to react but with incomplete conversion of branched aldehydes.
  • the process further includes hydrogenating the product to produce alcohols.
  • the oxo stage of the process is conducted under usual conditions pertaining to cobalt catalyzed hydroformylation reactions, i.e., pressures from 1000 psig to 5000 psig.
  • U.S. Patent Nos. 3,527,809 and 3,917,661 disclose an oxo process having high normal to iso isomer ratios for ⁇ -olefin feedstock and using a rhodium containing complex in the presence of tertiary organo-containing ligands containing a trivalent atom of Group VA including phosphorus, arsenic and antimony.
  • ligands includes trialkylphosphites and triarylphosphites.
  • sterically hindered olefins and particularly sterically hindered C 6 -C ⁇ olefins from refinery olefinic feedstock having low alpha olefin content and large amounts of skeletal carbon branching and particularly where the ratio of alpha olefins to the sum of branched chain and internal olefins is less than about 3/1 are capable of hydro formylation, i.e., aldehyde formation, via hydroformylation using a group VIII transition metal containing catalyst and an effective amount of a ligand selected from a triarylphosphites, sterically hindered tri-organophosphites containing at least one aryl group and fluorophosphites.
  • such hydroformylation reactions of the present invention involve the production of aldehydes by reacting an olefinic unsaturated compound with carbon monoxide and hydrogen in the presence of a solubilized Group VIII transition metal- phosphite complex catalyst in a liquid medium that may contain a solvent for the catalyst, and free phosphite ligand, i.e. ligand that is not complexed with the Group VIII metal in the active complex catalyst.
  • the catalysts which are contemplated consist of rhodium in complex combination with an effective amount of a ligand containing trivalent atom of a Group VA element which preferably is phosphorous.
  • the ligand is selected from a fluorophosphite or triarylphosphite a compound.
  • the fluorophosphite is represented by the formula:
  • Ri and R 2 are independently selected from alkyl of up to 8 carbon atoms, benzyl, cyclopentyl, cyclohexyl, cycloheptyl or an aryl group having the formula:
  • R 3 and R 4 are independently selected from alkyl, alkoxy, halogen, cycloalkoxy, formyl, alkanoyl, cycloalkyl, aryl, aryloxy, aroyl, carboxyl, carboxylate salts, alkoxycarbonyl, alkanoyloxy, cyano, sulfonic acid and sulfonate salts in which the alkyl moiety of such alkyl, alkoxy, alkanoyl, alkoxycarbonyl and alkanoyloxy groups contains up to 8 carbon atoms; m and n independently are 0, 1 or 2.
  • the total carbon atom content of the hydrocarbyl radicals represented by i and R 2 is from 2 to 35.
  • the Ri and R groups may also be bound to each other by a carbon atom to carbon atom bridge linkage, whereby the Ri and R 2 groups may be connected together by 0, 1, or 2 carbon atoms linked between the two R groups.
  • the fluorophosphite is 2,2'-ethylidenebis(4,6-di-tert-butyl ⁇ henyl)fluorophosphite.
  • the ratio of gram moles fluorophosphite ligand to gram atoms rhodium is about 1 : 1 to 70: 1.
  • fluorophosphite ligands are described in greater detail in U.S. Patent No.
  • triarylphosphite ligands and certain sterically hindered triorgano-phosphites incorporating at least one aryl group represent the preferred class of ligands.
  • Suitable examples of such include triphenylphosphite, trinaphthylphosphite, tri(p-methoxyphenyl)phosphite, bis(2,4-di-tert-butylphenyl) pentaerithyritol diphosphite, (2,4,6-tri-tert-butylphenyl)-2-butyl-2-ethyl-l,3-propanediol phosphite, tetra(2,4-di-tert- butyl)biphenylene diphosphite and phenyl neopentylglycol phosphite.
  • the preferred triarylphosphite ligand is tris(2,4-di-tert-butylphenyl)phosphite.
