EP0971868A1 - Procede de production de n-butyraldehyde et/ou de n-butanol - Google Patents

Procede de production de n-butyraldehyde et/ou de n-butanol

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Publication number
EP0971868A1
EP0971868A1 EP98913678A EP98913678A EP0971868A1 EP 0971868 A1 EP0971868 A1 EP 0971868A1 EP 98913678 A EP98913678 A EP 98913678A EP 98913678 A EP98913678 A EP 98913678A EP 0971868 A1 EP0971868 A1 EP 0971868A1
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EP
European Patent Office
Prior art keywords
reaction
catalyst
butadiene
partial
liquid phase
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EP98913678A
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German (de)
English (en)
Inventor
Jürgen KANAND
Rocco Paciello
Michael Röper
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/32—Preparation of ethers by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/54—Preparation of compounds having groups by reactions producing groups by addition of compounds to unsaturated carbon-to-carbon bonds
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group

Definitions

  • the present invention relates to a process for the preparation of n-butyraldehyde and / or n-butanol.
  • n-Butyraldehyde and n-butanol are large products in the chemical industry and are used in many different ways.
  • n-butyraldehyde e.g. is produced worldwide in quantities of over 4 million t / year and serves among other things as a raw material for the manufacture of plasticizer alcohols.
  • n-Butanol is widely used as a solvent, for example for paints.
  • n-Butanol is one of the most important by-products of n-butyraldehyde in terms of quantity and is obtained from it by hydrogenation.
  • Other processes for the production of n-butanol, such as the hydrogenation of crotonaldehyde, which in turn is produced by aldol condensation of acetaldehyde, are only of historical interest today or, like the microbiological production of n-butanol by fermenting molasses, are only regional Meaning (Kirk-Othmer: Encyclopedia of Chemical Technology, 4th ed., Volume 4, pp. 694-696, John Wiley & Sons, New York 1992).
  • 1,3-butadiene is a basic chemical that is produced in large quantities in steam crackers and is extracted from the C 4 section of the steam cracker extractively, for example using N-methylpyrrolidone.
  • 1,3-butadiene is available in large quantities and is a very inexpensive raw material.
  • the production of butanol and / or butyraldehyde starting from the raw material 1,3-butadiene has a number of difficulties.
  • One reason for this is the tendency of 1,3-butadiene to dimerize and polymerize as well as the formation of mixtures of 1,2- and 1,4-adducts in addition reactions.
  • Phenolates used as cocatalysts.
  • alkyl palladium (II) complexes with trialkyl or triaryl phosphine or phosphite ligands are used in the presence of alkali metal alcoholates for the reaction of isoprene with alcohols.
  • Kawazura et al. J. Chem. Soc. Chem. Com. 2213, (1972)
  • rhodium (III) chloride as a catalyst, as does Dewhirst (J. Org. Chem. 3_2., 1297 (1967)).
  • a disadvantage of this process is that the cobalt carbonyls also act as aldolization catalysts in the hydrolysis, which leads to the formation of undesired aldolization by-products in the hydrolysis of the acetals.
  • Another disadvantage is that the cobalt carbonyl compounds used are relatively volatile and some are discharged during the distillative workup of the product mixture with the aldehyde or alcohol, which is why it has to be freed of cobalt carbonyls contained therein before it is used in a complex decobalization step. This process is therefore not economical.
  • US Pat. No. 4,658,069 relates to a process for converting allyl ethers which additionally contain a formyl or carboxy group into the corresponding diacetals, the allyl ether being reacted with an alkanol under anhydrous conditions in a first stage and then the water formed in this reaction removed and in a second stage, the allyl ether acetal obtained in the first stage is converted to a saturated diacetal using a ruthenium halide catalyst and an alkanol. Iridium halides are also mentioned as suitable catalysts. Only the saturated acetals are formed under the reaction conditions specified in this patent.
  • JP-A 25114/1972 relates to a process for the preparation of acetals from allyl ethers by reacting them with an alkanol in the presence of a ruthenium (III) chloride catalyst.
  • a ruthenium (III) chloride catalyst In the example of this application, 1-methoxy-2,7-octadiene with methanol and converted to 1,1-dimethoxyoct-7-ene using RuCl 3 under a nitrogen atmosphere.
  • the double bond is hydrogenated on a palladium catalyst and then in a third stage the caprylaldehyde dimethyl acetal thus obtained is hydrolyzed to sulfuric acid to form the caprylaldehyde.
  • WO 95/19334 relates to a process for the preparation of butyric aldehyde and / or butanol, an alkanol adding 1,3-butadiene and the allyl ether thus obtained isomerizing to the enol ether and converted into butyraldehyde and by reaction with water or water and hydrogen / or butanol is converted.
  • the present invention was therefore based on the object of finding an economical process for the preparation of n-butyraldehyde and / or n-butanol that can be used on a large industrial scale, starting from the raw material 1, 3-butadiene, and which makes it possible to produce these products with high
  • the amount of by-products formed in the process should be low or these by-products themselves should be sought-after commercial products.
  • the process should be flexible to allow n-butyraldehyde and / or n-butanol to be optionally produced as needed for these compounds.
  • the practice of the process should not depend on the presence of a synthesis gas plant and without high pressure plants or additional purification stages, e.g. one decobinding stage.
  • radical R is an unsubstituted or substituted by 1 to 2 C 1 -C 10 -alkoxy or hydroxyl groups C - to C 2 o -alkyl or alkenyl, a ⁇ - to Cio-aryl or a C 7 - to Cn Aralkyl group or the methyl group, at elevated temperature and at elevated pressure in the presence of a Bronsted acid or in the presence of a complex of an element from Group Ia, VIIA or VIIIA of the Periodic Table of the Elements with ligands containing phosphorus or nitrogen a mixture of the adducts of the formulas II OR II
  • the process according to the invention is thus composed of 4 partial reactions a) to d).
  • the partial reactions a) and b) can optionally be carried out individually, in succession, in at least 2 process steps or practically simultaneously in a single process step, the isomerization of adduct III to adduct II according to partial reaction b) after returning adduct III to process step the addition of the alcohol ROH I to 1,3-butadiene takes place simultaneously with the addition according to partial reaction a).
  • the partial reactions c) and d) are expedient carried out in succession, in two process stages.
  • process stage is used in this application for a plant unit in which a single one of the partial reactions a) to d) takes place on the catalyst or catalysts used in this plant unit or in which several, in particular 2, of these partial reactions, run side by side on the catalyst or catalysts used in this plant unit.
  • the hydrolysis or the combined hydrolysis / hydrogenation of the acetal IV according to partial reaction d) is, unless otherwise mentioned in this application, regarded as a single partial reaction.
  • a plant unit can comprise both a single reactor and a plurality of reactors connected in series, which are filled with the same or, if appropriate, with different catalysts and are operated in the same mode of operation and at the same or different temperature and pressure conditions.
  • the mode of operation is understood to mean working in the liquid phase using a homogeneous catalyst or working in the liquid phase using a heterogeneous catalyst. It follows that this application does not speak of a "reaction in a single process step", for example, if catalysts are used in the individual, successive reactors which are capable only of catalyzing a specific partial reaction or if these reactors have different operating modes is worked.
  • the conversion of butenyl ether II to n-butyraldehyde and / or n-butanol can also be carried out starting from butenyl ether II, which have been prepared in a different manner than by the integrated process described above, for example by the reaction of allyl halides and an alcohol ROH I in the presence of a base. Accordingly, a process for the preparation of n-butyraldehyde and / or n-butanol was also found, which is characterized in that an ether of the formula II
  • radical R is an unsubstituted or substituted by 1 to 2 C f to Cio-alkoxy or hydroxy groups C 2 - to C 20 alkyl or alkenyl, a C ⁇ - to Cirj-aryl or a C 7 - to Cn -Aralkyl group or the methyl group, in the presence of a to form the acetal IV
  • step a) 1,3-butadiene or a butadiene-containing hydrocarbon mixture is in the presence of a catalyst with the alcohol ROH I according to equation (1) OR
  • adducts II and III are generally formed in a molar ratio of 1: 1 to 1: 3.
  • the type of alcohol ROH I used in the reaction is generally not critical to the process. Both primary and secondary alcohols can be used, but primary alcohols are preferred. Aliphatic, cycloaliphatic, aromatic and araliphatic alcohols can be used; aliphatic and araliphatic alcohols are preferably used.
  • alcohols ROH I are used in the process according to the invention, in which the radical R is a C 1 -C 2 -alkyl, C 3 - to Cio-alkenyl, for example the allyl, the but-2-enyl, a C 5 - to C 2 o "alkadienyl -, advantageously without cumulative double bonds, for example an octa-2, 7-dien-1-yl -, preferably a C - to C 4 -alkyl, in particular the n-butyl group C 6 - to Cio-aryl, preferably the phenyl group or a C - to Cn-aralkyl, preferably the benzyl group
  • the radicals R can optionally be substituted with substituents such as C 1 -C 8 -alkoxy and / or hydroxyl groups Diols or triols or alkoxy alcohols can thus also be used as alcohols ROH I.
  • alcohols ROH I with unsubstituted radicals R are preferably used.
  • alcohols can also be used a higher number of carbon atoms are used, as such higher If higher alcohols are generally more expensive than lower alcohols, lower alcohols are preferred for economic reasons.
  • Catalysts are used, for example Bronsted acids or also phosphine complexes of transition metals from groups IA, VIIA or VIIIA of the Periodic Table of the Elements, in particular phosphine complexes of palladium and nickel.
