WO2008056501A1 - Procédé de coproduction de butanol normal et d'isobutyraldéhyde - Google Patents

Procédé de coproduction de butanol normal et d'isobutyraldéhyde Download PDF

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WO2008056501A1
WO2008056501A1 PCT/JP2007/069711 JP2007069711W WO2008056501A1 WO 2008056501 A1 WO2008056501 A1 WO 2008056501A1 JP 2007069711 W JP2007069711 W JP 2007069711W WO 2008056501 A1 WO2008056501 A1 WO 2008056501A1
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group
compound
reaction
liquid
catalyst
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Japanese (ja)
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Tomohiko Inoue
Yoshiyuki Tanaka
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Mitsubishi Chemical Corporation
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Priority to CN2007800364966A priority Critical patent/CN101522598B/zh
Priority to BRPI0718007-1A priority patent/BRPI0718007B1/pt
Publication of WO2008056501A1 publication Critical patent/WO2008056501A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Definitions

  • the present invention relates to a method for co-production of normal butanol and isobutyraldehyde, and more particularly to a method for co-production of normal butanol and isobutyraldehyde using propylene as a raw material.
  • a method for producing aldehydes by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a catalyst comprising a transition metal belonging to Groups 8 to 10 of the periodic table and an organophosphorus ligand Is widely known as a hydroformylation reaction.
  • a catalyst comprising a transition metal belonging to Groups 8 to 10 of the periodic table and an organophosphorus ligand
  • organophosphorus ligands Is widely known as a hydroformylation reaction.
  • aldehydes having higher linearity are useful among the obtained aldehydes, and various organophosphorus ligands have been developed to enhance the linearity selectivity.
  • the high linearity aldehyde obtained in this way usually has the ability to make an alcohol by a hydrogenation reaction, and a hydrogenation reaction after converting it to an aldehyde having a high molecular weight by a condensation reaction. By converting it to alcohol, it is used as a raw material for plasticizers, adhesives and paints.
  • Patent Document 1 European Patent No. 0420510
  • Non-patent document 1 Journal ⁇ Ob ⁇ The ⁇ Chemical Society ⁇ Chemical ⁇ Communications (J. Chem. 3 ⁇ 4oc., Chem. Commun.), 1990
  • Non-Patent Document 2 Journal ⁇ Ob ⁇ The ⁇ Chemical Society ⁇ Dalton'Transactions (J. Chem. Soc., Dalton Trans.), 1996, 1st dish
  • the reaction process is also one step, and if a new method that can produce the by-product to be produced in a more valuable form is presented, it will become one of the economically advantageous and effective methods and is very important. It can be said that it is expensive.
  • isobutyraldehyde which is a similar compound to isobutanol, is an extremely valuable product compared to isobutanol!
  • isobutyraldehyde from isobutanol In order to achieve this, a dehydrogenation reaction step is required, and accordingly, the production cost is increased.
  • the conventional method for producing butyraldehyde from propylene by hydroformylation has a certain power. In this method, isobutyraldehyde can be obtained in the first stage, but in order to obtain normal butanol, normal butylation produced by hydroformylation of propylene is required. As described above, this method has a high manufacturing cost.
  • the present invention has been made in view of the above problems.
  • an object of the present invention is to provide a new and simple method capable of co-producing normal butanol and isobutyraldehyde by reacting propylene with hydrogen and carbon monoxide in the presence of a catalyst.
  • the present inventors have found that propylene in a proton solvent in the presence of a compound of a metal element belonging to Group 8 to Group 10 of the periodic table and an organophosphorus compound. This was reacted with hydrogen and carbon monoxide to find a method for producing both normal butanol and isobutyraldehyde in a yield of 10% or more, and the present invention was completed based on the strength and knowledge. That is, the gist of the present invention resides in the following (1) to (11).
  • Step A React propylene with hydrogen and carbon monoxide in a proton solvent in the presence of the catalyst containing a metal element compound belonging to Groups 8 to 10 of the periodic table in the reactor.
  • organophosphorus compounds, proton solvents normal butanol, isobutanol, normal butyraldehyde, isobutyraldehyde and low boiling point compounds.
  • Step B The reaction product stream obtained in Step A is flowed into the first distillation column, and a column containing normal butyraldehyde, isobutyraldehyde and a low boiling point compound from the top of the first distillation column.
  • the top distillate is withdrawn, a liquid containing normal butanol and isobutanol is withdrawn as a side stream, and a column bottom liquid containing a compound of a metal element belonging to Group 8 to Group 10 and an organophosphorus compound is obtained. Circulating to the reactor;
  • Step C The column top distillate obtained in Step B is allowed to flow into a second distillation column, and a low boiling point compound is withdrawn as a distillate from the top of the second distillation column. Extracting aldehyde as a side stream and extracting normal butyraldehyde as a bottom liquid;
  • Step D The side stream obtained in Step B is allowed to flow into a third distillation column, isobutanol is extracted as a distillate from the top of the third distillation column, and normal butanol is removed from the bottom of the column.
  • isobutanol is extracted as a distillate from the top of the third distillation column, and normal butanol is removed from the bottom of the column.