  • the Group VIII metals of the catalyst compound may be provided in the form of various metal compounds such as carboxylate salts of the transition metal.
  • the Group VIII metal is rhodium.
  • Rhodium compounds that may be used as a source of the rhodium for the active catalyst include rhodium II or rhodium III salts of carboxylic acids.
  • suitable materials include di-rhodium tetraacetate dihydrate, rhodium(II) acetate, rhodium(II) isobutyrate, rhodium(II) 2-ethylhexanoate, rhodium(II) benzoate and rhodium(II) octanoate.
  • rhodium carbonyl species such as Rh 4 (CO) ⁇ 2 , Rh ⁇ (CO)i6 and rhodium(I) acetylacetonate dicarbonyl may be suitable rhodium feeds.
  • rhodium sources are rhodium salts of strong mineral acids such as chlorides, bromides, nitrates, sulfates, and phosphates.
  • the concentration of the rhodium and ligand in the hydro formylation reaction mixture is not critical for the production of oxygenated hydrocarbons in accordance with the present invention.
  • the concentration of rhodium in the reaction mixture may vary from 1 mg/liter up to 5000 mg/liter or more.
  • the concentration of rhodium in the reaction solution is in the range of about 20 to about 1000 mg/liter, preferably from about 20 to about 500 mg/liter and most preferably from about 20 to about 300 mg/liter. Concentrations of rhodium lower than this range generally do not yield acceptable reaction rates with most olefin reactants and/or require reactor operating temperatures that are so high as to be detrimental to catalyst stability.
  • the ratio of gram moles of ligand to the gram atoms of the transition metal can vary over a wide range, e.g., gram mole ligand:gram atom transition metal ratios of about 1 : 1 to 200: 1.
  • the gram mole ligand:gram atom rhodium ratio preferably is in the range of about 1 :1 up to 70:1 with ratios in the range of about 1 :1 to 12:1 being particularly preferred.
  • a gram mole ligand:gram atom rhodium ratio of at least 1 : 1 normally is maintained in the reaction mixture. Concentrations of rhodium lower than this range generally do not yield acceptable reaction rates with most olefin reactants and/or require reactor operating temperatures that are so high as to be detrimental to catalyst stability.
  • Solvents are not required in the practice of the invention but often times their use is desirable and practical. Normally liquid, organic solvents which are inert or which do not interfere to any substantial degree with the desired hydroformylation reaction under the operative conditions employed are acceptable. Such compounds and materials include various alkanes, cycloalkanes, alkenes, cycloalkenes, carbocyclic aromatic compounds, alcohols, esters, ketones, acetals, ethers and water.
  • solvents include alkane and cycloalkanes such as dodecane, decalin, octane, iso-octane mixtures, cyclohexane, cyclooctane, cyclododecane, methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene isomers, tetralin, cumene, alkyl-substituted aromatic compounds such as the isomers of diisopropylbenzene, triisopropylbenzene and tert- butylbenzene.
  • alkane and cycloalkanes such as dodecane, decalin, octane, iso-octane mixtures, cyclohexane, cyclooctane, cyclododecane, methylcyclohexane
  • aromatic hydrocarbons such as benzene, tolu
  • reactant alkenes and cycloalkenes such as 1,7-octadiene, dicyclopentadiene, 1,5-cyclooctadiene, octene-1, octene-2, 4-vinylcyclohexene, cyclohexene, 1,5,9-cyclododecatriene, 1-pentene and the like may be used as solvents.
  • suitable solvents include: crude hydrocarbon mixtures such as naphtha; mineral oils and kerosene; high-boiling esters such as 2,2,4-trimethyl-l,3- pentanediol diisobutyrate.
  • the aldehyde product of the hydroformylation process also may be used.
  • the preferred solvent is the higher boiling by-products that are naturally formed during the process of the hydro fonnylation reaction and the subsequent steps, e.g., distillations, that are required for aldehyde product isolation.
