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WO2001005735A1 - Procede de production de melanges d'alcools - Google Patents

Procede de production de melanges d'alcools Download PDF

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Publication number
WO2001005735A1
WO2001005735A1 PCT/EP2000/006896 EP0006896W WO0105735A1 WO 2001005735 A1 WO2001005735 A1 WO 2001005735A1 EP 0006896 W EP0006896 W EP 0006896W WO 0105735 A1 WO0105735 A1 WO 0105735A1
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Prior art keywords
mixture
alcohol
reaction
mixtures
olefin fraction
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PCT/EP2000/006896
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German (de)
English (en)
Inventor
Heiko Maas
Michael Röper
Peter Schwab
Michael Schulz
Jürgen Tropsch
Hans-Ulrich JÄGER
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BASF SE
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BASF SE
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Priority to JP2001511396A priority Critical patent/JP2003505354A/ja
Priority to EP00956211A priority patent/EP1196362A1/fr
Publication of WO2001005735A1 publication Critical patent/WO2001005735A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/38—Alcohols, e.g. oxidation products of paraffins
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/14—Derivatives of phosphoric acid
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C11/00—Fermentation processes for beer
    • C12C11/02—Pitching yeast

Definitions

  • the present invention relates to a process for the preparation of alcohol mixtures and the mixtures obtained by this process. It further relates to a process for the functionalization of these alcohol mixtures, the functionalized alcohol mixtures thus obtained and their use.
  • fatty alcohols with about 8 to 20 carbon atoms for the production of nonionic and anionic surfactants.
  • the alcohols are subjected to a corresponding functionalization, for example by alkoxylation or glycosidation.
  • the resulting alkoxylates can either be used directly as nonionic surface-active substances or by further functionalization, e.g. can be converted into anionic surface-active substances by sulfation or phosphating.
  • the application properties of this side e.g. their wetting capacity, foaming, fat-dissolving capacity, biodegradability etc. are essentially determined by the chain length and the degree of branching of the hydrophilic hydrocarbon residue of the alcohol used.
  • Alcohols that are well suited for further processing into effective surfactants are also known as surfactant alcohols.
  • Fatty alcohols can be obtained both from native sources and synthetically, for example by building up from starting materials with a lower number of carbon atoms.
  • SHOP process Shell higher olefine process
  • ethene gives olefin fractions with a carbon number suitable for further processing into surfactants.
  • the functionalization of the olefins to give the corresponding alcohols takes place, for example, by hydroformylation and hydrogenation, it being possible, depending on the reaction procedure, to work in one stage or in two separate reaction stages.
  • An overview of hydroformylation processes and suitable catalysts can be found in Beller et al. Journal of Molecular Catalysis A 104 (1995), pp. 17-85.
  • a disadvantage of the ethylene-based processes for the production of fatty alcohols the high cost of the raw material, which makes these processes economically disadvantageous.
  • a hydrocarbon mixture called a Cs cut with a total olefin content of, for example, about 50% is obtained, of which approx. 15% is based on cyclopentene and the rest on acyclic monoolefins, especially n-pentene ( approx. 15% by weight) and further isomeric methylbutenes (approx. 20% by weight) are omitted.
  • the industrial processing of the C 5 cut has been carried out essentially by distillation to obtain the cyclopentane contained therein. Processes of this type are very complex in terms of process engineering. There is therefore a need for the non-distillative removal of the cyclopentene and optionally further acyclic monoolefins from the Cs cut to obtain valuable products.
  • DE-A-196 54 166 describes oligomer mixtures with ethylenically unsaturated double bonds which are derived from cyclopentene and which are obtained by metathesis reaction of a Cs cut in the presence of a transition metal catalyst.
  • DE-A-196 54 167 describes a process for the functionalization of such oligomer mixtures derived from cyclopentene, e.g. by hydroformylation and, if appropriate, subsequent hydrogenation. This results in alcohol mixtures with a high proportion of dihydric and higher alcohols. Such alcohol mixtures are not suitable for use as surfactant alcohols.
  • the object of the present invention is to provide a process for the preparation of surfactant alcohols.
  • a large-scale starting hydrocarbon mixture is to be used in the process according to the invention.
  • the object is achieved by a process in which a hydrocarbon mixture which contains cyclopentene and at least one aeyclic monoolefin is subjected to a metathesis, a Cs-C o-01efin fraction is isolated from the metathesis mixture and then one undergoes catalytic hydroformylation and hydrogenation.
  • the invention thus relates to a process for the preparation of alcohol mixtures, wherein a) reacting a hydrocarbon mixture which contains cyclopentene and at least one acyclic monoolefin in a metathesis reaction,
  • the, optionally selectively hydrogenated, olefin fraction is catalytically hydroformylated and hydrogenated by reaction with carbon monoxide and hydrogen.
  • the total olefin content of the hydrocarbon mixture used for the metathesis is preferably at least 30% by weight, preferably at least 40% by weight, in particular at least 50% by weight. Hydrocarbon mixtures with a total olefin content of up to 100% by weight are suitable.
  • the hydrocarbon mixtures used for metathesis preferably contain at least one acyclic monoolefin.
  • Preferred acyclic monoolefins are selected from Cs-monoolefins, such as 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene and mixtures thereof.
  • the proportion of Cs-monoolefins in the acyclic monoolefins is preferably at least 70% by weight, preferably at least 80% by weight, in particular at least 90% by weight.