  • Bronsted acids for example conventional, non-oxidizing Bronsted acids such as hydrohalic acids, for example hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, hydrofluoric acid, tetrafluoroboric acid, methanesulfonic acid or toluenesulfonic acid can be used, but solid Bronsted acids are preferred. Acids, especially organic or inorganic cation exchangers, are used.
  • Organic cation exchangers are powdery, gel-like or macroporous, polymeric polyelectrolytes which carry Brönsted acidic functional groups, such as sulfonic acid, phosphonic acid or carboxyl groups on a polymer matrix, for example sulfonated phenol-formaldehyde resins, sulfonated styrene -Divinylbenzene copolymers, sulfonated polystyrene,
  • these cation exchangers can be used in the form of commercially available products, such as, for example, under the trade names Amberlite®, Dowex®, Amber-lyst®, Lewatit®, Wofatit®, Per utit®, Purolite®, and Nafion® im
  • cation exchangers are expediently used in the process according to the invention in their protonated form, the so-called H + form.
  • suitable organic cation exchangers are the commercial products Amberlite® 200, Amberlite® IR 120, Amberlite® IR 132 E,
  • Lewatit® SC 102 Lewatit® SC 104, Lewatit® SC 108, Lewatit® SPC 108, Lewatit® SPC 112, Lewatit® SPC 118, Purolite® CT 145, Purolite® CT 171, Purolite® CT 175 and Amberlyst® Called 15.
  • modified organic cation exchangers for example those which additionally contain Lewis acids, such as copper (II) halides, in particular copper (II) chloride, copper (II) bromide, copper (II) iodide, or copper (II) salts, such as
  • Such Lewis acid containing cationic ion exchangers can e.g. can be prepared by the method of GB-A 943 160.
  • the Lewis acid-containing ion exchangers are preferably used in a form in which only some of the water
  • the organic ion exchangers are doped with an amount of Lewis acid such that 5 to
  • zeolite the, such as ⁇ -zeolites or Y-zeolites in the H + form
  • bleaching earths such as bentonites, montmorillonites or attapulgites, non-zeolite - see phosphate-based molecular sieves, as described, for example, in US Pat. No.
  • Preferred Bronsted acidic inorganic solids are ⁇ -zeolites or Y-zeolites in the H + form, in particular ⁇ -zeolites in the H + form. ⁇ -zeolites are available, for example, by the process of US Pat. No. 4,891,458.
  • Organic ion exchangers are particularly preferably used in the process according to the invention for the addition of alcohols ROH I to 1,3-butadiene or butadiene-containing hydrocarbon mixtures in partial reaction a).
  • the procedure is generally such that 1,3-butadiene or the butadiene-containing hydrocarbon mixture introduces them in gaseous or preferably in liquid form into the acid / alcohol mixture and removes the adducts of the formulas II and III from the reaction zone by distillation or by stripping.
  • 1,3-butadiene or the butadiene-containing hydrocarbon mixture introduces them in gaseous or preferably in liquid form into the acid / alcohol mixture and removes the adducts of the formulas II and III from the reaction zone by distillation or by stripping.
  • conventional reactors such as bubble columns, loop reactors, etc. be used.
  • the alcohol / 1,3-butadiene mixture can advantageously be e.g.
  • Adducts II and III can also be separated from the aqueous solution of Bronsted acid using phase separators.
  • stirred tank cascades can also be used, it being advantageous to work at a pressure at which the 1,3-butadiene is liquid under the selected reaction conditions.
  • solid Bronsted acids in the form of the abovementioned organic or inorganic catalysts are preferably used in the process according to the invention.
  • These are preferably arranged in a fixed bed and flowed through by the liquid reaction mixture in the bottom or preferably trickle mode.
  • the fixed catalyst bed can be installed, for example, in tubular reactors or preferably in reactor cascades. It is also possible to pass the reactants in gaseous form through the catalyst bed; preference is given to working in the liquid phase. It goes without saying that the addition of the alcohol ROH I to 1,3-butadiene or butadiene-containing Hydrocarbon mixtures according to partial reaction a) can be carried out either continuously or batchwise.
  • the molar ratio of alcohol / 1,3-butadiene can be selected from a wide range in the process according to the invention.
  • a molar ratio of alcohol ROH / 1,3-butadiene is from 0.5: 1 to 8.0: 1, preferably from 1: 1 to 5.0: 1 and particularly preferably from 1.5: 1 to 3.0: 1 applied.
  • the reaction of the alcohol ROH I with 1,3-butadiene is generally carried out at from 20 to 150 ° C., preferably from 50 to 120 ° C., in particular from 60 to 110 ° C., and at a pressure from generally 1 to 100 bar, preferably from 3 to 50 bar, in particular from 5 to 30 bar.
  • the pressure is expediently chosen so that the 1,3-butadiene or the butadiene-containing hydrocarbon mixtures are liquid at the reaction temperature used.
  • the application of a higher pressure is possible.
  • the reaction temperature used is expediently optimized in a preliminary test with regard to the Bronsted acid catalyst used in each case.
  • the addition of a solvent to the reaction mixture is possible, but generally not necessary, since the alcohol used and the adducts II and III can also act as solvents.
  • the residence time of the alcohol ROH / 1,3-butadiene mixture in the reactor is generally 1 to 6 hours and is generally dependent on the reaction temperature used.
  • the reaction gas can be mixed with a gas which is inert under the reaction conditions, for example nitrogen, in general the reaction gas is used undiluted.
  • the addition may be of the alcohol ROH I by means of a homogeneous Re ⁇ action medium dissolved or heterogenized transition metal - element catalyst containing an element from Group IA, VIIA or VIIIA of the Periodic Table of the Elements, such as copper, nickel, Rho - Contains dium, palladium, platinum or iridium, preferably palladium or nickel.
  • transition metal element catalysts in particular the palladium and nickel catalysts, are expediently used in the form of their complexes which are homogeneously soluble in the reaction medium, with, for example, phosphine, 2,2′-bipyridine or 1,10-phenanthroline ligands.
  • phosphine 2, 2'-bipyridine or 1, 10-phenantholine
  • phosphine ligands Both monodentate or multidentate, in particular bidentate, phosphine ligands can be used as ligands.
  • Suitable phosphine ligands are, for example, trialkylphosphines, triarylphosphines, alkyldiarylphosphines, aryldialkylphosphines, aryldiphosphines, alkyldiphosphines and arylalkyldiphosphines.
  • the aryl group-bearing phosphine ligands can contain the same or different C 6 to C 2 aryl groups, in particular the phenyl or naphthyl group but also diphenyl groups. Furthermore, phosphine ligands can be used to complex the group IA, VIIA or VIIIA elements, the heterocycloaliphatic groups such as pyrrolidine, imidazolidine, piperidine, morpholine, oxazolidine, piperazine or triazolidine groups or heteroaromatic groups Groups such as pyrrole, imidazole, oxazole, indole, pyridine, quinoline, pyrimidine, pyrazole, pyrazine, pyridazine or quinoxaline groups together with other alkyl or aryl groups.
  • the heterocycloaliphatic groups such as pyrrolidine, imidazolidine, piperidine, morpholine, oxazolidine, piperazine or tri
  • the alkyl or aryl groups of the ligands can be unsubstituted or substituents which are inert under the reaction conditions, such as C 1 -C 4 -alkoxy- or di-C 1 -C 4 -alkyl ino-, Ci- to C ⁇ -alkyl- , Nitro, cyano or sulfonate groups.
  • suitable sulfonated phosphine ligands in the process according to the invention are triphenylphosphine trisulfonate (TPPTS) and triphenylphosphine monosulfonate (TPPMS) (Angew. Chem. 105, 1588 (1993)).
  • trimethylphosphine triethylphosphine, tri-propylphosphine, triisopropylphosphine, tributylphosphine, trioctylphosphine, tridecylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tri-phenylphosphine, tri-phenylphosphine phenylphosphine, tetraphenyldiphosphinomethane, 1, 2-bis (diphenylphosphino) ethane, tetramethyldiphosphinomethane, tetraethyldiphosphine phinomethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, tetra-t-butyl- diphosphinomethane, 1,2-bis (dimethylphosphine,
  • phosphine ligands described in EP-A 71 281.
  • preferred phosphine ligands are bidentate phosphine ligands of the general formula which are bridged via Ci to C -alkylene groups
  • n is an integer from 1 to 4 and the radicals A are identical or different Ci to Cio alkyl or C 5 to C 6 "cycloalkyl groups, some of which have been mentioned above by way of example.
  • alkyl or arylphosphine ligands can be prepared by methods which are conventional per se, for example according to the methods described in Houben-Weyl, Methods of Organic Chemistry, Volume XII / 1, 4th Edition , Pp. 17-65 and pp. 182-186, Thieme, Stuttgart, 1963 and
  • 2, 9-dimethyl-4, 7-diphenyl-l, 10-phenanthroline, 4, 5-diazafluorene, dipyrido [3, 2-a: 2 ', 3' -c] phenazine, 2, 2 ', 6', 2 '' terpyridine and others can be used.
  • Some of these ligands are commercially available, for example 2, 2'-bipyridine or 1, 10-phenanthroline, or can be prepared according to the methods described in Synthesis 1, (1976) or Aust. J. Chem. 23., 1023 (1970).