  • the main criteria for the solvent is that it dissolves the catalyst and olefin feedstock and does not act as a poison to the catalyst. Accordingly, recycle olefins in combination with fresh olefin reactor feed is a suitable solvent.
  • Preferred solvents for the production of aldehydes are those that have a sufficiently high boiling point to remain, for the most part, in a gas sparged reactor.
  • Solvents and solvent combinations that are preferred for use in the production of less volatile and non-volatile aldehyde products include 1- methyl-2-py ⁇ olidinone, dimethyl-formamide, perfluorinated solvents such as perfluoro- kerosene, sulfolane, water, and high boiling hydrocarbon liquids as well as combinations of these solvents. It has been have found that non-hydroxylic compounds, in general, and hydrocarbons, in particular, may be used advantageously as the hydroformylation solvent since their use can minimize decomposition of the fluorophosphite ester ligands.
  • a desirable and unique feature of the present invention is the low operating pressure of the hydroformylation process.
  • Acceptable total pressures of carbon monoxide and hydrogen for the process range from about atmospheric to less than about 450 psig. Desirably, total pressures range from atmospheric to about 350 psig and preferably less than about 300 psig.
  • the molar ratio of hydrogen to carbon monoxide in the reactor can be varied and is generally selected depending upon the operating parameters of the reaction system. Typically, however, such hydrogenxarbon monoxide ratios are from 1 : 10 to 10:1.
  • the process may be carried out at temperatures in the range of about 20° to 200°C.
  • Preferred hydroformylation reaction temperatures are from about 50°C to about 135°C, and more preferred temperatures range from about 75° to about 125°C. Higher reactor temperatures are not favored because of increased rates of catalyst decomposition while lower reactor temperatures result in relatively slow reaction rates.
  • the olefins that may be hydroformylated by means of our novel process comprise aliphatic, including ethylenically-unsaturated, refinery distillation cuts which will contain a mixture of olefins over a range of several carbon numbers, preferably in the range of C 6 through C 12 and desirably have from 75 mole % to about 100 mole % unsaturated hydrocarbons.
  • the alpha olefin content of the feedstock can be less than about 40 mole %, as little as less than about 5 mole % or contain essentially 0 mole % alpha olefins, i.e. where all the detectable olefins in the mixture may be internal olefins or have at least one carbon-skeletal branch.
  • the present invention is particularly useful in the hydroformylation of refinery olefins, such as those derived from Polygas or Dimersol as olefin mixtures. Depending on the hydro carbonaceous feedstocks and the degree of refining, these olefins may consist of predominantly one carbon number fraction, or may cover a range of different molecular weights.
  • feeds with high alpha-olefin contents are preferred.
  • substantially linear olefins with lower alpha-olefin contents are acceptable feedstocks.
  • An advantage of the present invention is the ability to use refinery olefins containing very little alpha-olefin and which have high amounts of skeletal carbon branching.
  • the catalysts described in this invention are effective with olefin mixtures that contain little, or no alpha-olefin. These catalysts are effective with olefin mixtures that may contain a high level of highly branched components.
  • the refinery olefins are economically advantaged as feeds for hydroformylation, when compared to pure alpha-olefins or olefin mixtures that are predominantly linear.
  • the catalyst and ligand system can also be used for hydroformylation of such olefinic feedstocks having ethylenically-unsaturated, low molecular weight polymers, such as poly-butadiene, alicyclic, aromatic and heterocyclic mono-, di- and tri-olefms containing up to about 40 carbon atoms.
  • aliphatic olefins examples include straight and branched, unsubstituted and substituted, aliphatic mono- ⁇ -olefins containing up to about 20 carbon atoms.
  • Aliphatic di-olefins may contain up to about 40 carbon atoms.