  • Step A Propylene is hydrogenated and monooxidized in a proton solvent in the presence of the catalyst containing a compound of a metal element belonging to Groups 8 to 10 of the periodic table in the reactor. Reaction with carbon and reaction products containing the above-mentioned compounds of metal elements belonging to Group 8 to Group 10, organophosphorus compounds, proton solvents, normal butanol, isobutanol, normal butyraldehyde, isobutyraldehyde and low boiling point compounds A process of obtaining logistics;
  • Step ⁇ The reaction product stream obtained in step ⁇ is flowed into the first distillation column, and isobutanol, normal butyraldehyde, isobutyl aldehyde, and low boiling point from the top of the first distillation column.
  • a column top distillate containing a compound is withdrawn, normal butanol is withdrawn as a side stream, and a column bottom liquor containing a metal compound belonging to Group 8 to Group 10 and an organic phosphorous compound is added to the reactor.
  • Step C ' The column top distillate obtained in step B' is caused to flow into a second distillation column, and a low boiling point compound is withdrawn as a distillate from the top of the second distillation column.
  • both normal butanol and isobutyraldehyde can be simultaneously produced in a yield of 10% or more.
  • FIG. 1 is a diagram illustrating a reaction flow in the present embodiment.
  • FIG. 2 is a view showing a preferred embodiment in the reaction flow of FIG.
  • FIG. 3 is a diagram for explaining a second reaction flow in the present embodiment.
  • FIG. 4 is a view showing a preferred embodiment in the reaction flow of FIG.
  • the method of co-production of normal butanol and isobutyraldehyde is a compound of a metal element belonging to Group 8 to Group 10 of the periodic table (hereinafter simply referred to as “metal compound” or “Group 8 to Group 10”.
  • metal compound a metal element belonging to Group 8 to Group 10 of the periodic table
  • propylene is reacted with hydrogen and carbon monoxide in the presence of an organic phosphorus compound, and the propylene feed rate F (mol / hr) and isobutyl are reacted with the reaction system.
  • Aldehyde formation rate F (mol / hr) is
  • a compound of a metal element belonging to Group 8 to Group 10 of the periodic table and an organophosphorus compound is a catalyst used in the present embodiment.
  • the metal compound used in the present embodiment is a transition metal compound selected from the group consisting of metal elements belonging to Groups 8 to 10 of the periodic table (according to the IUPAC Inorganic Chemical Nomenclature Revised Edition (1998)). Can be mentioned. As a force and metal compound, it contains one or more transition metals. Compound is used.
  • Such metal compounds include iron compounds, ruthenium compounds, osmium compounds, cobalt compounds, rhodium compounds, iridium compounds, nickel compounds, palladium compounds, and platinum compounds.
  • a ruthenium compound, a rhodium compound, an iridium compound, a nickel compound, a noradium compound, and a platinum compound are preferable, and a rhodium compound is particularly preferable.
  • the types of these metal compounds are arbitrary, but specific examples include the above transition metal acetates, acetyl acetylates, halides, sulfates, nitrates, organic salts, inorganic salts, alkene coordination compounds.
  • Iron compounds include Fe (OAc), Fe (acac),
  • Ruthenium compounds include RuCl, Ru (OA
  • cobalt compound examples include Co (OAc), Co (acac), CoBr, Co (NO), and the like.
  • Rhodium compounds include RhCl, Rhl, Rh (NO), Rh (OAc), RhCl (CO)
  • Examples of the iridium compound include IrCl, Ir (OAc), and [IrCl (cod)].
  • Compounds include NiCl, NiBr, Ni (NO), NiSO, Ni (cod) NiCl (PPh), etc.
  • Palladium compounds include PdCl, PdCl (cod), PdCl (PPh), P
  • Platinum compounds include Pt (acac), PtCl (cod), PtCl (CH CN), PtCl (PhCN
  • cod is 1,5-cyclooctagen and dba is dibenzylic.
  • Acac is acetylylacetonate
  • Ac is a acetylyl group
  • Ph Each group represents a phenyl group.
  • the type of the metal compound is not particularly limited, and any monomer, dimer and / or multimer can be used as long as they are active metal complex species.
  • the amount of the metal compound used is not particularly limited, but from the viewpoint of catalyst activity and economy, the concentration of the metal compound in the reaction medium is usually 0.1 ppm or more, preferably Ippm or more, more preferably ⁇ 10 ppm.
  • the above is usually 10, OOOppm or less, preferably ⁇ 1, OOOppm or less, more preferably 500ppm or less.
  • organophosphorus compound used in this embodiment examples include phosphine or phosphite having the ability as a monodentate ligand or a polydentate ligand.
  • the organic phosphine compound (hereinafter, sometimes referred to as “monodentate phosphine”) having the ability as a monodentate ligand used in the present embodiment is represented by the following general formula.
  • the organic phosphine compound preferably has a molecular weight of 1,500 or less, preferably 1,000 or less, which is preferably dissolved under the reaction conditions in order to sufficiently exhibit the catalytic activity.
  • it is 800 or less.
  • R, R and R each independently represent a C 1 to C 30 alkyl group or aryl group which may have a substituent.
  • a halogen atom hydroxy group, formyl group, chain or cyclic alkyl group, aryl group, alkoxy group, aryl group alkoxy group, aryl group. It is selected from a single-oxy group, an alkylary single-oxy group, an alkylthio group, an arylthio group, an amino group, an amide group, an acyl group or an acyloxy group.