  • the complexes of the elements of group IA, VIIA or VIIIA, in particular palladium and nickel, which can be used for the partial reaction a) in the process according to the invention, can be generated in situ in the reaction mixture or added to the reaction mixture in preformed form.
  • the procedure is generally such that compounds of group IA, VIIA or VIIIA elements, for example their halides, preferably their chlorides, bromides or iodides, the nitrates, cyanides or sulfates or, in particular preferably, complex compounds of these metals, such as acetylacetonates, carboxylates, carbonyl complexes or olefin complexes, such as ethene or butadiene complexes, are fed together with the ligand in question to the reaction mixture, whereupon the complexes which can be used according to the invention in partial reaction a) form in the reaction mixture.
  • the ligand in question is added with respect to the Group IA, VIIA or VIIIA element in a molar ratio of 1 to 200, preferably 1 to 50, in particular 1 to 10.
  • a molar ratio of 1,3-butadiene / Group IA, VIIA or VIIIA element from 100: 1 to 100000: 1, preferably from 200: 1 to 5000: 1 and particularly preferably from 400: 1 to 2500: 1, this molar ratio being based on the steady 1,3-butadiene concentration in the liquid reaction mixture if the process is carried out continuously.
  • the molar ratio of alcohol ROH 1/1, 3-butadiene can be selected within wide limits in this process design and is generally not critical.
  • the alcohol to be added to 1,3-butadiene can function not only as a reagent but also as a solvent for the complex catalyst.
  • the addition of the alcohol ROH I to 1,3-butadiene in accordance with partial reaction a) of the process according to the invention with the aid of the complex catalysts mentioned is preferably carried out in the liquid phase.
  • the catalyst is dissolved in liquid reaction medium, introduced and 1,3-butadiene or the butadiene-containing hydrocarbon mixture in liquid or gaseous form, introduced together with the alcohol I into the reaction mixture.
  • the alcohol to be added to 1,3-butadiene or an inert solvent under the reaction conditions, preferably a high-boiling solvent, can serve as the reaction medium.
  • Suitable solvents are, for example, condensation products which are formed in the course of the reaction, such as alkoxyoctadienes, alkoxydodecatrienes, furthermore ethers, such as dibutyl ether or dioctyl ether, diethylene glycol dibutyl ether, low molecular weight, liquid polyethylene glycol ethers and sulfones, such as sulfolane or hydrocarbons, such as mihagol.
  • Mihagol is a commercially available CIO to C14 hydrocarbon mixture. Mixtures of different solvents can of course also serve as the reaction medium.
  • the reaction is generally carried out in a stirred autoclave.
  • the adducts of the formulas II and III formed in this process are then expediently separated off from the reaction mixture by distillation, the homogeneous catalyst containing the group IA, VIIA or VIIIA element, in particular palladium or nickel, in the bottom of the distillation, dissolved in the high-boiling solvent , remains.
  • the catalyst solution thus remaining in the distillation sump can, if desired, be reused for further reactions.
  • the 1,3-butadiene or the butadiene-containing hydrocarbon mixture is preferably in liquid form under pressure in the alcohol
  • the reaction is advantageously carried out in a tubular reactor, loop reactor or preferably in a reactor cascade. Unreacted 1,3-butadiene is advantageously circulated.
  • the alcohol ROH I is advantageously metered in continuously in accordance with its consumption during the reaction of the reaction mixture.
  • the 1,3-butadiene or the butadiene-containing hydrocarbon mixture can be passed in gaseous form through the liquid reaction medium containing the catalyst, unreacted 1,3-butadiene and the volatile hydrocarbons being used to strip from the reaction mixture during the reaction with the relatively volatile adducts of the formulas II and III formed.
  • the Alcohol ROH I can, depending on its consumption during the reaction, be metered continuously into the reaction mixture.
  • the addition of the alcohol ROH I to 1,3-butadiene in the presence of the said complexes of group IA, VIIA or VIIIA elements, in particular palladium or nickel, is generally carried out at a temperature of 20 to 180 ° C., preferably of 40 to 150 ° C and, particularly preferably, from 60 to 120 ° C and at a pressure of preferably 1 to 20 bar and, particularly preferably, carried out under the autogenous pressure of the reaction system.
  • heterogeneous complex catalysts can be used, preferably those in which the group IA, VIIA or VIIIA element, in particular the palladium or nickel , is fixed to polymer matrices.
  • Such polymeric matrices can be resins, such as styrene-divinylbenzene resins or phenol-formaldehyde resins, to which the ligands in question, that is to say phosphines, 1, 10-phenanthrolines or 2, 2'-bipyridines, are generally covalently bound, which in turn form complexes with the group IA, VIIA or VIIIA elements, in particular palladium or nickel, and quasi immobilize them in this way.
  • resins such as styrene-divinylbenzene resins or phenol-formaldehyde resins, to which the ligands in question, that is to say phosphines, 1, 10-phenanthrolines or 2, 2'-bipyridines, are generally covalently bound, which in turn form complexes with the group IA, VIIA or VIIIA elements, in particular palladium or nickel, and quasi immobilize them in this way.
  • Inorganic support materials after previous hydrophobization and chemical modification of their surfaces by means of organic reagents, can also serve as heterogeneous matrices for immobilizing the group IA, VIIA or group VIIIA element complexes, in particular the palladium or nickel complexes .
  • Such heterogenized, polymer-bound Group IA, VIIA or Group VIIIA element complexes, in particular palladium and nickel complexes are, for example, by the method of Zhuangyu et al. (Reactive Polymers £, 249 (1988)) or according to Wang et al. (J. Org. Chem. 59th, 5358 (1994)) are available.
  • Immobilized phosphine complexes of the group IA, VIIA and VIIIA elements are, for example, by the method of Hartley, Adv. Organomet. Chem. 15 . , 189 (1977), Hartley FR “Supported Metal Complexes", Riedel, Dordrecht 1985, K. Smith, "Solid Supports and Catalysis in Organic Synthesis", Ellis Horwood, Prentice Hall, NY 1992, CH Pittman “Polymer supported Reactions in Organic Synthesis ", p. 249, Wiley, Chichester 1980 and CH Pittmann J. Am. Chem. Soc. £ 8. » 5407 (1976) and Ann. NY Acad. Be. 245, 15 (1977).
  • the advantage of using such heterogenized catalysts is in particular the easier and gentler separability of the catalyst from the reaction products.
  • This can be arranged in a fixed bed and flowed through by the reaction mixture or but also suspended in the reaction mixture and mechanically separated after the reaction.
  • 1,3-butadiene-containing hydrocarbon mixtures can also be used as raw material in the process according to the invention.
  • Such hydrocarbon mixtures are obtained, for example, as a so-called C 4 cut in steam crackers.
  • These hydrocarbon mixtures are expediently freed of any acetylenic or allenic hydrocarbons contained therein by their partial hydrogenation (Weissermel, Arpe: Industrielle Organische Chemie; 3rd edition, VCH Verlagsgesellschaft, Weinheim 1988) and, if desired, of isobutene before their use in the process according to the invention.
  • the 1,3-butadiene-containing hydrocarbon mixtures can then be introduced in an analogous manner to pure 1,3-butadiene in partial reaction a) of the process according to the invention.
  • the saturated or monoolefinic hydrocarbons contained in these hydrocarbon mixtures which did not react during the reaction in partial reaction a) are expediently removed from the reaction discharge from partial reaction a), for example by means of a gas-liquid separator.
  • adducts of the formulas II and III obtained in the reaction of these hydrocarbon mixtures in partial reaction a) of the process according to the invention can, as described below, be processed further in the same manner to give n-butyraldehyde and / or n-butanol as that with pure 1,3-butadiene in partial reaction a) generated adducts II and III.
  • the reaction product from partial reaction a) of the process according to the invention generally contains, in addition to unreacted 1,3-butadiene or saturated or olefinic hydrocarbons, the adducts of the formulas II and III and, if appropriate, in particular when using Bronsted acids as catalysts in a partial reaction a), several isomers of the alkoxyoctadiene in question, of which is referred to below under the collective name alkoxyoctadiene.
  • the alkoxyoctadiene is formed during the addition of the alcohol ROH I to 1,3-butadiene in a side reaction, in which 1,3-butadiene first dimerizes to octatriene, to which the alcohol ROH I then adds to form an alkoxyoctadiene.
  • reaction product from partial reaction a) can also contain small amounts of other by-products, for example dibutyl ether, octatriene, vinylcyclohexene, alkoxydodecatrienes, formed by trimerization of 1,3-butadiene to dodecatetraene and subsequent addition of the alcohol ROH I, and also dodecatetraene , Dialkoxyoctene and dialkoxybutane.
  • dibutyl ether octatriene
  • vinylcyclohexene vinylcyclohexene
  • alkoxydodecatrienes formed by trimerization of 1,3-butadiene to dodecatetraene and subsequent addition of the alcohol ROH I, and also dodecatetraene , Dialkoxyoctene and dialkoxybutane.
  • the adduct required for the preparation of n-butyraldehyde and / or n-butanol in the process according to the invention is 1-alkoxybutene-2 of the formula II, which for the preparation of the target compounds in the process according to the invention contains the same amount in the reaction output Isomer 3-alkoxybutene-1 of formula III can be separated. Since the
  • Adducts II and III are formed in the addition of the alcohol ROH I to 1,3-butadiene in approximately the same amounts, the process according to the invention would not be economically viable if the 3-alkoxybutene-l III could not be economically rather to convert the desired l-alkoxybutene-2 II. It has been found that the conversion of adduct III into the desired adduct II can be carried out in a simple and economical manner.