  • a hydrocarbon mixture which is obtained on a large industrial scale in petroleum processing is preferably used. If desired, such mixtures can be subjected to a catalytic partial hydrogenation to remove dienes beforehand. For example, a mixture enriched in saturated and unsaturated Cs hydrocarbons, in particular a C 5 cut, is particularly suitable.
  • pyrolysis gasoline is preferably suitable, for example occurs when steam cracking naphtha. If desired, this pyrolysis gasoline can first be subjected to a selective hydrogenation in order to essentially convert the dienes and acetylenes contained therein into the corresponding alkanes and alkenes.
  • step a) of the process according to the invention is followed by a separation step, for example a fractional distillation, on the one hand the C 6 -C 8 cut which is important for further chemical syntheses and which contains the aromatic hydrocarbons and on the other hand a Cs cut which can be used in step a) of the process according to the invention ,
  • a total olefin content of e.g. 50 to 60% by weight such as 56%
  • a cyclopentene content of e.g. 10 to 20% by weight such as about 15% by weight
  • Cs monoolefins e.g. 33 to 43% by weight
  • a hydrocarbon mixture which comprises a cyclopentene-containing hydrocarbon mixture, in particular the Cs cut, and a mixture containing acyclic C 4 -01efins.
  • the C 4 -01efin mixture is preferably a petroleum fraction, in particular raffinate II. Raffinate II can be obtained, for example, by cracking high molecular weight hydrocarbons, such as crude oil.
  • a C 4 -01efin mixture is preferably used which contains 60 to 85% by volume of butene-1 and butene-2.
  • the C 4 -01efin mixture preferably contains at most 40% by volume, preferably at most 20% by volume, of saturated hydrocarbons, such as n-butane, isobutane, Cs-alkanes, etc.
  • the metathesis reaction of the hydrocarbon mixture in step a) preferably comprises i) the disproportionation of acyclic monoolefins by cross metathesis, ii) the oligomerization of cyclopentene by ring-opening metathesis, iii) chain termination by reaction of an oligomer from ii) with an acyclic olefin of the hydrocarbon mixture or a product from i), steps i) and / or ii) and / or iii) being able to be carried out several times on their own or in combination.
  • Step i) Combinations of cross-metathesis of different and self-metathesis of the same acyclic olefins and repeated runs of this reaction result in a large number of monoolefins with different structure and number of carbon atoms, which form the end groups of the oligomers in the reaction mixture resulting from the metathesis.
  • a catalyst is used for the metathesis, which enables the formation of cross-metathesis products.
  • These preferably include the metathesis catalysts described below as being particularly active. According to this embodiment, metathesis mixtures with a higher proportion of oligomers without terminal double bonds are obtained than when using a less active catalyst.
  • the average number of cyclopentene insertions in the growing chain in the sense of a ring-opening metathesis polymerization determines the average molecular weight of the cyclopentene-oligomer mixture formed.
  • Oligomer mixtures with an average molecular weight in a range from about 138 to 206 are preferably formed by the process according to the invention, which corresponds to an average number of one to two cyclopentene units per oligomer.
  • the chain is terminated by reacting an oligomer which still has an active chain end in the form of a catalyst complex (alkylidene complex) with an acyclic olefin, an active catalyst complex generally being recovered.
  • a catalyst complex alkylidene complex
  • the acyclic olefin may originate unchanged from the hydrocarbon mixture originally used for the reaction or may have been modified beforehand in a cross metathesis according to stage i).
  • Suitable catalysts for metathesis are known and include homogeneous and heterogeneous catalyst systems.
  • catalysts based on a transition metal of the 6th, 7th or 8th subgroup of the periodic table are suitable for the process according to the invention, preference being given to using catalysts based on Mo, W, Re and Ru.
  • Catalyst / cocatalyst systems based on W, Mo and Re are preferably used, which can comprise at least one soluble transition metal compound and / or an alkylating agent.
  • These include, for example, MoCl 2 (NO) 2 (PR 3 ) 2 / Al 2 (CH 3 ) 3 Cl 3 ; WCl 6 / BuLi; WCl 6 / EtAlCl 2 (Sn (CH 3 ) 4 ) / EtOH; WOCl 4 / Sn (CH 3 ) 4 ; WOCl 2 (0- [2,6-Br 2 -C 6 H 3 ]) / Sn (CH 3 ) 4 and CH 3 Re0 3 / C 2 H 5 AlCl 2 .
  • Preferred catalysts are furthermore four-coordinate Mo and W alkylidene complexes, which additionally have two bulky alkoxy and one imido ligands, in particular
  • a particularly preferred heterogeneous catalyst is Re 2 0 on Al 2 0 3 as the support material.
  • oligomer mixtures with changing double bond proportions and changing proportions of terminal double bonds can be obtained in the metathesis.
  • the metathesis reaction mixtures obtained in step a) have an iodine value in the range of about 200 to 400 g I 2/100 g oligomers.
  • the metathesis reaction in step a) preferably results in an oligomer mixture that essentially contains cyclopentene-derived oligomers of the general formula I.
  • n is an integer from 1 to 15, and
  • R 1 , R 2 , R 3 , R 4 are independently hydrogen or alkyl.
  • the radicals R 1 , R 2 , R 3 and R 4 in the formula I independently of one another represent hydrogen or alkyl, the term "alkyl” encompassing straight-chain and branched alkyl groups.