  • the groups that may be present on the substituted mono- ⁇ -olefins include hydroxy; alkoxy including ethers and acetals; alkanoyloxy such as acetoxy; amino including substituted amino; carboxy; alkoxycarbonyl; carboxamido; keto; and cyano.
  • the cyclic olefins which may be used in the hydroformylation process of the present invention may be cycloalkenes, e.g., cyclohexene, 1,5-cyclooctadiene, and cyclodecatriene, and from various vinyl-substituted cycloalkanes, cycloalkenes, heterocyclic and aromatic compounds.
  • cyclic olefins include 4- vinylcyclohexene, 1,4-cyclohexadiene, 4-cyclohexene-carboxylic acid, methyl 4- cyclohexene-carboxylic acid, 1,4-cyclooctadiene and 1,5,9-cyclododecatriene.
  • any of the known hydro formylation reactor designs or configurations may be used in carrying out the process provided by the present invention.
  • a gas- sparged, vapor take-off reactor design may be used.
  • the catalyst which is dissolved in a high boiling organic solvent under pressure does not leave the reaction zone and the aldehyde product taken overhead by the unreacted gases.
  • the overhead gases are chilled in a vapor/liquid separator to condense and/or collect the aldehyde product and the gases can be recycled to the reactor.
  • the liquid product is let down to atmospheric pressure for separation and purification using conventional techniques known to those skilled in the separation art.
  • the process also may be practiced in a batchwise manner using an autoclave and contacting the olefin, hydrogen and carbon monoxide with the catalyst and ligand described herein and under hydroformylation conditions.
  • Another acceptable hydroformylation reactor design is a liquid overflow where catalyst and feedstock are pumped into a reactor and are allowed to overflow with product aldehyde.
  • the aldehyde product may be separated from the catalyst by conventional means such as by distillation or extraction.
  • the catalyst is then recycled back to the reactor.
  • two or more liquid overflow reactors may be used in series to give high conversions of the olefin feedstock.
  • the aldehydes made by the process of the present invention can be hydrogenated to form alcohols, which may be converted to useful plasticizers such as diisoheptylphthalate or diisodecylphthalate and the like.
  • the aldehydes made may further be oxidized using an appropriate oxygenation source, such as air, to form the corresponding carboxylic acids.
  • a particular advantage of the catalyst of the present invention is the production of aldehydes having minimal carbon branching on the carbon atom alpha to the aldehyde group using low pressure hydroformylation conditions.
  • the corresponding alcohol derivatives are particularly desirable for plasticizer applications due to their greater reactivity to form plasticizer esters.
  • the present invention is further illustrated by the following example.
  • a catalytic solution was prepared under nitrogen using 0.52 grams (1.0 mmol) of dicarbonylacetylacetonato rhodium (I) (available from Strem Chemicals, Newburyport, MA, ACS number 14874-82-9), 4.6 grams (5mmole) of tris(2,4-di-t-butyl) phosphite (Tradename Irgafosl 68 available from Ciba-Geigy Corporation or Ultranox 668 available from General Electric Specialty Chemicals) and 125 mL of polygas nonene having 99.6% olefin content and a bromine number (as per ASTM 1 159) of 148 as a solvent.
  • I dicarbonylacetylacetonato rhodium
  • the catalytic solution was warmed to assure all components dissolved.
  • the catalytic solution was charged to a 1.0 L stainless steel Parr Series 4520 mini-reactor equipped with a magnetic drive and gas entrainment impeller along with another 525mL of the polygas nonene and 20 mL n-heptane, as internal standard.
  • the reactor was loaded and unloaded in a glove box.
  • the reactor was sealed and pressurized to 300 psig using a 1 : 1 premixture of hydrogen and carbon monoxide (syngas).