  • the adduct III is first separated from the isomeric adduct II contained in the reaction discharge from partial reaction a). This can advantageously be done in such a way that the reaction product from partial reaction a), after prior removal of unreacted 1,3-butadiene, for example in a gas-liquid separator, is passed into a distillation apparatus and separated therein by fractional distillation.
  • the by-products, 1,3-butadiene dimers and trimers contained in the reaction discharge from partial reaction a) and their adducts with the alcohol ROH I and optionally multiply alkoxylated by-products can also be separated off from the adduct II. Since these by-products generally do not have a disruptive effect in the further course of the process according to the invention, their separation can also be omitted.
  • the distillation can also be carried out in such a way that, apart from adduct III, only a part of the by-products, in particular the olefinic 1,3-butadiene dimers and trimers and multiply alkoxylated by-products, are removed, but other by-products, in particular the alkoxyoctadiene and if desired, the alkoxydodecatriene, further processed together with the adduct II in the subsequent partial reactions, octanols or dodecanols, which are desired as plasticizer alcohols, being produced as end products from these by-products of the partial reaction a).
  • Adduct III like the unreacted 1,3-butadiene, can then be returned to the process step of partial reaction a) of the process according to the invention.
  • the return of the adduct III in the process step of the partial reaction a) of the process according to the invention causes the isomerization of the adduct III to the adduct II in this process step and ultimately leads to the suppression of the formation of the undesired adduct III, so that when using this cycle procedure in the overall balance of this cycle practically only the desired adduct II, but not its undesired isomer III is formed.
  • the isomerization of the adduct III can also be accomplished in a separate isomerization stage instead of by recycling it to the process stage of the partial reaction a) of the process according to the invention, by adding the adduct III separated from the adduct II e.g. through an isomerization reactor charged with one of the catalysts which can be used in partial reaction a), the discharge of this reactor, which consists of the isomerization mixture formed therein from adduct III and
  • Adduct II exists, for example by distillation into adduct II and adduct III, the newly formed adduct II is further processed in the further course of the process according to the invention to n-butyraldehyde and / or n-butanol and the adduct III is returned to the isomerization reactor.
  • the isomerization of adduct III to adduct II in the isomerization reactor can take place in the presence or absence of a solvent.
  • a solvent can be advantageous as an isomerization catalyst, in particular when using one of the aforementioned complexes of an element from Group IA, VIIA or VIIIA of the Periodic Table of the Elements.
  • high-boiling solvents such as ethers, for example di- or triethylene glycol dimethyl ether, di- or triethylene glycol dibutyl ether, sulfoxides, e.g.
  • Dimethyl sulfoxide or sulfones such as sulfolane, high-boiling aromatic or aliphatic hydrocarbons or halogenated aliphatic or aromatic solvents, e.g. Dichlorobenzene.
  • sulfoxide or sulfones such as sulfolane, high-boiling aromatic or aliphatic hydrocarbons or halogenated aliphatic or aromatic solvents, e.g. Dichlorobenzene.
  • the use of low-boiling solvents is also possible, but as a rule requires an increased outlay in the separation by distillation of the discharge from the isomerization reactor into adducts II and III.
  • the adduct II is catalytically reacted with an alcohol ROH I in the partial reaction c) Acetal of the formula IV implemented, which is then hydrolyzed in partial reaction d) catalytically in the presence of water to n-butyraldehyde and / or converted catalytically in the presence of water and hydrogen to n-butanol.
  • the partial reactions c) and d) in the process according to the invention can optionally be carried out successively in two process stages or successively in a single reactor.
  • reaction equations (2) the partial reactions c), the isomerization and acetalization of the adduct II to the acetal IV and d), its reaction with water or hydrogen and water to give n-butyraldehyde and / or n-butanol are preferably carried out successively.
  • These partial reactions include the following chemical reactions according to reaction equations (2):
  • the enol ether by-product can also be removed from the process cycle, for example after separation by distillation from the end product as the process according to the invention, and other uses, for example for the production of the corresponding saturated ethers selective hydrogenation of the double bond are supplied.
  • ethers are used, for example, as solvents.
  • the same alcohols ROH I can be used for the reaction according to partial reaction c), which can be used to carry out partial reaction a) and were described in this application in the explanation of partial reaction a).
  • the alcohol ROH I used to carry out the partial reaction c) can be the same alcohol as was used in the previous partial reaction a), but it can also be different from this. Mixtures of several alcohols ROH I can of course also be fed to partial reaction c).
  • the same alcohol ROH I is used in partial reaction c) as is used in partial reaction a), particularly preferred as alcohol ROH I is also in partial reaction c) n-butanol.
  • cyclic acetals IV can also be formed.
  • the last reaction step i.e. the hydrolysis of the acetal IV to n-butyraldehyde on the one hand or the combined hydrolysis / hydrogenation of the acetal IV to n-butanol on the other hand can be made possible by the choice of the reaction conditions, in particular by the choice of the catalyst and the choice of those made available during the reaction
  • Amount of water and hydrogen reactants are controlled so that either the end product n-butyraldehyde or n-butanol is selectively formed or that mixtures of these two valuable products are formed as the end product of the process according to the invention.
  • the catalysts to be used according to the invention which catalyze the conversion of adduct II to acetal IV, are generally also good as catalysts for the hydrolysis of acetal IV to n-butyraldehyde or for the combined hydrolysis / hydrogenation of acetal IV to n -Butanol are suitable. Accordingly, in a particularly preferred embodiment of the process according to the invention, the same catalysts can be used both in partial reaction c) and in partial reaction d), irrespective of whether n-butyraldehyde and / or n-butanol are produced as the end product should.
  • the acetalization of adduct II to acetal IV and its hydrolysis or combined hydrolysis / hydrogenation to n-butyraldehyde and / or n-butanol is carried out in succession using a homogeneous catalyst.
  • transition metal element compounds can be used as homogeneous catalysts for the acetalization of adduct II to acetal IV and its hydrolysis or combined hydrolysis / hydrogenation to n-butyraldehyde and / or n-butanol, in particular those which contain elements from VI. and VIII.
  • Subgroup of the Periodic Table of the Elements preferably molybdenum, iron, cobalt, nickel, in particular of platinum metals, ruthenium, rhodium, palladium, platinum, osmium and / or iridium, particularly preferably ruthenium, rhodium, iridium or osmium. This does not apply to dicobalt octacarbonyl (Co 2 (CO) 8 ) and hydridocobalt tetracarbonyl (HCo (C0) 4 ).
  • Suitable catalysts are, for example, the salts of these transition metals, preferably those of the platinum metals, in particular their halides, nitrates, sulfates, phosphates, carboxylates soluble in the reaction medium, for example their C 1 -C 2 carboxylates, such as formates, acetates, trichloroacetates, propionates, 2-Ethylhexanoate, 2-Propylheptanoate, Dekanoate, further sulfonates such as methanesulfonates, benzenesulfonates, naphthalenesulfonates, toluenesulfonates, Trifluormethylbenzolsulfo- nate or trifluoromethanesulfonates, cyanides, tetrafluoroborates, perchlorates or hexafluorophosphates, soluble inorganic complex compounds of these elements, in particular their aqua, amine
  • Preferred salt-like homogeneous catalysts are the halides, in particular the chlorides, nitrates, sulfates, sulfonates, carboxylates and cyanides of rhodium, ruthenium, palladium, platinum and iridium.
  • Inorganic complex compounds which are preferably used in the process according to the invention for carrying out the partial reactions c) and d) are, for example Ruthenium trichloride, rhodium trichloride or iridium hexaaquaditosylate.
  • the phosphine or phosphite complexes in particular the phosphine complexes of the platinum metals ruthenium, rhodium, iridium and osmium, are particularly preferred.
  • Suitable phosphine ligands are, for example, the phosphine ligands which are suitable for carrying out the partial reaction a) of the process according to the invention and are mentioned in the description of this partial reaction in this application, to which reference is hereby made.
  • Triphenylphosphine and the alkylene-bridged bisphosphine ligands mentioned at the stated site are particularly preferred.
  • Suitable 2, 2 '-bipyridine or 1, 10-phenanthroline ligands are, for example, the 2, 2' -bipyridine or 1, 10-phenant- suitable for carrying out the partial reaction a) of the process according to the invention and mentioned in the description of this partial reaction.
  • Suitable phosphite ligands are, for example, trialkyl phosphites, alkyl diaryl phosphites, triaryl phosphites, alkyl bisphosphites, aryl bisphosphites, alkyl aryl bisphosphites.
  • the alkyl group-bearing phosphite ligands can contain the same or different Ci to C ⁇ 0 -, preferably C ⁇ ⁇ to C 6 alkyl or cycloalkyl groups.
  • the aryl group-bearing phosphite ligands can contain identical or different Cg to C i aryl groups, in particular the phenyl or naphthyl group, but also the diphenyl group or the binaphthyl group. Phosphite ligands can also be used Complexation of the transition metals are used, the heterocycloaliphatic groups such as pyrrolidine, imidazolidine, piperidine, morpholine, oxazolidine, piperazine or triazolidine groups or heteroaromatic groups such as pyrrole, imidazole, oxazole, indole , Pyridine, quinoline, pyrimidine, pyrazole,
  • the alkyl or aryl groups of the phosphite ligand may be unsubstituted or under the reaction conditions inert substituents, such as C ⁇ ⁇ to C 4 alkoxy, di-Ci alkylamino- to C 4, C ⁇ ⁇ to C alkyl ⁇ ,
  • phosphite ligands Hydroxy, nitro, cyano or sulfonate groups.