  • organic phosphine compound examples include triphenylphosphine, tri-tolylphosphine, 1-naphthyldiphenylphosphine, 4-methoxyphenyldiphenylphosphine, and tris (2, 4, 6 trimethoxyphenylenole).
  • Phosphine Tris (3,5 Diphenylenolene) Triaryl type monodentate phosphine such as phosphine, 4-dimethylaminophenyl 2-naphthylphosphine; diphenyl-n-propylphosphine, n-octadecyldiphenylphosphine
  • Triaryl type monodentate phosphine such as phosphine, 4-dimethylaminophenyl 2-naphthylphosphine; diphenyl-n-propylphosphine, n-octadecyldiphenylphosphine
  • Diaryl monoalkyl-type monodentate phosphines such as di (3-t-butyl-2-naphthinore) methylphosphine, isopropyl-1-naphthyl-p-tolylphosphine, 2-ethylhexyl
  • At least one of the substituents is a dialyl monoalkyl type monodentate phosphine, a monoaryldialkyl type monodentate phosphine, or tri Alkyl-type monodentate phosphines are preferred.
  • Trialkyl-type monodentate phosphines in which all substituents of R, R, and R are alkyl groups are more preferred.
  • R, R, and R are primary alkyl groups, that is, alkyl groups in which the carbon atom bonded to the P atom is a CH group.
  • Tri (primary alkyl) type monodentate phosphines are more preferred.
  • it is most preferable that all the substituents of R, R, and R are unsubstituted linear alkyl groups.
  • the most preferred monodentate phosphines are trimethylphosphine, tritylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, tree-n.
  • Jetyl-n-octylphosphine ethylmethyl-n-propylphosphine are listed with the power S.
  • a phosphine having the ability as a bidentate ligand or a polydentate ligand can also be used as the phosphine compound.
  • Examples of phosphites having the ability as monodentate ligands include phosphite compounds represented by the following formulas (2) to (5).
  • examples of the optionally substituted monovalent hydrocarbon group include an alkyl group, an aryl group, a cycloalkyl group, and the like.
  • Specific examples of the compound represented by the formula (2) include, for example, trimethyl phosphite, triethyl phosphite, n-butyl jetyl phosphite, tri-n butyl phosphite, tri-n-propyl phosphite, tricyclo Trialkyl phosphites such as hexyl phosphite, tri-n-octyl phosphite, tri-n dodecyl phosphite; triaryl phosphites such as triphenyl phosphite, trinaphthyl phosphite; dimethyl phenyl phosphite, dimethyl Examples thereof include alkyl phosphites such as phenyl phosphite and ethyl diphenyl phosphite.
  • a substituent may be present on the aryl group of these phosphites.
  • bis (3, 6, 8 tri-t-butyl 2- Naphthinole) phenyl phosphite, bis (3, 6, 8 tri-tert-butyl-2-naphthyl) (4-biphenyl) phosphite, etc. may be used. The most preferred of these! / Is triphenyl phosphite.
  • R 4 is substituted! /, May be! /
  • a divalent hydrocarbon group, R 5 is substituted! /, May be monovalent carbon Represents a hydrogen group.
  • the optionally substituted divalent hydrocarbon group represented by R 4 includes an alkylene group which may contain an oxygen, nitrogen, sulfur atom or the like in the middle of the carbon chain; A cycloalkylene group which may contain an oxygen, nitrogen, sulfur atom or the like in the middle; a divalent aromatic group such as phenylene or naphthylene; a divalent aromatic ring directly or in the middle of an alkylene group, oxygen, nitrogen A divalent aromatic group bonded through an atom such as elemental or sulfur; a divalent aromatic group and an alkylene group bonded directly or in the middle through an atom such as oxygen, nitrogen or sulfur Is
  • Examples of the optionally substituted monovalent hydrocarbon group represented by R 5 include an alkyl group, an aryl group, and a cycloalkyl group.
  • Specific examples of the compound represented by the formula (3) include, for example, ethylene (2, 4, 6 tri-t-butyl-phenolino phosphite), 1, 2 butylene (2, 6-di-t-butyl thiolene). And enyl) phosphites and the like, which are described in US Pat. No. 3,415,906.
  • R 1 () has the same meaning as R 5 in formula (3), and Ar 1 and Ar 2 each independently represent an optionally substituted arylene group.
  • X and y each independently represent 0 or 1
  • Q is a bridging group selected from the group consisting of CR U R 12 OS—, — NR 13 —, — SiR 14 R 15 and one CO.
  • R 11 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group, or an anisyl group
  • R 13 , R 14, and R 15 each independently represent Represents a hydrogen atom or a methyl group, and n represents 0 or 1.
  • Specific examples of the compound represented by the formula (4) include, for example, US Patent No. 4 such as 1, 1 ′ bif ⁇ nluo 2, 2 ′ diluo (2, 6 di-tert-butyl-4-methylphenyl) phosphite. No. 599206, 3, 3′-di-t-butyl-5,5′-dimethoxy 1,1,2′-biphenyl 1,2,2,1-di-yl (2-t-butyl 4-methoxyphenyl) Nore) Phosphite and the like are described in US Pat. No. 4,717,775.