  • Ci-Cis-alkyl preferably C ⁇ -C ⁇ o-alkyl, particularly preferably C ⁇ -C 5 alkyl groups.
  • alkyl groups are in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2 -Dimethylpropyl, 1, 1-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl , 1, 3-dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3, 3-dimethylbuty
  • n in formula I stands for the number of cyclopentene units introduced into the oligomer mixtures derived from cyclopentene by ring-opening metathesis reaction.
  • the value n and thus the degree of ring-opening metathesis can be influenced by the activity of the metathesis catalyst used and the ratio of acyclic to cyclic olefins.
  • n is preferably in a range from approximately 1 to 4, in particular 1 to 2.
  • Preferred oligomer mixtures of the formula I are those in which at least 50% by weight, in particular at least 70% by weight (determined by the area integration of the gas chromatograms) of the components has a value of n> 1.
  • the reaction mixture from step a) is subjected to one or more separation steps.
  • Suitable separation devices are the usual apparatuses known to the person skilled in the art. These include e.g. B. distillation columns, such as tray columns which, if desired, can be equipped with bells, sieve plates, sieve trays, valves, side draws, etc., Evaporators such as thin film evaporators, falling film evaporators, wiper blade evaporators, Sambay evaporators etc. and combinations thereof.
  • the olefin fraction is preferably isolated by fractional distillation.
  • an olefin fraction is isolated which essentially contains olefins having 9 to 18 carbon atoms, preferably 10 to 15 carbon atoms.
  • the olefin fraction isolated in step b) preferably has the highest possible olefin content.
  • the olefin content is preferably at least 40% by weight, preferably at least 50% by weight. According to a particularly preferred embodiment, the olefin content is about 100% by weight.
  • a hydrocarbon mixture can be used for the metathesis in step a) which, in addition to cyclopentene and acyclic monoolefins, also has saturated compounds. If the olefin fraction isolated in step b) contains part of these saturated compounds, this is generally not critical for the further processing to the olefin mixtures according to the invention.
  • the olefin fraction isolated in step b) preferably has a proportion of saturated compounds in the range from approximately 0 to 60% by weight, preferably approximately 0.1 to 50% by weight.
  • the metathesis in step a) generally results in reaction mixtures which, in addition to monoolefins and optionally saturated compounds from the reactant hydrocarbon mixture, also contain two- and polyunsaturated compounds.
  • the olefin fraction isolated in step b) preferably has a proportion of di- and polyunsaturated compounds in the range from about 60 to 100% by weight.
  • At least one further olefin fraction can be isolated from the reaction mixture of the metathesis in step b). These are preferably fractions which are present in the reaction mixture obtained in step a) in an amount of at least 5% by weight, based on the total amount of the mixture.
  • step b) at least one further olefin fraction is preferably isolated, which essentially contains olefins having more than 20, preferably more than 18, in particular more than 15 carbon atoms.
  • This fraction preferably contains essentially olefins with at most 75, particularly preferably at most 50, in particular at most 40 carbon atoms.
  • these olefin fractions can preferably be subjected to cross metathesis with at least one acyclic olefin which has at most 9, preferably at most 8, in particular at most 7 carbon atoms.
  • Low molecular weight olefins and olefin mixtures suitable for cross metathesis are, for example, ethene, raffinate II or corresponding olefin fractions from the metathesis from step a).
  • these higher molecular weight further olefin fractions can, if desired, also be partially or completely fed back in step a) of the process according to the invention.
  • step b) at least one further olefin fraction is preferably isolated, which essentially has olefins having at most 9, preferably at most 8, in particular at most 7 carbon atoms.
  • This fraction preferably contains essentially olefins having at least 5, preferably at least 6, carbon atoms.
  • these low molecular weight further olefin fractions can preferably be subjected to cross metathesis with at least one acyclic olefin which contains more than 20, preferably more than 18, in particular more than 15 carbon atoms.
  • Suitable higher molecular weight olefins and olefin mixtures are e.g. the previously described higher molecular weight further olefin fractions from the metathesis from step a).
  • cross-metathesis reactions of the further olefin fractions isolated in step b) preferably result in turn in fractions which essentially contain olefins having 8 to 20, preferably 9 to 18, in particular 10 to 15 carbon atoms. These can be used for further processing in step c) of the method according to the invention.
  • the olefin fraction isolated in step b) by the process according to the invention can also contain, in addition to monoolefins, a proportion of two- or polyunsaturated compounds.
  • the olefin fraction is further processed to the alcohol mixtures according to the invention, the corresponding di- or polyhydric alcohols result from these di- and polyunsaturated compounds. Too high a proportion of these dihydric and polyhydric alcohols may be undesirable if the alcohol mixtures according to the invention are used for the preparation of surface-active compounds.
  • the olefin fraction from step b) can therefore be subjected to a selective hydrogenation.
  • the di- and polyunsaturated compounds are at least partially in Monoolefins convicted. The proportion of monoolefins in the olefin fraction is thus advantageously increased.
  • Suitable catalysts for the selective hydrogenation are known from the prior art and include conventional homogeneous and heterogeneous hydrogenation catalyst systems.
  • the catalysts suitable for the process according to the invention are preferably based on a transition metal of the 8th or 1st subgroup, preference being given to using catalysts based on Ni, Pd, Pt, Ru or Cu. Catalysts based on Cu or Pd are particularly preferably used.