  • the sulfonate-substituted phosphite ligands and their complexes are generally water-soluble.
  • Suitable phosphite ligands are e.g.
  • the aforementioned organometallic compounds of the transition metals contain phosphorus-containing ligands, in particular phosphine ligands, containing carbonyl complexes of the platinum metals, such as HRh (PPh 3 ) 3 (CO), IrCl (CO) (PPh 3 ) 3 , [Ir (cod) PPh 3 ) 2 ] PF 6 (cod is the abbreviation for the 1,5-cyclooctadiene ligand) HRuCl (PPh 3 ) 3 (CO), HRu (CO) (CH 3 COO) (PPh 3 ) 2 , H 2 Ru ( CO) (PPh 3 ) 3 , RuCl 2 (CO) 2 (PPh 3 ) 3 or RuH (CO) (C 9 H 19 COO) (PPh 3 ) 2 - C 9 H 19 COO is the capric acid anion - as homogeneous catalysts for the Carrying out the partial reactions c) and d) is particularly preferred.
  • halogen-free complexes are again preferred, for example those which contain the conjugate base of an OH-acidic, organic compound as ligands, OH-acidic, organic compounds being understood as meaning those compounds which give an acidic reaction in aqueous solution, such as monocarboxylic acids, monosulfonic acids or non-chelating phenols.
  • ligands can advantageously be C - to C 3 o-carboxylic acid anions, which preferably derive from a monocarboxylic acid, such as acetate, propionate, butyrate, isobutyrate, valerianate, pivaloate, capronate, enanthate, caprylate , 2-ethylhexanoate, 2 -propylheptanoate, caprinate, laurate, myristate, palmitate, stearate, oleate, benzoate, alkylbenzoate, naphthoate and alkylnaphthoate anions or non-chelating phenolate anions or sul serve onate anions.
  • a monocarboxylic acid such as acetate, propionate, butyrate, isobutyrate, valerianate, pivaloate, capronate, enanthate, caprylate , 2-ethylhexanoate, 2 -
  • Phenolates which can advantageously be used as ligands in such transition metal-organic compounds which are effective as homogeneous catalysts for the partial reactions c) and d) are, for example, the phenolate and naphtholate anions and on the aromatic nucleus with phenolate substituted under the reaction conditions of the partial reactions c) and d) - And naphtholate anions, for example Ci to C 2 o-alkyl, preferably Ci- to Cio-alkyl-substituted phenolates or naphtholates, such as methylphenolate, nonylphenolate -, 2, 6 -ditert. -butylphenolate- or 2, 6 -ditert. - Butyl-4-methylphenolate anions.
  • Sulfonate ligands which can advantageously be used for this purpose are e.g. Alkyl sulfonates such as the methanesulfonate or octylsulfonate, dodecylsulfonate, octadecylsulfonate or trifluromethanesulfonate anion or arylsulfonates such as the toluenesulfonate anion.
  • These complexes containing carboxylate ligands can, for example, starting from RuH 2 (PPh 3 ) 3 (CO), which is accessible, for example, according to Uttley et al, Inorganic Syntheses, Vol. XVII, 125 (1977), by reaction with the corresponding carboxylic acids analogously to by Robinson et al, J. Chem. Soc, Dalton Trans. 1912 (1973), Frediani et al, ib. 165 (1990), ib. 1705 (1990), ib. 3663 (1990) and Frediani et al, J. Organomet Chem. 454, C17-C19 (1993) developed methods.
  • the corresponding complexes containing phenolate ligands can accordingly be obtained by reacting H 2 Ru (CO) (PPh 3 ) 3 with the phenols in question.
  • Complexes containing sulfonate ligands can be obtained, for example, by the process described in US Pat. No. 4,892,955.
  • the halogen-containing homogeneous catalysts can be prepared, for example, by the process of Uttley et al, Inorganic Syntheses, Vol.XV, 45 (1974) by the reaction of RuCl 3 with formaldehyde.
  • the aforementioned catalysts can be added as such to the reaction mixture or - this applies in particular to the homogeneous carboxylate or phenolate ligands containing catalysts - also in situ in the reaction mixture, by reacting RuH 2 (PPH 3 ) 3 (CO) with the carboxylic acid or phenol in question.
  • RuH 2 (PPH 3 ) 3 (CO) with the carboxylic acid or phenol in question.
  • complexes containing hydrido ligands can be generated in situ in the presence of elemental hydrogen H, for example under the conditions of the hydrogenation reaction according to partial reaction d).
  • Transition organometallic compounds especially organic ruthenium compounds, which are modified with carboxylate, sulfonate or phenolate ligands and contain additional carbonyl- and / or phosphorus-containing ligands, in particular phosphine or phosphite ligands, preferably phosphine ligands, are distinguished in the process according to the invention as homogeneous catalysts for the catalysis of the partial reactions c) and d) both by a high activity and selectivity as well as by a high stability and thus a long service life.
  • the high activity and selectivity of these homogeneous catalysts relates equally to the conversion of adduct II to acetal IV and to the hydrolysis or combined hydrolysis / hydrogenation of acetal IV to butyric aldehyde or butanol. This also has a favorable influence on the selectivity and the economy of the overall process.
  • the acidic compound in question is present in free form in equilibrium with the transition metal-organic compound serving as a homogeneous catalyst in the reaction mixture.
  • the same acidic compound is expediently used as is bound to the transition metal in the transition metal-organic compound, but the addition of other acidic organic compounds is equivalent to this measure.
  • the acidic organic compound is used in a molar ratio of 1: 1 with respect to the transition metal-organic compound which functions as a homogeneous catalyst.
  • the phosphine or phosphite is generally used in a 2 to 100 molar range, preferably in a 2 to 100 molar range, with respect to the phosphine or phosphite complex of the transition metal element 20 molar and particularly preferably added in a 2 to 10 molar amount.
  • the transition metal element complex serving as a homogeneous catalyst in situ in the
  • catalysts are generally used in amounts of 0.001 to 1.0 mol%, preferably of 0.01 to 1.0 mol%, with respect to the adduct II fed to the reactor. It goes without saying for the person skilled in the art that the amount of homogeneous catalyst to be added depends on the catalytic activity of the particular one used
  • homogeneous catalyst is dependent. Depending on the type of homogeneous catalyst used, a greater or lesser amount of catalyst can therefore advantageously be added to the reaction mixture. The optimum amount for the particular homogeneous catalyst used is expediently determined in a preliminary test.
  • the partial reactions c) and d) can be carried out batchwise using the homogeneous catalysts mentioned, e.g. in stirred tanks or continuously, e.g. in loop reactors or stirred tank cascades, at temperatures of generally 20 to
  • solvents such as aliphatic or aromatic hydrocarbons , for example toluene, benzene or cyclohexane, alcohols, preferably in excess alcohol ROH I used for the acetalization, in particular n-butanol, higher fatty alcohols or glycols, ethers, for example dibutyl ether, tetrahydrofuran, dioxane or
  • halogenated aliphatic or aromatic hydrocarbons eg chloro- form, dichloromethane, chlorobenzene, dichlorobenzene, sulfoxides or sulfones, for example dimethyl sulfoxide or sulfolane.
  • the isomerization and acetalization of the adduct II to the acetal IV and its conversion to n-butyraldehyde and / or n-butanol can also take place in a phosphine melt.
  • This procedure can advantageously be used with homogeneous catalysts containing phosphine.
  • the phosphine which serves as a solvent can in principle be chosen arbitrarily, but preferably that phosphine is used in the melt which serves as a ligand in the transition metal element complex serving as a homogeneous catalyst.
  • the addition of the alcohol ROH I can be varied widely.
  • the aquimolar amount required to form the acetal IV can, if desired, also be exceeded.
  • the alcohol ROH I for carrying out the partial reaction c) is the reactor, based on the adduct II used in this partial reaction, in a molar ratio I / II of 1: 1 to 30 100: 1, preferably 1: 1 to 10 : 1, in particular from 1: 1 to 5: 1.
  • Higher molar excesses of the alcohol ROH I with respect to the adduct II generally have no adverse effect on the result of the reaction in the partial reactions c) and d), but the alcohol ROH I is expediently used in the context of the 35 proportions mentioned above.
  • the reaction mixture from partial reaction c) is mixed with water in a molar ratio, based on the adduct II fed to the reactor, which 40 in partial reaction c) in the course of the process according to the invention to give the acetal intermediate IV has been added, generally from 1: 1 to 100: 1, preferably 1: 1 to 20: 1 and particularly preferably from 1: 1 to 10: 1.
  • Partial reaction c) is accordingly carried out under essentially anhydrous conditions, ie in the absence of technically effective amounts of water. It goes without saying that the presence of small traces of water, which have no measurable influence on the yield and economy of the process according to the invention, can be tolerated.
  • the batchwise procedure can be carried out by first adding the adduct II with the alcohol ROH I in a reactor, e.g. a stirred kettle, converted to acetal IV under the specified conditions and, after the reaction has ended, introduces the reactants water into the reaction mixture obtained for further conversion of the acetal IV to n-butyraldehyde in accordance with partial reaction d).