  • R 6 represents a cyclic or acyclic trivalent hydrocarbon group which may be substituted.
  • multidentate phosphite examples include phosphite compounds represented by the formulas (6) to (11).
  • R 7 has the same meaning as R 4 in Formula (3), R 8 and R 9 each independently represent a hydrocarbon group that may be substituted; And b each represents an integer of 0 to 6, the sum of a and b is 2 to 6, and X represents a (a + b) -valent hydrocarbon group.
  • Preferred examples of the compound represented by the formula (6) include, for example, 6, 6 ′-[[3,3 ′, 5,5, -tetrakis (1,1, -dimethylethyl)-[1,1, -biphenyl] 2, 2, benzyl] bis (oxy)] bis-benzo [d, f] [l, 3, 2] dioxaphosphevin and the compounds described in JP-A-2-231497 Is mentioned.
  • X represents alkylene, arylene, and one Ar 1 — (CH) x-Qn- (CH) y-Ar 2
  • R 16 and R 17 each independently represent an optionally substituted hydrocarbon group.
  • Ar 2 , Q, x, y, n are synonymous with the formula (4).
  • Specific examples of the compound represented by formula (7) include, for example, JP-A-62-116535. And compounds described in JP-A-62-116587.
  • R iy and R 2 ° each independently represents an aromatic hydrocarbon group, and at least one of the aromatic hydrocarbon groups is bonded to a carbon atom to which an oxygen atom is bonded. It has a hydrocarbon group at the adjacent carbon atom, m represents an integer of 2 to 4, and each —O—P (OR 19 ) (OR 2 °) group may be different from each other.
  • M) -valent hydrocarbon group which may be represented by the formula (9)
  • the compounds represented by the formula (9) for example, compounds described in JP-A-5-178779 and 2,2′-bis (Di 1-naphthyl phosphite) 3, 3 ', 5, 5'-tetra-t-butyl 6, 6'-dimethyl-1, 1' Biphenyl etc. are described in Japanese Patent Laid-Open No. 10-45776! Preferable compounds such as /!
  • R 21 to R 24 represent an optionally substituted hydrocarbon group, and even if they are independent of each other, R 21 and R 22 , R 23 and R 24 may be bonded to each other to form a ring
  • W represents a divalent aromatic hydrocarbon group which may have a substituent
  • L represents a substituent! / Y! / Represents a saturated or unsaturated divalent aliphatic hydrocarbon group.
  • R 25 to R 28 represent an optionally substituted monovalent hydrocarbon group, and R 25 and R 26 , R 27 and R 28 are bonded to each other to form a ring.
  • W and B which may be formed independently represent a divalent aromatic hydrocarbon group which may have a substituent, and n represents an integer of 0 or 1.
  • a combination of these organic phosphorus compounds can also be used.
  • the catalyst system used in the method for co-production of normal butanol and isobutyraldehyde to which the present embodiment is applied is provided. It is formed.
  • the amount of the organophosphorus compound used in the catalyst system is not particularly limited, but is arbitrarily set so that desirable results can be obtained with respect to reaction results, catalyst activity and catalyst stability.
  • the organophosphorus compound is usually 0.1 mole or more, preferably 1 mole or more, more preferably 2 moles or more, usually 1,000 moles or less, preferably 500 moles or less, more preferably 1 mole or more per mole of the metal compound. Is less than 100 moles.
  • the catalyst used in the present embodiment may be prepared in advance in a catalyst preparation zone provided separately, and then the catalyst may be added to the reaction zone, or each catalyst may be individually added to the reaction zone to prepare the catalyst in the reaction zone. It's okay to go!
  • the preferred method for preparing the catalyst is as follows: normal butanol and isobutyl After the aldehyde co-production reaction, there is a method of separating the product system and the catalyst system and recycling the catalyst to the reaction zone again. In this case, depending on the degree of deterioration or disappearance of the catalyst, a metal compound is appropriately used. Desirable to supplement with organic phosphorus compounds! /
  • the metal compound and the organic phosphorus compound may be mixed as they are to prepare the catalyst, or those previously dissolved in an organic solvent or the like are mixed. May be.
  • the catalyst is guided to the reaction zone in a dissolved state so that the catalyst reaction is quickly started in the reaction zone.
  • a gas treatment necessary for heat treatment or conversion to a catalytically active species for example, a pressure contact with a gas such as hydrogen or carbon monoxide is performed in advance. Once done, the catalyst may be introduced into the reaction zone.
  • the co-production of normal butanol and isobutyraldehyde to which this embodiment is applied is carried out in a protic solvent.
  • the protic solvent is a solvent that can be dissociated and easily release protons (H +).
  • protic solvent examples include methanol, ethanol, n propanol, isopropanol, n butanol, isobutanol, t butyl alcohol, n pentanol, neopentyl alcohol, n hexanol, 2-ethylhexanol, and n otano.
  • alcohol is a preferred protic solvent.
  • Load of purification process From the viewpoint of reduction, it is preferable to use alcohol produced as a product as a protic solvent.
  • the amount of the protic solvent used in the present embodiment is usually 5% by weight or more, preferably 10% by weight or more, and usually 95% by weight or less, preferably based on the total weight of the reaction medium. 90% by weight or less.