  • Suitable heterogeneous catalyst systems generally comprise one of the aforementioned transition metal compounds on an inert support.
  • Suitable inorganic carriers are the oxides customary for this, in particular silicon and aluminum oxides, aluminosilicates, zeolites, carbides, nitrides etc. and mixtures thereof. Al 2 O 3 , Si0 2 and mixtures thereof are preferably used as carriers.
  • heterogeneous catalysts are used in the process according to the invention, such as those described in US Pat. Nos. 4,587,369; US-A-4,704,492 and US-A-4, 493, 906, which are incorporated by reference in their entirety.
  • Suitable Cu-based catalyst systems are sold by Dow Chemical as KLP catalysts.
  • olefin fractions which have a proportion of di- and polyunsaturated compounds in the range from 60 to 100% by weight.
  • an olefin fraction isolated in step b) and optionally selectively hydrogenated in step c) is hydroformylated and hydrogenated.
  • the alcohol mixtures can be prepared in one step or in two separate reaction steps.
  • the step in) d olefin used has an iodine value in the range of 175 to 350 g I 2/100 g.
  • the olefin fraction used in step d) preferably has a proportion of unbranched olefins in the range from 10 to 90% by weight, preferably 30 to 70% by weight.
  • Suitable catalysts for hydroformylation are known and generally comprise a salt or a complex compound of an element of subgroup VIII of the periodic table.
  • the metal of subgroup VIII is preferably selected from cobalt, ruthenium, iridium, rhodium, nickel, palladium and platinum. Salts and in particular complex compounds of rhodium or cobalt are preferably used for the process according to the invention.
  • Suitable salts are, for example, the hydrides, halides, nitrates, sulfates, oxides, sulfides or the salts with alkyl or aryl carboxylic acids or alkyl or aryl sulfonic acids.
  • Suitable complex compounds are, for example, the carbonyl compounds and carbonyl hydrides of the metals mentioned and complexes with amines, amides, triarylphosphines, trialkylphosphines, tricycloalkylphosphines, olefins, or dienes as ligands.
  • the ligands can also be used in polymeric or polymer-bound form. Catalyst systems can also be prepared in situ from the salts mentioned and the ligands mentioned.
  • Suitable alkyl residues of the ligands are the linear or branched Ci-Cis-alkyl described above, in particular Ci-Cs-alkyl residues.
  • Cycloalkyl is preferably C 3 -C ⁇ o-cycloalkyl, in particular cyclopentyl and cyclohexyl, which can optionally also be substituted with C ⁇ -C 4 alkyl groups.
  • Aryl is preferably understood to mean phenyl (Ph) or naphthyl, optionally with 1, 2, 3 or 4 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, for example methoxy, halogen, preferably chloride, or hydroxy, the may optionally also be ethoxylated.
  • Suitable rhodium catalysts or catalyst precursors are rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate (rhodium alum), rhodium (II) and Rhodium (III) carboxylate, preferably rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid and trisammonium hexachloro-rhodate (III).
  • rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate (
  • rhodium complexes of the general formula RhX m L 1 L 2 (L 3 ) n , where X is halide, preferably chloride or bromide, alkyl or aryl carboxylate, acetylacetonate, aryl or alkyl sulfonate, in particular phenyl sulfonate and toluenesulfonate, hydride or the diphenyltriazine anion,
  • L 1 , L 2 , L 3 independently of one another for CO, olefins, cycloolefins, preferably cyclooctadiene (COD), dibenzophosphole, benzonitrile, PR 3 or R 2 PA-PR 2 , m for 1, 2 or 3 and n for 0.1 or 2 stand.
  • R (the radicals R can be the same or different) are to be understood as meaning alkyl, cycloalkyl and aryl radicals, preferably phenyl, p-tolyl, m-tolyl, p-ethylphenyl, p-cumyl, pt.-Butylphenyl, p -C-C -alkoxyphenyl, preferably p-anisyl, xylyl, mesityl, p-Hydroxyphenyl, which may also be ethoxylated, isopropyl, C 1 -C 4 alkoxy, cyclopentyl or cyclohexyl.
  • A stands for 1,2-ethylene or 1,3-propylene.
  • L 1 , L 2 or L 3 are preferably independently of one another CO, COD, P (phenyl) 3 , P (i-propyl) 3 , P (anisyl) 3 , P (OC 2 H 5 ) 3 , P ( Cyclohexyl) 3 , dibenzophosphole or benzonitrile.
  • X preferably represents hydride, chloride, bromide, acetate, tosylate, acetylacetonate or the diphenyltriazine anion, in particular hydride, chloride or acetate.
  • Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates such as cobalt acetate, cobalt ethyl hexanoate, cobalt naphthanoate, and the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tecacoblobium and hexacobalt hexadecacarbonyl.
  • the cobalt carbonyl complexes and in particular dicobalt octacarbonyl are preferably used for the process according to the invention.
  • a hydroformylation catalyst based on rhodium is used, it is generally used in an amount of 1 to 150 ppm, preferably 1 to 100 ppm.
  • the reaction temperature for a hydroformylation catalyst based on rhodium is generally in the range from room temperature to 200 ° C., preferably 50 to 150 ° C.