  • a reactor e.g. a stirred kettle
  • the introduction of the water and its reaction with the acetal IV can take place in the same reactor as was used for the partial reaction c), that is to say in a "one-pot reaction", and it is also possible for the partial reactions c) and d) to be carried out successively different reactors.
  • the water is fed via a separate inlet into the reaction tube or a reactor of the reactor cascade after the dwell time required for the reaction according to partial reaction c).
  • reaction mixture from partial reaction c) in addition to the water required for the hydrolysis of acetal IV, is also fed with hydrogen in a molar ratio, based on that of partial reaction c)
  • Adduct II generally from 1: 1 to 100: 1, preferably from 1: 1 to 50: 1 and particularly preferably from 1: 1 to 10: 1, is added. This admixture can be carried out in batchwise operation of the process by injecting the required amount of hydrogen into the reactor or by dispersing the hydrogen in the
  • Reaction medium for example by means of bubble columns or by loop reactors equipped with jet nozzles for dispersing the hydrogen.
  • the hydrogen can be admixed together with the water required for the combined hydrolysis / hydrogenation in partial reaction d), as described above, after the reaction in accordance with partial reaction c).
  • the hydrolysis of the acetal IV to n-butyraldehyde or the combined hydrolysis / hydrogenation of the acetal IV in partial reaction d) can be carried out using the same catalyst as the formation of the acetal IV from the adduct II, the reaction mixture has to be worked up from partial reaction c) it is generally not necessary to add the reactants water or hydrogen and water, that is to say before initiating the partial reaction d).
  • the quantitative ratio of these products in the product mixture can be adjusted, for example, by adding hydrogen and / or the reaction temperature used. If substoichiometric amounts of hydrogen are used, of course only part of the starting material is hydrogenated to n-butanol, and by using a lower reaction temperature the rate of the hydrogenation reaction can be slowed down to such an extent that only part of the starting material is hydrogenated to n-butanol.
  • the reaction product is generally worked up by distillation, the homogeneous catalyst used being recovered from the bottom of the distillation and, if desired, can be reused, for example by recycling the catalyst solution into the partial reaction c) of the acetalization of the adduct II to the acetal IV and / or Partial reaction d), that is, its hydrolysis and optionally hydrogenation.
  • a solvent preferably a solvent which boils at a higher temperature than the reaction products n-butanol and n-butyraldehyde, can advantageously be added to the reaction mixture.
  • the addition of a high-boiling solvent can be dispensed with and the homogeneous catalyst e.g. be returned to the reaction in the form of a triphenylphosphine melt.
  • reaction product n-butyraldehyde and / or n-butanol is furthermore separated from the alcohol ROH I which is released or added from the acetal IV by hydrolysis or hydrogenation in the preceding partial reactions c) and d), where the amount of alcohol ROH I added for the acetalization is advantageously returned to the first process stage of the process according to the invention, the addition of the alcohol ROH I to 1,3-butadiene and / or to the partial reaction c) of the process according to the invention.
  • Valuable by-products of the process according to the invention can be obtained in the working up of the reaction product by distillation, the octanols or dodecanols formed as a result of the partial dimerization and trimerization of the butadiene, or the aldehydes corresponding to these alcohols.
  • the octanols or dodecanols formed as a result of the partial dimerization and trimerization of the butadiene, or the aldehydes corresponding to these alcohols Possible not Fully converted acetal IV or, if appropriate, as a by-product in the work-up of isolated enol ethers V by distillation can be recycled back into the partial reactions c) or d).
  • the isomerization and acetalization of the adduct II to the acetal IV and its hydrolysis or hydrogenation to n-butyraldehyde and / or n-butanol is carried out using a heterogeneous catalyst in the liquid phase.
  • hydrogenation catalysts preference is given to those which contain one or more elements from group IA, VIA, VIIA or VIIIA, if appropriate in combination with one or more elements from group VA, from the periodic table of the elements, in particular chromium, molybdenum, tungsten, rhenium, Ruthenium, cobalt, nickel, rhodium, iridium, osmium, palladium and / or platinum, optionally in combination with iron and / or copper.
  • Particularly active hydrogenation catalysts such as nickel or the platinum metals can advantageously be doped with main group elements, which act as catalyst poison, and in this way partially poisoned. This measure allows a higher selectivity in the combined hydrolysis / hydrogenation of the acetal IV to n-butanol.
  • Main group elements suitable for partial poisoning of such particularly active hydrogenation catalysts are e.g. the chalcogens, such as sulfur, selenium and tellurium, as well as the elements phosphorus, arsenic, antimony, bismuth, tin, lead and thalium.
  • Subgroup elements suitable for this purpose are e.g. Mercury and cadmium.
  • So-called precipitation catalysts can be used as heterogeneous catalysts in the process according to the invention.
  • Such catalysts can be produced by their catalytically active components from their salt solutions, in particular from the solutions of their nitrates and / or acetates, for example by adding solutions of alkali metal and / or alkaline earth metal hydroxide and / or carbonate solutions, for example sparingly soluble hydroxides, oxide hydrates, basic salts or carbonates precipitates, the precipitates obtained subsequently dry and these are then calcined at generally 300 up to 700 ° C, in particular 400 to 600 ° C in the oxides, mixed oxides and / or mixed-valent oxides in question, which, for example, by treatment with reducing agents such as hydrogen or hydrogen-containing gases, usually at 50 to 5 700 ° C, in particular at 100 to 400 ° C., to the metals in question and / or to oxidic compounds of a low oxidation state and reduced to the actual, catalytically active form.
  • the catalytically active components can be precipitated in the presence of the support material in question.
  • the catalytically active components can, however, advantageously also be precipitated from the relevant salt solutions at the same time as the support material, as is the case, for example, when the catalytically active components are precipitated using a water glass solution.
  • suitable support catalysts for the process according to the invention are generally those in which the catalytically active components are e.g. have been applied to a carrier material by impregnation.
  • the way in which the catalytically active metals are applied to the support is generally not critical to the result of the process and can be accomplished in a variety of ways.
  • the catalytically active metals can be applied to these support materials, for example by impregnation with solutions or suspensions of the salts or oxides, drying and subsequent reduction of the metal compounds to the relevant metals or oxidic compounds at a low oxidation level using a reducing agent, preferably with Hydrogen, hydrogen-containing gases or hydrazine can be applied.
  • catalytically active metals can be deposited on the catalyst support by vapor deposition or by flame spraying.
  • solutions of salts which are easily decomposable thermally for example with nitrates or with complex compounds which are easily decomposable thermally, for example carbonyl or hydrido complexes of the catalytically active metals impregnate and heat the soaked carrier to 5 temperatures of 300 to 600 ° C for the thermal decomposition of the adsorbed metal compounds.
  • This thermal decomposition is preferably carried out under a protective gas atmosphere. Suitable protective gases include nitrogen, carbon dioxide, Hydrogen or the noble gases.
  • the catalytically active metals can be deposited on the catalyst support by vapor deposition or by flame spraying.
  • supported catalysts in the catalytically active metals are in principle not critical for the success of the process according to the invention. It goes without saying for a person skilled in the art that higher levels of these supported catalysts in catalytically active metals lead to higher space-time conversions than lower levels. In general, however, supported catalysts are used whose content of catalytically active metals is 0.1 to 80% by weight, preferably 0.5 to 30% by weight, based on the total catalyst. Since this content information relates to the entire catalyst including support material, but the different support materials have very different specific weights and specific surfaces, this information can also be exceeded or fallen short of, without this having a disadvantageous effect on the result of the process according to the invention .
  • the catalytically active metals can also be applied to the respective carrier material.
  • the catalytically active metals can be applied to the support, for example by the processes of DE-A 2 519 817, EP-A 147 219 and EP-A 285 420.
  • the catalytically active metals are present as an alloy, which can be obtained by thermal treatment and / or reduction of e.g. by impregnation on a support deposited salts or complexes of the aforementioned metals.
  • the precipitation catalysts and also the supported catalysts can also be activated in situ in the reaction mixture by the hydrogen present there, but these catalysts are preferably activated before they are used in the process according to the invention.
  • the oxides of aluminum or titanium, zirconium dioxide, silicon dioxide, diatomaceous earth, silica gel, clays, for example montmorillonites, silicates, such as magnesium or aluminum silicates, zeolites, such as ZSM-5 or ZSM-10 zeolites and activated carbon can generally be used as carrier materials.
  • Preferred carrier materials are aluminum oxides, titanium dioxide, zirconium dioxide and activated carbon.
  • Mixtures of different support materials can of course also serve as supports for catalysts which can be used in the process according to the invention.
  • the following catalysts may be mentioned as examples of heterogeneous catalysts which can be used for carrying out the partial reactions c) and d):
  • Hydrogenation catalysts which contain Bronsted and / or Lewis acids can also advantageously be used in the process according to the invention.
  • Lewis acidic centers e.g. the catalytically active metals themselves act if they are not completely reduced to the metals in question when the catalyst is activated with gases containing hydrogen or hydrogen.
  • Such Lewis or Bronsted acidic or basic centers can also be introduced into the catalyst via the support material used.
  • Support materials containing Lewis or Bronsted acidic centers are e.g. the aluminum oxides, titanium dioxide, zirconium dioxide, silicon dioxide, the silicates, clays, zeolites, magnesium-aluminum mixed oxides and activated carbon.
  • supported catalysts as hydrogenation catalysts which contain elements from subgroups I, VI, VII and / or VIII.
  • Subgroup of the Periodic Table of the Elements in particular elements of subgroups VII and VIII.