  • the solvent may be formed of a single compound or a mixture of a plurality of compounds, but it is at least 1% by weight, preferably 5% by weight or more, more preferably, based on the total weight of the solvent. It is necessary to contain 10% by weight or more of a protic solvent.
  • the other solvent that can be used is one that dissolves the catalyst and the raw material compound and does not adversely affect the catalyst activity. Any solvent can be used, and the type is not particularly limited.
  • solvents include, for example, ethers such as diglyme, diphenyl ether, dibenzyl ether, dialyl ether, tetrahydrofuran (THF), dioxane; N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, etc.
  • ethers such as diglyme, diphenyl ether, dibenzyl ether, dialyl ether, tetrahydrofuran (THF), dioxane; N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, etc.
  • Ketones such as acetone, methyl ethyl ketone, methyl t-butyl ketone, cyclohexanone, etc .
  • esters such as ethylhexyl terephthalate; aromatic hydrocarbons such as benzene, toluene, xylene, and dodecylbenzene; aliphatic hydrocarbons such as pentane, hexane, and octane.
  • the reaction pressure formed by the sum of the partial pressure of hydrogen, carbon monoxide, vapor pressure of raw materials, products, solvents, etc. is usually 0. OlMPa or higher, preferably 0. IMPa or higher, more preferably 0.5 MPa
  • the above is usually 30 MPa or less, preferably 20 MPa or less, more preferably lOMPa or less. If the reaction pressure is excessively low, there is a concern that the metal compound may be deactivated and metallized, and the catalytic activity itself is not sufficiently exhibited, and the alcohol yield is expected to decrease. Further, when the reaction pressure is excessively high, the straight chain selectivity of the resulting alcohol tends to decrease.
  • the hydrogen partial pressure is preferably 0.005 MPa or more, more preferably 0. OlMPa or more, preferably 20 MPa or less, more preferably lOMPa or less. If the hydrogen partial pressure is too low, there is a concern that the reaction activity will decrease, and if it is too high, waste due to the hydrogenation reaction of the raw olefinic compound is expected.
  • the carbon monoxide partial pressure is preferably 0.005 MPa or more, more preferably 0.0 OlMPa or more, preferably 15 MPa or less, more preferably 8 MPa or less. If the carbon monoxide partial pressure is too low, there is a concern that the reaction activity will decrease, particularly metalation of metal compounds, and if the hydrogen partial pressure is too high, the linear selectivity of the resulting alcohol is expected to decrease.
  • the molar ratio of hydrogen to carbon monoxide is 1:10 to 10: 1, more preferably 1: 2 to 8: 1, and still more preferably 1:;! To 5: 1.
  • the reaction temperature is usually 25 ° C or higher, preferably 50 ° C or higher, more preferably 70 ° C or higher, and usually 300 ° C or lower, preferably 250 ° C or lower, more preferably. 200 ° C or less. If the reaction temperature is too low, it is expected that the reaction activity itself will not be sufficiently obtained, and if the reaction temperature is too high, it will be caused by a decrease in the linear selectivity of the resulting alcohol or thermal decomposition of the ligand. Disappearance is expected.
  • any of a continuous type, semi-continuous type or batch type operation can be easily carried out in a stirred tank type reaction tank or a bubble column type reaction tank.
  • the yields of normal butanol and isobutyraldehyde are both 10% or more.
  • reaction conditions such as reactor scale, catalyst concentration, feed amount, reaction temperature, and reaction pressure.
  • a process that produces both normal butanol and isobutyraldehyde often takes a flow reaction process because of its cost advantage.
  • the raw material propylene is supplied to the reaction system at a supply rate of F (mol / hr).
  • isoformaldehyde, normal butyraldehyde, isobutanol, and normal butanol are produced by the hydroformylation reaction and subsequent hydrogenation reaction in the reaction system, respectively, and each component from the reaction system is F (mol / hr), F (mol / hr), F (mol / hr),
  • Outflow amount (mol / hr) The amount calculated by the amount flowing into the reaction system (mol / hr) ⁇ When the desired product such as S, isobutyl aldehyde, normal butyraldehyde, isobutanol, normal butanol is not supplied
  • the amount of each component flowing out from the reaction system, that is, F 1, F 2, F 3, and F (mol / hr) is the production rate of each component.
  • the increase rate (mol / hr) per unit time for each component is the production rate.
  • Methods for controlling the F / F value include the size of the reactor and the catalyst used in the reaction.
  • the value By manipulating the reaction conditions such as selection and catalyst concentration, feed amount, reaction temperature, reaction pressure, etc., the value can be controlled. In addition, if the optimum conditions are selected from these reaction conditions according to the process in which isobutyraldehyde and normal butanol are co-produced, the condition of formula (in) can be satisfied.
  • As a guideline for selecting reaction conditions it is preferable to first employ a catalyst system capable of adding hydrogen to aldehyde. Even in the case of a catalyst system that is slightly poor in hydrogenation capacity, It is preferable to increase the residence time and increase the catalyst concentration. Furthermore, it is preferable that normal butyraldehyde is separated from the reaction product flowing out of the reactor and recycled to the reactor.
  • the value of F / F is a force S that is 0.5 or more, preferably 0.7 or more,
  • Methods for controlling the F / F value include the size of the reactor and the catalyst used in the reaction.
  • the value can be controlled.