  • the reactor was heated to 120°C and maintained between 300-400 psi by adding syngas. After 6.2 hours, the supply of syngas was stopped, stirring ceased, the reactor was cooled and vented.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Un procédé de préparation d'un aldéhyde consiste à mettre un mélange d'oléfines C6-C12 provenant d'une substance oléfinique de raffinerie, de l'hydrogène, du monoxyde de carbone, avec un catalyseur d'hydroformylation dans des conditions d'hydroformylation. Ledit catalyseur comprend un métal de Groupe VIII et un ligand en dose efficace, choisi parmi les triarylphosphites, les tri-organophosphites à encombrement stérique contenant au moins un groupe aryle et les fluorophosphites.
PCT/US2001/000135 2000-01-12 2001-01-03 Procedes d'hydroformylation, pour la production d'aldehydes a partir d'olefines a encombrement sterique Ceased WO2001051441A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2003061822A3 (fr) * 2002-01-22 2003-12-18 Eastman Chem Co Stabilisation de catalyseurs contenant du fluorophosphite
WO2004024662A1 (fr) * 2002-09-16 2004-03-25 Eastman Chemical Company Procede de reduction d'impuretes renfermant des fluorures consecutivement a l'emploi de catalyseurs au fluorophosphite
US7674937B2 (en) 2008-05-28 2010-03-09 Eastman Chemical Company Hydroformylation catalysts
US8513468B2 (en) 2010-12-30 2013-08-20 Eastman Chemical Company Process for removing degradation acids from hydroformylation reactions
US10766839B2 (en) 2016-02-11 2020-09-08 Dow Technology Investments Llc Process for converting olefins to alcohols, ethers, or combinations thereof

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EP0503564A2 (fr) * 1991-03-14 1992-09-16 Mitsubishi Chemical Corporation Méthode pour la préparation d'un aldéhyde
EP0518241A2 (fr) * 1991-06-11 1992-12-16 Mitsubishi Chemical Corporation Procédé d'hydroformylation et composé bisphosphite utilisé
US5648554A (en) * 1995-04-12 1997-07-15 Mitsubishi Chemical Corporation Method for producing aldehydes
US5840647A (en) * 1997-09-15 1998-11-24 Eastman Chemical Company Hydroformylation process using novel phosphite-metal catalyst system
WO2000047590A1 (fr) * 1999-02-10 2000-08-17 Centre National De La Recherche Scientifique (Cnrs); Tris [(1h,1h, 2h,2h-perfluoroalkyl) aryl]phosphites et leurs applications en catalyse

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003061822A3 (fr) * 2002-01-22 2003-12-18 Eastman Chem Co Stabilisation de catalyseurs contenant du fluorophosphite
US6831035B2 (en) 2002-01-22 2004-12-14 Eastman Kodak Company Stabilization of fluorophosphite-containing catalysts
US6906225B2 (en) 2002-01-22 2005-06-14 Eastman Chemical Company Stabilization of fluorophosphite-containing catalysts
CN1315572C (zh) * 2002-01-22 2007-05-16 伊斯曼化学公司 包含氟亚磷酸酯的催化剂的稳定作用
WO2004024662A1 (fr) * 2002-09-16 2004-03-25 Eastman Chemical Company Procede de reduction d'impuretes renfermant des fluorures consecutivement a l'emploi de catalyseurs au fluorophosphite
US6995292B2 (en) 2002-09-16 2006-02-07 Eastman Chemical Company Process for reducing fluoride impurities resulting from use of fluorophosphite catalysts
CN1326825C (zh) * 2002-09-16 2007-07-18 伊斯曼化学公司 减少由使用氟亚磷酸酯催化剂而产生的氟化物杂质的方法
US7674937B2 (en) 2008-05-28 2010-03-09 Eastman Chemical Company Hydroformylation catalysts
US8513468B2 (en) 2010-12-30 2013-08-20 Eastman Chemical Company Process for removing degradation acids from hydroformylation reactions
US10766839B2 (en) 2016-02-11 2020-09-08 Dow Technology Investments Llc Process for converting olefins to alcohols, ethers, or combinations thereof

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