  • hydroformylation catalyst based on cobalt it is generally used in an amount of 0.0001 to 0.5
  • reaction temperature for a hydroformylation catalyst based on cobalt is generally in the range from about 100 to 250 ° C., preferably 150 to 200 ° C.
  • the reaction can be carried out at an elevated pressure of about 10 to 650 bar.
  • the molar ratio of H 2 : CO is generally about 1: 5 to about 5: 1.
  • the aldehydes or aldehyde / alcohol mixtures resulting from the hydroformylation can, if desired, be isolated and, if appropriate, purified by conventional methods known to the person skilled in the art before the hydrogenation.
  • the hydroformylation catalyst is preferably removed from the reaction mixture before the hydrogenation. In general, if necessary after working up, it can be used again for the hydroformylation.
  • the reaction mixtures obtained in the hydroformylation are reacted with hydrogen in the presence of a hydrogenation catalyst.
  • Suitable hydrogenation catalysts are generally transition metals such as e.g. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc., or their mixtures, which increase the activity and stability on supports, such as Activated carbon, aluminum oxide, diatomaceous earth, etc., can be applied.
  • transition metals such as e.g. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc.
  • supports such as Activated carbon, aluminum oxide, diatomaceous earth, etc.
  • Fe, Co, and preferably Ni can also be used in the form of the Raney catalysts as a metal sponge with a very large surface area.
  • a Co / Mo catalyst is preferably used for the process according to the invention.
  • the hydrogenation of the oxo aldehydes is preferably carried out at elevated temperatures and elevated pressure.
  • the reaction temperature is preferably about 80 to 250.degree.
  • the pressure is preferably about 50 to 350 bar.
  • the alcohol mixtures according to the invention are prepared in a one-step reaction.
  • an olefin fraction is reacted with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst which is also suitable for the further hydrogenation to the oxo alcohols.
  • a hydroformylation catalyst which is also suitable for the further hydrogenation to the oxo alcohols.
  • all hydroformylation catalysts are also suitable for carrying out catalytic hydrogenations, although, depending on the catalytic activity, generally higher temperatures and / or higher pressures and / or longer reaction times and a larger amount of catalyst than for an exclusive hydroformylation are used.
  • a cobalt carbonyl catalyst and in particular Co 2 (CO) 8 are preferably used.
  • the reaction temperature is generally 100 to 220 ° C, preferably 150 to 200 ° C, at an increased pressure of 50 to 650 bar, preferably 100 to 600 bar.
  • the invention further relates to the alcohol mixtures obtained by the process according to the invention.
  • the alcohol mixtures preferably have an OH number in the range from about 200 to 400 mg KOH / g product, preferably 250 to 350 mg KOH / g product.
  • the alcohol mixtures preferably have a degree of branching determined by means of NMR in the range from 0.5 to 2.5, preferably 0.7 to 2.0.
  • the hydrogenation preferably takes place as completely as possible so that the carbonyl number of the alcohol mixtures obtained by the process according to the invention is generally low.
  • the alcohol mixtures according to the invention have a carbonyl number of at most 5.
  • the alcohol mixtures according to the invention are preferably suitable for the functionalization for the preparation of surface-active mixtures.
  • Another object of the invention is a process for the preparation of functionalized alcohol mixtures, wherein one of the previously described alcohol mixtures according to the invention is subjected to alkoxylation, glycosidation, sulfation, phosphating, alkoxylation and subsequent sulfation or alkoxylation and subsequent phosphating.
  • the invention thus relates to a process for the preparation of functionalized alcohol mixtures, wherein
  • the, optionally selectively hydrogenated, olefin fraction is catalytically hydroformylated and hydrogenated by reaction with carbon monoxide and hydrogen,
  • step d) the alcohol mixture from step d) is subjected to alkoxylation, glycosidation, sulfation, phosphating, alkoxylation and subsequent sulfation or alkoxylation and subsequent phosphating.
  • the alcohol mixtures are alkoxylated by reaction with at least one alkylene oxide.
  • the alkylene oxides are preferably selected from compounds of the general formula II or CH ⁇ - CH R 7 (II)
  • R 7 represents hydrogen or a straight-chain or branched Ci to Ci 6 alkyl radical, and mixtures thereof.
  • the radical R 7 in the formula II preferably represents a straight-chain or branched C 1 -C 4 -alkyl radical, in particular C 1 -C 3
  • the alkylene oxides are preferably selected from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
  • the alcohol mixtures are reacted with the alkylene oxide (s) by customary methods known to the person skilled in the art and in equipment customary for this.
  • the average chain length of the polyether chains of the alcohol mixtures thus functionalized can be determined by the molar ratio of alcohol to alkylene oxide.
  • Alkoxylated alcohol mixtures having about 1 to 200, preferably about 1 to 50, in particular 1 to 10, alkylene oxide units are preferably prepared. If desired, the alcohol mixtures can only be reacted with one alkylene oxide or with two or more different alkylene oxides. When the alcohol mixtures are reacted with a mixture of two or more alkylene oxides, the resulting alkoxylates contain the alkylene oxide units essentially randomly distributed. If the alkylene oxides are used separately one after the other, this results in alkoxylates which, in the order in which they are added, contain the alkylene oxide units in the form of blocks in copolymerized form.
  • the alkoxylation can be catalyzed by strong bases, such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AICI 3 , BF 3 etc.
  • strong bases such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AICI 3 , BF 3 etc.