  • the condition of formula (IV) can be satisfied.
  • As a guideline for selecting the reaction conditions it is preferable to employ a catalyst system that has a high selectivity for normal to the iso form.
  • isobutanol is produced sequentially from propylene via isobutyraldehyde, it is also preferable to reduce the catalyst concentration, which is preferable to shorten the residence time in the reactor.
  • normal butyraldehyde is separated from the reaction product flowing out of the reactor and recycled to the reactor.
  • the value of F / F is 0.5
  • it is 0.7 or more, More preferably, it is 1.0 or more.
  • Methods for controlling the F / F value include the size of the reactor and the catalyst used in the reaction.
  • the value can be controlled by manipulating the reaction conditions such as selection and catalyst concentration, feed amount, reaction temperature, and reaction pressure.
  • the condition of formula (V) can be satisfied.
  • isobutanol is produced sequentially from propylene via isobutyraldehyde, so it is preferable to reduce the residence time in the reactor. .
  • normal methyl aldehyde is separated from the reaction product flowing out of the reactor and recycled to the reactor.
  • F / F is 0.
  • the force S is 5 or more, preferably 0.7 or more, more preferably 1.0 or more.
  • FIG. 1 is a diagram for explaining a reaction flow in the present embodiment.
  • FIG. 1 shows a reactor 2, a separator (first distillation column) 5, a separator (second distillation column) 10, and a separator (third distillation column) 14.
  • the raw materials propylene, hydrogen and carbon monoxide are supplied to the reactor 2 via the line 1. These raw materials may be supplied to the reactor 2 all at once or may be supplied separately. Most of the catalyst solution may be supplied from the line 8 to the reactor 2 as a circulating catalyst, or may be supplied from the line 9 as necessary. The supplied raw material reacts in the reactor 2 in the presence of a catalyst to obtain a reaction liquid containing normal butanol and isobutanol.
  • reaction liquid containing the unreacted raw material is supplied to the reactor by the line 4 provided on the side of the reactor 2.
  • the gas component may be supplied to the separator (first distillation column) 5 using the line 4 or recycled to the reactor 2 using the line 3 provided at the top of the reactor 2. Moyo! /, And all or part of it may be purged out of the system.
  • the catalyst solution is also supplied to the separator (first distillation column) 5 through the line 4 together with the reaction solution.
  • the separator first distillation column
  • the catalyst remains in the reactor 2 and components other than the catalyst flow out of the reactor 2.
  • a reaction product containing a Group 8 to Group 10 metal compound, an organophosphorus compound, a protic solvent, a normal low boiling point compound is separated through a line 4 provided on the side of the reactor 2 (first Of the distillation column).
  • the separator (first distillation column) 5 the separator (second distillation column) 10
  • the separator (third distillation column) 14 the unreacted raw material olefinic compound, products, Separation of the catalyst or the like is performed.
  • These separation operations are usually carried out by distillation operations such as simple distillation, rectification, thin film distillation, and steam distillation.
  • Distillation conditions are not particularly limited.
  • Product volatility, thermal stability, and catalyst Force arbitrarily set to obtain the desired result in consideration of the volatility and thermal stability of the components Usually selected at a temperature of 50 ° C 300 ° C, IMPa ⁇ ;! ⁇ Pressure condition of OOmmHg
  • the separator (first distillation column) 5 is subjected to distillation separation to extract a separator (first distillation and a distillate containing a low-boiling point compound (column top distillate)).
  • a separator first distillation and a distillate containing a low-boiling point compound (column top distillate)
  • First distillation column A liquid containing normal butanol and isobutanol is withdrawn as a side stream through a line 7 provided on the column side of 5.
  • the bottom liquid containing Group 8 to Group 10 metal compound, organophosphorus compound and proton solvent is circulated to reactor 2 through line 8 provided at the bottom of separator (first distillation column) 5.
  • the distillate (column distillate) extracted from the top of the separator (first distillation column) 5 through the line 6 is allowed to flow into the separator (second distillation column) 10.
  • a low boiling point compound is withdrawn from the top of the separator (second distillation column) 10 as a distillate, and from the column side of the separator (second distillation column) 10.
  • Isobutyraldehyde is withdrawn from line 12 as a side stream
  • normal butyraldehyde is withdrawn from line 13 from the bottom of the separator (second distillation column) 10 as line bottom liquid.
  • the side stream extracted from the column side of the separator (first distillation column) 5 through the line 7 is caused to flow into the separator (third distillation column) 14.
  • isobutanol is extracted as a distillate through a line 15 provided at the top of the separator (third distillation column) 14, and the separator (third distillation column).
  • Tower) Normal butanol is withdrawn from line 16 from the bottom of 14 as bottom liquid.
  • FIG. 2 is a diagram showing a preferred embodiment in the reaction flow of FIG. That is, as shown in FIG. 2, the total amount or a part of the normal methyl aldehyde extracted as the bottom liquid from the bottom of the separator (second distillation column) 10 is recycled to the reactor 2 via the line 13. Do it Yes.
  • FIG. 3 is a diagram for explaining a second reaction flow in the present embodiment.
  • FIG. 3 shows a reactor 2, a separator (first distillation column) 5, and a separator (second distillation column) 10.