  • Subgroup of the Periodic Table of Elements contain a Bronsted or Lewis acidic carrier material.
  • catalysts are, for example, ruthenium on activated carbon, ruthenium on aluminum oxide, ruthenium on silicon dioxide, ruthenium on magnesium oxide, ruthenium on zirconium dioxide, ruthenium on titanium dioxide, palladium on aluminum oxide, palladium on silicon dioxide, palladium on zirconium dioxide, palladium on barium sulfate and palladium partially poisoned with selenium or lead on activated carbon catalysts.
  • Hydrogenation catalysts which themselves have no such Bronsted or Lewis acidic centers can be added to Lewis or Bronsted acidic components such as zeolites, aluminum or silicon oxides, phosphoric acid or sulfuric acid. They are generally used in amounts of from 0.01 to 5% by weight, preferably from 0.05 to 0.5% by weight and particularly preferably from 0.1 to
  • heterogeneous catalysts are suitable for converting the adduct II to the acetal IV and its subsequent hydrolysis or combined hydrolysis / hydrogenation to give n-butyraldehyde and / or n-butanol, which complex compounds of transition metal elements from the group VIA and VIIIA des usable for the homogeneous catalysis of these partial reactions
  • Periodic table of the elements in heterogeneous form for example those in which the transition metal element in question is fixed to a polymeric matrix.
  • Such polymeric matrices can be resins, such as styrene-divinylbenzene resins or phenol-formaldehyde resins, to which the ligands in question which serve to complex the transition metal element are preferably covalently bound, which in turn form complexes with the transition metals in question and quasi immobilize them in this way.
  • Such heterogenized, polymer-bound transition metal complex catalysts with 2, 2 '-bipyridine or 1, 10-phenanthroline ligands or heterogenized phosphine or phosphite complexes of the catalytically active transition metal elements can e.g. according to the literature processes mentioned in the explanation of partial reaction a) for the preparation of these catalysts.
  • the acetalization of the adduct II to the acetal IV and then its hydrolysis or hydrogenation to n-butyraldehyde and / or n-butanol can be carried out either continuously or batchwise.
  • the heterogeneous catalyst can either be suspended in the liquid reaction medium or preferably arranged in a fixed bed or several fixed beds. The process can be carried out using a suspension in the liquid reaction medium.
  • Heterogeneous catalyst can be carried out, for example, in stirred tanks or loop reactors.
  • the reaction mixture is generally passed in the bottom or trickle way over the fixed catalyst bed.
  • Both the hydrolysis of acetal IV and its combined hydrolysis and hydrogenation can be carried out in reactors operated adiabatically or isothermally.
  • the catalyst is loaded with the liquid reaction mixture at a space velocity of 0.01 to 10, preferably 0.02 to 3 and particularly preferably 0.03 to 1 kg of reaction mixture / 1 catalyst-h.
  • the reaction can take place in the presence or absence of a solvent.
  • the same solvents can be used as solvents which can also be used in carrying out the process under homogeneous catalysis.
  • the addition of the water required for partial reaction d) has a disadvantageous effect on the formation of acetal IV from adduct II and the alcohol ROH I in accordance with partial reaction c). For this reason, even in the case of heterogeneous catalysis, the water is only added after the partial reaction c) has ended and the partial reaction d) is initiated with the addition of water or the addition of hydrogen and water. Accordingly, in the batchwise mode of operation under heterogeneous catalysis, the addition of water or the addition of hydrogen and water is carried out in an analogous manner to that described above for carrying out the partial reactions c) and d) using homogeneous catalysis.
  • Sub-reaction c) is consequently also carried out in the case of heterogeneous catalysis under essentially water-free conditions, ie in the absence of technically effective amounts of water. It goes without saying it goes without saying that the presence of small traces of water, which have no measurable influence on the yield and economy of the process according to the invention, can be tolerated.
  • the addition of the alcohol ROH I to produce the acetal IV from the adduct II can also be varied within wide limits in the heterogeneous catalysis of partial reaction c).
  • the required equimolar amount can, if desired, also be exceeded.
  • the alcohol ROH I for carrying out the partial reaction c) becomes the reactor, based on the adduct II used in this partial reaction, in a molar ratio I / II of 1: 1 to 100: 1, preferably from 1: 1 to 10: 1, in particular 1: 1 to 5: 1.
  • the amount of water added for the hydrolysis of the acetal IV in accordance with partial reaction d) is expediently based on the amount of adduct II originally added to partial reaction c), since the discharge from partial reaction c) is generally used without further workup for the reaction in accordance with partial reaction becomes.
  • the combined isomerization and acetalization of the adduct II to the acetal IV as well as its subsequent hydrolysis to n-butyraldehyde over the heterogeneous catalyst in the liquid phase are generally carried out at a temperature of 20 to 300 ° C., preferably 50 to 280 ° C. and particularly preferably 80 to 250 ° C and at a pressure of generally 1 to 100 bar, preferably from 1 to 50 bar, in particular from 2 to 10 bar.
  • the hydrogen required for the preparation of n-butanol in partial reaction d) in addition to the water is, when carrying out the process under heterogeneous catalysis, the discharge from partial reaction c) with respect to the adduct II originally fed to partial reaction c) in a molar ratio of generally 1 to 100, preferably from 1.5 to 80, in particular from 2 to 40, added.
  • the amount of hydrogen to be used in partial reaction d) for the production of n-butanol is more appropriately based on the amount of adduct II supplied to partial reaction c), since the discharge from partial reaction c) is generally carried out without prior work-up. tion is implemented in partial reaction d).
  • the combined isomerization and acetalization of adduct II to acetal IV and its subsequent hydrolysis / hydrogenation to n-butanol over the heterogeneous catalyst in the liquid phase is generally carried out at a temperature of from 20 to 300 ° C., preferably from 50 to 280 ° C. and particularly preferably from 80 to 250 ° C and at a pressure of generally 1 to 300 bar, preferably from 5 to 250 bar, in particular from 20 to 200 bar. It goes without saying that the amount of water and alcohol I required to prepare n-butanol based on adduct II is equal to the amount of water or alcohol required to prepare n-butyraldehyde from adduct II.
  • the desired end product is a mixture of n-butyraldehyde and n-butanol
  • water, alcohol I and hydrogen are generally mixed with respect to the adduct II introduced into partial reaction c), in an analogous manner to that described above, in a ratio which is appropriate for the recovery both end products in the desired product ratio.
  • the product ratio of these two end products in the reactor discharge can also be controlled via the use of certain heterogeneous catalysts, for example by using heterogeneous catalysts which have a high hydrolysis activity and a relatively low hydrogenation activity in comparison therewith.
  • inactivated or partially poisoned catalysts e.g. Palladium partially poisoned with selenium or lead can advantageously be used on activated carbon catalysts.
  • the liquid reaction product from partial reaction d) is generally worked up by distillation in an analogous manner to that which has already been described for carrying out this partial reaction with homogeneous catalysts.
  • heterogeneous catalysts there is naturally no need to recycle the catalyst, as may be expedient and advantageous when using homogeneous catalysts.
  • the recycling of the alcohol ROH I released or added again in partial reaction d) to the process step of adding the alcohol ROH I to 1,3-butadiene and / or to the reaction according to partial reaction c) can advantageously be carried out in an analogous manner , as already described for the implementation of this partial reaction with homogeneous catalysts.
  • one advantage of the process according to the invention is that both for the combined isomerization / acetalization in partial reaction c) and for the hydrolysis of the acetal IV to n-butyraldehyde or for the combined hydrolysis / hydrogenation of the acetal VI in partial reaction d ) the same heterogeneous catalyst can be used, which can save catalyst costs.
  • the partial reactions c) and d) are carried out in successive process stages, different modes of operation can be used in the individual process stages.
  • the conversion of the adduct II to the acetal IV can optionally be carried out using homogeneous catalysis or on heterogeneous catalysts, and the hydrolysis or the combined hydrolysis / hydrogenation of the acetal IV to n-butyraldehyde and / or n-butanol can optionally be used in the liquid phase of homogeneous or heterogeneous catalysts.
  • the alcohol ROH I liberated from the acetal IV in the hydrolysis or combined hydrolysis / hydrogenation is preferably recycled back into the reaction according to partial reaction a) and / or into the reaction according to partial reaction c).
  • a butenyl ether of the formula II prepared in a different manner can also be used in the partial reaction c).
  • the above explanations for carrying out the partial reactions c) and d) naturally apply analogously if such a butenyl ether of the formula II which is prepared in a different manner outside the integrated process is used as the starting material in the partial reaction c). Such a procedure is advantageous if the butenyl ether of the formula II from another production process is available at a production site.
  • the process according to the invention is based on the flow diagram according to the drawing, which schematically shows an advantageous embodiment of the process according to the invention, in which both the addition of the alcohol ROH I to 1,3-butadiene or a butadiene-containing hydrocarbon mixture and the isomerization and acetalization of the adduct II to acetal IV and its hydrolysis or combined hydrolysis / hydrogenation to n-butyraldehyde and / or n-butanol in a single process step in the liquid phase • d ⁇ G ⁇ rH ⁇ ⁇ id -H ⁇ xi ⁇ T) 0 cn ⁇ ⁇ 3 ⁇
  • composition of the products to be distilled in these columns varies depending on the procedure used in reactors 2, 14 and 30, and it is a routine task of the person skilled in the art in view of the product composition present in each case the distillation column or distillation columns required for the separation of the products to dimension accordingly.