  • the alkoxylation is preferably carried out at temperatures in the range from approximately 80 to 250 ° C., preferably approximately 100 to 220 ° C.
  • the pressure is preferably between ambient pressure and 600 bar.
  • the alkylene oxide may contain an inert gas admixture, e.g. from about 5 to 60%.
  • the functionalized alcohol mixtures obtained by alkoxylation have a very good surface activity and can be used advantageously as nonionic surfactants in a large number of fields of application.
  • the alcohol mixtures are glycosidated by one, two or more reactions of the alcohol mixtures according to the invention with mono-, di- or polysaccharides.
  • the reaction is carried out using customary methods known to those skilled in the art. On the one hand, this includes acid-catalyzed conversion with dehydration.
  • Acids are, for example, mineral acids, such as HCl and H 2 S0 4 .
  • oligosaccharides with statistical chain length distribution are obtained.
  • the average degree of oligomerization is preferably 1 to 3 saccharide residues.
  • the saccharide can first be acetalized by reaction with a low molecular weight C ⁇ ⁇ to C 8 alkanol, such as ethanol, propanol or butanol.
  • the acetalization is preferably acid-catalyzed.
  • the resulting glycoside with the low molecular weight alcohol can then be reacted with the alcohol mixture according to the invention to give the corresponding glycosides.
  • Aqueous saccharide solutions are generally also suitable for this reaction.
  • the saccharide can first be converted into the corresponding O-acetylhalosaccharide by reaction with a hydrogen halide and then with a sen alcohol mixture in the presence of acid-binding compounds are glycosidated.
  • Monosaccharides are preferably used for the glycosidation.
  • hexoses such as glucose, fructose, galactose, mannose etc. and pentoses such as arabinose, xylose, ribose etc.
  • Glucose is particularly preferably used.
  • the saccharides can be used individually or in the form of mixtures. Saccharide mixtures generally result in glycosides with randomly distributed sugar residues. With multiple addition of saccharide to an alcoholic hydroxide group, polyglycosides of the alcohol mixtures according to the invention result.
  • saccharides can also be used in succession or as a mixture for polyglycosidation, so that the resulting functionalized alcohol mixtures contain the saccharides in the form of blocks or incorporated in a statistically distributed manner.
  • reaction conditions in particular reaction temperature, furanose or pyranose structures can result.
  • Suitable methods and reaction conditions for glycosidation are e.g. in Ulimann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A25 (1994), pp. 792-793 and the documents cited therein.
  • the functionalized alcohol mixtures obtained by glycosidation have a very good surface activity and can be used advantageously as a nonionic surfactant in a large number of fields of application.
  • alcohol mixtures or alkoxylated alcohol mixtures are sulfated or phosphated by reaction with sulfuric acid or sulfuric acid derivatives to give acidic alkyl sulfates or alkyl ether sulfates or by reaction with phosphoric acid or or phosphoric acid derivatives to give acidic alkyl phosphates or alkyl ether phosphates.
  • Suitable processes for the sulfation of alcohols are the customary ones known to the person skilled in the art, such as e.g. in US 3,462,525, US 3,420,875 or US 3,524,864, which are incorporated herein by reference. Suitable processes for sulfation are also described in Ulimann's Encyclopedia of Industrial Chemistry, 5th edition vol. A25 (1994), pp. 779-783 and the literature cited therein.
  • sulfuric acid is used to sulfate the alcohol mixtures according to the invention, this is preferably 75 to 100% by weight, in particular 85 to 98% by weight.
  • sulfur Acid is available under the names concentrated sulfuric acid and monohydrate.
  • a solvent or diluent can be used for sulfation with sulfuric acid.
  • Suitable solvents are e.g. those that form an azeotrope with water, e.g. Toluene.
  • the alcohol mixture is placed in a reaction vessel and the sulfating agent is added with constant mixing.
  • the molar ratio of alkanol to sulfating agent is preferably about 1: 1 to 1: 1.5, in particular 1: 1 to 1: 1.2.
  • the sulfating agent can also be used in a molar deficit, e.g. in the sulfation of alkoxylated alcohol mixtures if mixtures of nonionic and anionic surface-active compounds are to be produced.
  • the sulfation is preferably carried out at a temperature in the range from ambient temperature to 80 ° C., in particular 40 to 75 ° C.
  • Suitable sulfating agents are e.g. Sulfur trioxide, sulfur trioxide complexes, solutions of sulfur trioxide in sulfuric acid (oleum), chlorosulfonic acid, sulfuryl chloride, amidosulfonic acid etc. If sulfur trioxide is used as the sulfating agent, the reaction can advantageously be carried out in a falling film evaporator, preferably in countercurrent. The reaction can be carried out batchwise or continuously.
  • reaction mixtures formed in the sulfation are worked up by customary processes known to the person skilled in the art. This includes e.g. neutralization, separation of any solvents used, etc.
  • the phosphation of the alcohol mixtures and alkoxylated alcohol mixtures described above is generally carried out in an analogous manner to the sulfation.
  • Suitable processes for the phosphating of alcohols are the customary, known to the person skilled in the art, as described, for example, in Synthesis 1985, pp. 449 to 488, to which reference is made in full here.
  • Suitable phosphating agents are, for example, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, P0C1 3 etc.
  • POCI 3 the remaining acid chloride functions are hydrolyzed after the esterification.