  • reactor 2 contains Group 8 to Group 10 metal compounds, organophosphorus compounds, proton solvents, normal butanol, isobutanol, normal butyraldehyde, isobutyraldehyde, and low boiling point compounds.
  • a reaction product stream is obtained.
  • the obtained reaction product stream is allowed to flow from the reactor 2 through the line 4 to the separator (first distillation column) 5. Subsequently, a column top distillate containing isobutanol, normal butyraldehyde, isobutyraldehyde and a low-boiling point compound is withdrawn from the top of the separator (first distillation column) 5 through a line 6, and the separator (first distillation column).
  • the reactor 2 is filled with the total amount or one of them as necessary. Recycle the club and get ready.
  • FIG. 4 is a diagram showing a preferred embodiment in the reaction flow of FIG. That is, as shown in FIG. 4, the isobutanol and normal butyraldehyde extracted from the line 13 as the bottom liquid from the bottom of the separator (second distillation column) 10 are separated from the total amount or part of the separator ( (Third distillation column) 18 and normal butyraldehyde and isobutanol are separated. The separated normal butyraldehyde is also withdrawn from the top of the separator (third distillation column) 18, and all or a part thereof may be recycled to the reactor 2 using the line 19.
  • Normal butanol and isobutyraldehyde are obtained in high yields by carrying out the reaction under the reaction conditions as described above using the metal compound, organophosphorus compound, and protic solvent as described above.
  • the obtained reaction product can be obtained as normal butanol and isobutyraldehyde products as follows.
  • Rh ( acac ) (CO) (11.2 mg, 0.04 in a nitrogen atmosphere.
  • trioctenolephosphine 64.dmg, 0.174mmol
  • the mixed gas was introduced through the feed tube attached in the autoclave while being published into the reaction solution, and the reaction solution was stirred with a magnetic stirrer placed in advance in the autoclave. .
  • the mixed gas is automatically supplied from the accumulator through the secondary pressure regulator, so that the internal pressure can be constantly maintained at 2.0 MPa. I made it.
  • the reaction was monitored until the internal pressure of the pressure accumulator was monitored and the pressure drop due to gas consumption almost stopped.
  • the autoclave was cooled to room temperature, the reaction solution was taken out and analyzed by gas chromatography, and the product concentration was measured. As a result, the normal butanol yield was 56.5%, and the isobutyraldehyde yield was 16.4%.
  • Example 1 the amount of trioctylphosphine added was 370 ⁇ Omg (0. 998 mmol, R h (acac) (CO) 1 monole to 23 monole), and the reaction temperature was 160 ° C. Pressure 5MP
  • Example 5 [0087] In Example 1, triethyl phosphine was used instead of trioctyl phosphine, and the addition amount was 51.3 mg (0.0434 mmol, 10 mol relative to 1 mol of Rh (acac) (CO)).
  • Example 5 the reaction was carried out in the same manner except that the amount of triethylphosphine added was 20.5 mg (0.174 mmol, 4 mol relative to 1 mol of Rh (acac) (CO)). Analysis
  • the reaction is carried out at a temperature of 120 ° C. and a pressure of 2 MPa, the propylene conversion is 100%, and the product selectivity is the same as that of Example 1.
  • the separator (first distillation column) 5, the separator (second distillation column) 10, and the separator (third distillation column) 14 are all distillation columns, and the conditions are shown in Table 1.
  • Table 2 shows the results of simulation under the above conditions.
  • IBD Isobutyraldehyde
  • propylene is supplied at 10 kmol / hr
  • 7_K element is supplied at 20 kmol / hr
  • carbon monoxide is supplied at 10 kmol / hr from line 1 to reactor 2.
  • normal butanol is used as a solvent instead of ethanol, and the catalyst solution is circulated through the line 8 to the reactor 2 at 2,000 kg / hr.
  • the reaction is carried out at a temperature of 120 ° C. and a pressure of 2 MPa, the propylene conversion is 100%, and the product selectivity is the same as in Example 1.
  • the separator (first distillation column) 5, the separator (second distillation column) 10, and the separator (third distillation column) 14 are all distillation columns, and the conditions are shown in Table 3.
  • Table 4 shows the results of simulation under the above conditions.
  • Fig. 3 propylene is supplied at 10 kmol / hr, hydrogen is supplied at 20 kmol / hr, and carbon monoxide is supplied at 10 kmol / hr from line 1 to reactor 2. Further, in the catalyst of Example 1, normal butanol was used as a solvent instead of ethanol, and the catalyst solution was circulated through the line 8 to the reactor 2 at 2, 0 OO kg / hr.
  • the reaction is carried out at a temperature of 120 ° C. and a pressure of 2 MPa. It is assumed that the conversion of propylene is 100% and the selectivity of the product is the same as that of Example 1.
  • the separator (first distillation tower) 5 and the separator (second distillation tower) 10 are both distillation towers, and the conditions are shown in Table 5.
  • Table 6 shows the results of simulation under the above conditions.
  • Fig. 4 propylene is supplied to reactor 2 from line 1 at 10 kmol / hr, hydrogen at 20 kmol / hr, and carbon monoxide at 10 kmol / hr.
  • the catalyst of Example 1 normal butanol is used as a solvent instead of ethanol, and the catalyst solution is circulated through the line 8 to the reactor 2 at 2,000 kg / hr.