  • the end products n-butyraldehyde and n-butanol can be obtained with a higher selectivity starting from 1,3-butadiene than with the previously known processes which use butadiene as starting material for the production of these products.
  • a 0.3 1 stirred autoclave was charged with 67.0 g (0.90 mol) of n-butanol and 11.5 g Lewatit ® SPC 118 in the H + form which had been previously washed with water and n-butanol, and 3.5 g of copper (II) chloride doped Lewatit ® SPC 118-filled ion exchanger. Then 47.0 g (0.88 mol) of 1,3-butadiene were pressed into the autoclave. After a reaction for 10 h at 90 ° C. and under autogenous pressure, a selectivity of 46.8% for 3-butoxybut-l-ene and a selectivity of 44.3% for l-butoxybut-2- received (based on butadiene).
  • Table 2 relates to the use of various acidic undoped ion exchangers as catalysts
  • Table 3 shows the results of experiments in which different amounts of undoped Lewatit SPC 118 ion exchanger mixed with copper (II) chloride were used as catalysts
  • Table 4 lists the results obtained with mixtures of ion exchangers doped with various copper (II) salts with the undoped ion exchangers as catalysts.
  • Table 1 Continuous addition of n-butanol to butadiene
  • a stirred autoclave was charged with 6.0 g of n-butanol, 2.0 g of 3-butoxy but-l-ene and 1.2 g of dried Lewatit ® SPC 118 ion exchanger in the H + form filled.
  • the reaction mixture was heated to 105 ° C. and a sample was taken after a reaction time of 2 and 6 hours and the ratio of 3-butoxybut-1-ene / 1-butoxybut-2-ene was determined by gas chromatography. The change in this ratio with the reaction time is shown in Table 5.
  • Example 7 (comparison to Example 6)
  • Example 7 was carried out as in Example 6, with the difference that only 1,3-butadiene and n-butanol, but no butoxy-butenes, were fed to the reactor. The results are listed in Table 6.
  • VCH 3 vinylcyclohexene
  • the Y zeolite (H + form) obtained still contained 0.02% by weight of sodium and its X-ray diffractogram corresponded to the typical X-ray diffraction pattern of a Y zeolite in the H + form (FAU structure).
  • Example 8b In an analogous manner as in Example 8b), 0.90 mol of n-butanol and 0.88 mol of 1,3-butadiene were reacted in the H + form in the presence of 5 g of the zeolite prepared according to Example 8a). With a conversion of 40.0%, 3-butoxybut-l-ene with a selectivity of 42.5% and l-butoxybut-2-ene with a selectivity of 16.5% were formed.
  • a 0.3 l stirred autoclave was filled with 51.0 g (0.69 mol) of n-butanol and with 10.0 g of Bayer-Kat.® K 2441 in the H + form. Then 40.0 g of a 1,3-butadiene-containing hydrocarbon mixture (15.4% n / isobutane, 45.4% l- / 2-butenes, 1.0% isobutene, 38.2% butadiene) were added pressed the autoclave. To The reaction was terminated for 10 hours at 100 ° C. and 43 bar and the reaction mixture was analyzed by gas chromatography.
  • Example 10 Addition of n-butanol to 1,3-butadiene or butadiene-containing hydrocarbon mixtures in the presence of a homogeneous transition metal element catalyst
  • the reaction was stopped at a pressure of 9 bar and the reaction mixture was analyzed by gas chromatography.
  • Mihagol filled under a nitrogen atmosphere. Then 26.0 g (0.48 mol) of 1,3-butadiene were injected. After a reaction time of 10 hours at 80 ° C. and a pressure of 10 bar, the reaction was stopped and the reaction mixture was analyzed by gas chromatography.
  • Example 12 hydrolysis of acetal IV to n-butyraldehyde with a homogeneous catalyst
  • a glass autoclave was filled with 3.0 g of water, 0.022 g of the catalyst HRuCKCO) (PPh 3 ) 3 , 0.031 g of triphenylphosphine, 0.005 g of decanoic acid and 3.0 g of 1, 1-dibutoxybutane and stirred at 160 ° C. for 1 hour.
  • the reaction mixture was analyzed by means of calibrated gas chromatography. With a conversion of 90%, n-butyraldehyde was formed with a selectivity of 85%.
  • Example 13 Reaction of adduct II to acetal IV and hydrolysis of acetal IV to n-butyraldehyde in a single step using a homogeneous catalyst
  • a glass autoclave was filled with 3.0 g of water, 0.022 g of the catalyst HRuCKCO) (PPh 3 ) 3 , 0.031 g of triphenylphosphine, 0.005 g of decanoic acid and 3.0 g of 1, 1-dibutoxybutane and then 10 bar of hydrogen were injected. After a reaction time of 14 hours at 160 ° C., the reaction mixture was analyzed by means of calibrated gas chromatography. With a conversion of 99%, n-butanol was formed with a selectivity of 98.5%.
  • Example 15 (Aeetalization of Adduct II to Acetal IV and Hydrogenation of Acetal to n-Butanol in a Single Step Using a Homogeneous Catalyst)
  • a glass autoclave was charged with 0.022 g of the catalyst HRuCKCO) (PPh 3 ) 3 , 0.031 g triphenylphosphine, 0.005 g decanoic acid, 3.18 g (24.8 mmol) l-butoxybut-2-ene, 1.83 g (24.8 mmol) of n-butanol and 2.2 g (122 mmol) of water and then 10 bar of hydrogen were injected. After a reaction time of 16 hours at 155 ° C., the reaction mixture was analyzed by means of calibrated gas chromatography. With a conversion of 72%, n-butanol with a selectivity of 65%, n-butyraldehyde with a selectivity of 20% was formed.
  • Example 16 (Aeetalization of Adduct II to Acetal IV with a Heterogeneous Catalyst in the Liquid Phase)
  • a glass autoclave was mixed with 0.10 g of the heterogeneous catalyst palladium on activated carbon (10 wt.% Pd), 3.0 g (24 mmol) 1-butoxybut-2-ene and 1.73 g (24 mmol) n -Butanol filled. After 16 hours at 150 ° C. under a hydrogen atmosphere (1 bar), the reaction mixture was analyzed by means of calibrated gas chromatography. With a conversion of 21%, 1, 1-dibutoxybutane with a selectivity of 42%, dibutyl ether with 25% and 1-butoxybut-l-ene with 22% was formed.

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Abstract

L'invention concerne un procédé de production de n-butyraldéhyde et/ou de n-butanol selon lequel a) on fait réagir du butadiène-1,3 ou des mélanges d'hydrocarbures contenant du butadiène avec un alcool de formule (I) ROH, dans laquelle le reste R est un groupe alkyle C2 à C20 ou alcényle non substitué ou substitué par 1 ou 2 groupes alcoxy C1 à C10 ou hydroxy, un groupe aryle C6 à C10 ou un groupe aralkyle C7 à C11 ou le groupe méthyle, à une température et une pression élevées en présence d'un acide de Brönsted ou en présence d'un complexe d'un élément du groupe IA, VIIA ou VIIIA de la classification périodique des éléments avec des ligands contenant du phosphore ou de l'azote afin de former un mélange des adduits de formules (II) et (III); b) on isomère l'adduit (III) en adduit (II); c) on fait réagir l'adduit (II) en acétal de formule (IV) en présence d'un volume - suffisant pour la formation de l'acétal (IV) - d'un alcool ROH I et d'un catalyseur d'élément de métal de transition homogène ou hétérogène différent de dicobaltoctacarbonyle ou de hydridocobalttétracarbonyle en phase liquide dans un environnement essentiellement exempt d'eau; d) on génère ensuite du n-butyraldéhyde et/ou du n-butanol à partir de cet acétal (IV) par réaction de ce dernier avec de l'hydrogène et de l'eau ou avec de l'eau en présence d'un catalyseur d'élément de métal de transition homogène ou hétérogène différent de dicobaltoctacarbonyle ou de hydridocobalttétracarbonyle en phase liquide et on libère à nouveau l'alcool ROH I. L'alcool ROH I libéré est ramené dans la réaction selon la réaction partielle a) et/ou c).
EP98913678A 1997-03-17 1998-03-06 Procede de production de n-butyraldehyde et/ou de n-butanol Withdrawn EP0971868A1 (fr)

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GB9823853D0 (en) 1998-10-30 1998-12-23 Bp Chem Int Ltd A process for making n-butyl esters from butadiene
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US8962897B2 (en) 2012-12-19 2015-02-24 Celanese International Corporation Catalysts and processes for producing butanol
US9024090B2 (en) 2012-12-19 2015-05-05 Celanese International Corporation Catalysts and processes for producing butanol
US9018426B1 (en) 2013-12-19 2015-04-28 Celanese International Corporation Processes for producing multi-carbon alcohols
ES2835060T3 (es) * 2015-10-12 2021-06-21 Basf Se Procedimiento de hidroformilación para preparar derivados de hexano 1,6-disustituidos
WO2019180584A1 (fr) * 2018-03-19 2019-09-26 Sabic Global Technologies B.V. Procédé de production d'un additif de carburant
CN110937745B (zh) * 2019-12-12 2022-07-12 万华化学集团股份有限公司 一种柠檬醛合成过程中高浓度废水的处理方法
CN113877635B (zh) * 2021-10-27 2024-02-06 南京延长反应技术研究院有限公司 一种铱基催化剂及其制备方法、醛化方法

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