  • the functionalized alcohol mixtures and their salts obtained by sulfation or phosphation show a very good surface activity and can be used advantageously as anionic surfactants in a large number of application areas.
  • the invention further relates to the functionalized alcohol mixtures and their salts obtainable by the process described above.
  • Another object of the invention is the use of the functionalized alcohol mixtures as surfactants, dispersants, paper auxiliaries, soil solvents, corrosion inhibitors, auxiliaries for dispersions, incrustation inhibitors.
  • the mixtures of functionalized alcohols according to the invention are advantageously distinguished by very good surface-active properties.
  • the aqueous solutions of these mixtures show e.g. good surface tension values and / or cloud points.
  • a 5890 gas chromatograph from Hewlett Packard with a DB 5.30 mx 0.32 mm glass capillary acid and a flame ionization detector with connected integration unit was used to record the gas chromatograms.
  • the iodine number is defined as g iodine / 100 g product and was determined according to Kaufmann. For this purpose, about 0.2 g of test substance is precisely weighed into a 300 ml Erlenmeyer flask, dissolved in 20 ml of chloroform, mixed with exactly 20.00 ml of bromine solution and left to stand in the dark for 2 hours. Then 10 ml of potassium iodide solution and about 2 g of potassium iodate are added. The iodine which is excreted is titrated with sodium thiosulphate solution against starch solution until the blue color disappears.
  • acetylation reagent 810 ml of pyridine, 100 ml of acetic anhydride and 9 ml of acetic acid are mixed.
  • a 1: 1 mixture of cyclopentene and 1-pentene was pumped continuously at 60 ° C., 5 bar and residence times of 1-3 h into a tube reactor equipped with Re0 7 / Al 2 0 3 .
  • the reaction product was then separated into a light and a high boiler fraction and the former was returned to the metathesis process.
  • the high boiler fraction was freed from residual amounts of low boilers in vacuo.
  • space-time yields of 50-500 g 1 _1 h _1 slightly yellowish liquids were obtained, which were then chromatographed on Al 2 O 3 .
  • a sample taken had the following composition (GC area percent):
  • a metathesis reaction mixture according to Example 4 was subjected to fractional distillation under reduced pressure (60 theoretical plates; reflux ratio 5; fraction isolated at 100 mbar, top temperature 96-124 ° C, bottom temperature
  • the alcohol mixture was worked up by distillation and a fraction with a boiling range from 99 ° C./9 mbar to 144 ° C./40 mbar was isolated (40% by weight based on crude hydroformylation product). This fraction has an OH number of 296 mg KOH / g. An average degree of branching of 1.02 was determined using ⁇ -NMR.
  • olefin fraction from example 5 was subjected to a further fractional distillation (apparatus as example 5; fraction isolated at 200 mbar, top temperature 95-110 ° C., bottom temperature 130 ° C.).
  • An olefin fraction of the following composition (GC area percent) was isolated:
  • the iodine value was 295 g I 2/100 g. 2260 g of this olefin fraction were mixed with 8.5 g of Co 2 (CO) 8 at 185 ° C. and 280 bar with synthesis gas (CO / H 2 1: 1) with the addition of 226 g of water and 1.5 kg of heptane in a 20 l Rotary stirring autoclave hydroformylated, the reaction time was 7.5 hours. After cooling and releasing the pressure in the autoclave, the reaction mixture was decobtained with 10% acetic acid with introduction of air at 90 ° C. The resulting hydroformylation mixture was hydrogenated in a 2.5 1 tubular reactor in a trickle mode over a Co / Mo fixed bed catalyst at 175 ° C. and 280 bar with hydrogen with the addition of 10% by weight of water.
  • the alcohol mixture was worked up by distillation and a fraction with a boiling range from 80 ° C./2 mbar to 114 ° C./2 mbar was isolated (71% by weight based on crude hydroformylation product). This fraction has an OH number of 310 mg KOH / g. By means ! H-NMR showed an average degree of branching of 1.14.
  • Example 5 380 g of the alcohol mixture obtained in Example 5 were introduced into a dry 2 l autoclave with 1.5 g of NaOH. The contents of the autoclave were heated to 150 ° C. and 616 g of ethylene oxide were pressed into the autoclave under pressure. After filling the entire amount of ethylene oxide, the autoclave was at 150 ° C for 30 minutes held. After cooling, the reactor discharge was neutralized with sulfuric acid.
  • the surfactant mixture obtained had a cloud point of 46 ° C., measured in accordance with DIN 53917 on a 1% strength solution in water.
  • Example 6 270 g of the alcohol mixture obtained in Example 6 were introduced into a dry 2-1 autoclave with 1.5 g of NaOH. The contents of the autoclave were heated to 150 ° C. and 726 g of ethylene oxide were pressed into the autoclave under pressure. After the entire amount of ethylene oxide had been introduced, the autoclave was kept at 150 ° C. for a further 30 minutes. After cooling, the reactor discharge was neutralized with sulfuric acid. The mixture obtained had a cloud point of 95.5 ° C., measured in accordance with DIN 53917 on a 1% strength solution in water. The surface tension, measured according to DIN 53914, at a concentration of 1 g / 1, was 31.2 mN / m.