  • the reaction is carried out at a temperature of 120 ° C. and a pressure of 2 MPa. It is assumed that the conversion of propylene is 100% and the selectivity of the product is the same as that of Example 1.
  • the separator (first distillation column) 5, the separator (second distillation column) 10, and the separator (third distillation column) 18 are all distillation columns, and the conditions are shown in Table 7.

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

Abstract

L'invention porte sur un procédé pour la coproduction de butanol normal et d'isobutyraldéhyde par réaction de propylène avec de l'hydrogène et du monoxyde de carbone. Le procédé comprend l'étape (A) de réaction de propylène avec de l'hydrogène et du monoxyde de carbone dans un réacteur (2) en présence d'un catalyseur contenant un composé d'un élément métallique du Groupe 8, 9 ou 10 de la Classification Périodique, l'étape (B) de soutirage d'un produit de tête contenant du butyraldéhyde normal etc. et d'un courant latéral contenant de l'isobutanol etc. provenant du courant de produit de réaction avec un séparateur (la première colonne de distillation) (5), et l'étape (C) de séparation du produit de tête en butyraldéhyde normal et isobutyraldéhyde par distillation fractionnée avec un séparateur (la seconde colonne de distillation) (10) tout en séparant le courant latéral en isobutanol et butanol normal par distillation fractionnée avec un séparateur (la troisième colonne de distillation) (14), et en soutirant ceux-ci séparément.
PCT/JP2007/069711 2006-11-09 2007-10-09 Procédé de coproduction de butanol normal et d'isobutyraldéhyde WO2008056501A1 (fr)

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CN2007800364966A CN101522598B (zh) 2006-11-09 2007-10-09 正丁醇和异丁醛的联产方法
BRPI0718007-1A BRPI0718007B1 (pt) 2006-11-09 2007-10-09 Method of co-production of normal butanol and isobutylic village

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Cited By (4)

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CN102267873A (zh) * 2010-06-01 2011-12-07 中国石油化工集团公司 可切换副产异丁醇或异丁醛的方法
CN102267880A (zh) * 2010-06-01 2011-12-07 中国石油化工集团公司 可切换副产异丁醇或异丁醛的装置
US10435346B2 (en) 2016-04-21 2019-10-08 Johnson Matthey Davy Technologies Limited Process for the distillation of an aldehyde mixture
GB2575146A (en) * 2018-04-13 2020-01-01 Johnson Matthey Davy Technologies Ltd Process

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KR101338646B1 (ko) * 2010-03-03 2013-12-06 주식회사 엘지화학 올레핀으로부터 알데히드를 제조하는 방법
KR101253219B1 (ko) 2011-05-12 2013-04-16 (주)클레슨 대형 상자용 자동 세척기 및 자동 세척기의 세척방법
KR101640654B1 (ko) 2013-01-16 2016-07-18 주식회사 엘지화학 알칸올의 제조 장치
CN107032953B (zh) * 2017-05-10 2023-08-04 张家港市华昌新材料科技有限公司 一种适用于辛醇和丁醇转换生产的装置和转换方法

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JP2001026566A (ja) * 1999-06-02 2001-01-30 Oxeno Olefinchemie Gmbh 多相反応を接触的に実施する方法および得られた反応生成物の使用
JP2001163820A (ja) * 1999-11-30 2001-06-19 Oxeno Olefinchemie Gmbh オレフィンのヒドロホルミル化方法

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JP2001026566A (ja) * 1999-06-02 2001-01-30 Oxeno Olefinchemie Gmbh 多相反応を接触的に実施する方法および得られた反応生成物の使用
JP2001163820A (ja) * 1999-11-30 2001-06-19 Oxeno Olefinchemie Gmbh オレフィンのヒドロホルミル化方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102267873A (zh) * 2010-06-01 2011-12-07 中国石油化工集团公司 可切换副产异丁醇或异丁醛的方法
CN102267880A (zh) * 2010-06-01 2011-12-07 中国石油化工集团公司 可切换副产异丁醇或异丁醛的装置
CN102267873B (zh) * 2010-06-01 2013-11-06 中国石油化工集团公司 可切换副产异丁醇或异丁醛的方法
CN102267880B (zh) * 2010-06-01 2013-11-06 中国石油化工集团公司 可切换副产异丁醇或异丁醛的装置
US10435346B2 (en) 2016-04-21 2019-10-08 Johnson Matthey Davy Technologies Limited Process for the distillation of an aldehyde mixture
GB2575146A (en) * 2018-04-13 2020-01-01 Johnson Matthey Davy Technologies Ltd Process
GB2575146B (en) * 2018-04-13 2021-12-22 Johnson Matthey Davy Technologies Ltd Process for the production of normal butanol, iso-butanol and 2-alkyl alkanol
US11312674B2 (en) 2018-04-13 2022-04-26 Johnson Matthey Davy Technologies Limited Process for making a feed of normal butanol, iso-butanol and 2-alkyl alkanol

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KR20090078779A (ko) 2009-07-20
CN101522598B (zh) 2012-06-27
BRPI0718007B1 (pt) 2017-10-24
TW200827329A (en) 2008-07-01
CN101522598A (zh) 2009-09-02
KR101539779B1 (ko) 2015-07-27

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