  • Example 6 360 g of the alcohol mixture obtained in Example 6 were heated to 60 ° C. in a stirred vessel under a nitrogen atmosphere and 167 g of polyphosphoric acid were slowly added. A temperature of 65 ° C was not exceeded. At the end of the addition, the temperature was raised to 70 ° C. and the reaction mixture was stirred at this temperature for another hour. A surfactant mixture was obtained with a surface tension determined according to DIN 53914 of 32.1 mN / m at a concentration of 1 g / 1.
  • Example 7 490 g of the fatty alcohol ethoxylate obtained in Example 7 were heated to 60 ° C. in a stirred vessel under a nitrogen atmosphere and 85 g of polyphosphoric acid were slowly added. A temperature of 65 ° C was not exceeded. At the end of the addition, the temperature was raised to 70 ° C. and the batch was stirred at this temperature for a further hour. A surfactant mixture was obtained with a surface tension of 35.7 m / N / m, measured according to DIN 53914, measured at a concentration of 1 g / 1.

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Abstract

La présente invention concerne un procédé de production de mélanges d'alcools, selon lequel: a) on transforme un mélange d'hydrocarbures qui contient du cyclopentène et au moins une mono-oléfine acyclique, en une réaction de métathèse; b) on isole, à partir du mélange résultant de la métathèse, une fraction oléfinique qui contient essentiellement des oléfines C8-C20; c) éventuellement on soumet les composés bi-insaturés ou poly-insaturés contenus dans la fraction oléfinique au moins partiellement à une hydrogénation sélective pour former des mono-oléfines; d) on soumet la fraction oléfinique ayant éventuellement subi une hydrogénation sélective à une hydroformulation et à une hydrogénation catalytiques par réaction avec du monoxyde de carbone et de l'hydrogène. L'invention concerne également des mélanges d'alcool pouvant être obtenus selon ledit procédé, ainsi qu'un procédé de production de mélanges d'alcools fonctionnalisés et l'utilisation de ceux-ci.
PCT/EP2000/006896 1999-07-20 2000-07-19 Procede de production de melanges d'alcools Ceased WO2001005735A1 (fr)

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DE19933828A DE19933828A1 (de) 1999-07-20 1999-07-20 Verfahren zur Herstellung von Alkoholgemischen
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7041864B2 (en) 2002-12-11 2006-05-09 Shell Oil Company Linear and branched olefin production from cyclic olefin feedstocks
US10183899B2 (en) 2016-11-10 2019-01-22 Chevron Phillips Chemical Company Lp Normal alpha olefin synthesis using metathesis and dehydroformylation
US10723672B2 (en) 2018-02-26 2020-07-28 Chervon Phillips Chemical Company Lp Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation
US11123723B2 (en) 2018-02-26 2021-09-21 The Regents Of The University Of California Oxidative dehydroxymethylation of alcohols to produce olefins
US12151993B2 (en) 2021-09-10 2024-11-26 Chevron Phillips Chemical Company Lp Selective 1-hexene/1-octene production with 1-decene

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240199986A1 (en) * 2021-04-15 2024-06-20 Conopco, Inc., D/B/A Unilever Composition

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Publication number Priority date Publication date Assignee Title
DE19629369A1 (de) * 1996-07-20 1998-01-22 Basf Ag Verfahren zur Herstellung von Alkoholen und/oder Aldehyden aus Olefinen
WO1998003456A1 (fr) * 1996-07-20 1998-01-29 Basf Aktiengesellschaft Procede de preparation d'alcools et/ou d'aldehydes a partir d'olefines
DE19654166A1 (de) * 1996-12-23 1998-06-25 Basf Ag Von Cyclopenten abgeleitete Oligomerengemische, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19654167A1 (de) * 1996-12-23 1998-06-25 Basf Ag Funktionalisierte von Cyclopenten abgeleitete Oligomerengemische, Verfahren zu ihrer Herstellung und ihre Verwendung

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
DE19629369A1 (de) * 1996-07-20 1998-01-22 Basf Ag Verfahren zur Herstellung von Alkoholen und/oder Aldehyden aus Olefinen
WO1998003456A1 (fr) * 1996-07-20 1998-01-29 Basf Aktiengesellschaft Procede de preparation d'alcools et/ou d'aldehydes a partir d'olefines
DE19654166A1 (de) * 1996-12-23 1998-06-25 Basf Ag Von Cyclopenten abgeleitete Oligomerengemische, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19654167A1 (de) * 1996-12-23 1998-06-25 Basf Ag Funktionalisierte von Cyclopenten abgeleitete Oligomerengemische, Verfahren zu ihrer Herstellung und ihre Verwendung

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7041864B2 (en) 2002-12-11 2006-05-09 Shell Oil Company Linear and branched olefin production from cyclic olefin feedstocks
US10183899B2 (en) 2016-11-10 2019-01-22 Chevron Phillips Chemical Company Lp Normal alpha olefin synthesis using metathesis and dehydroformylation
US10435334B2 (en) 2016-11-10 2019-10-08 Chevron Phillips Chemical Company Lp Normal alpha olefin synthesis using metathesis and dehydroformylation
US10723672B2 (en) 2018-02-26 2020-07-28 Chervon Phillips Chemical Company Lp Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation
US11123723B2 (en) 2018-02-26 2021-09-21 The Regents Of The University Of California Oxidative dehydroxymethylation of alcohols to produce olefins
US12151993B2 (en) 2021-09-10 2024-11-26 Chevron Phillips Chemical Company Lp Selective 1-hexene/1-octene production with 1-decene

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