EP2007491A2 - Procédé de séparation de complexes de nickel(0) et de ligands contenant du phosphore à partir de mélanges de nitriles - Google Patents

Procédé de séparation de complexes de nickel(0) et de ligands contenant du phosphore à partir de mélanges de nitriles

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Publication number
EP2007491A2
EP2007491A2 EP07727428A EP07727428A EP2007491A2 EP 2007491 A2 EP2007491 A2 EP 2007491A2 EP 07727428 A EP07727428 A EP 07727428A EP 07727428 A EP07727428 A EP 07727428A EP 2007491 A2 EP2007491 A2 EP 2007491A2
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EP
European Patent Office
Prior art keywords
nickel
phosphorus
complexes
ligands
separation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP07727428A
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German (de)
English (en)
Inventor
Gerd Haderlein
Tobias Aechtner
Michael Bartsch
Hermann Luyken
Peter Pfab
Jens Scheidel
Andreas Leitner
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BASF SE
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BASF SE
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Priority to EP07727428A priority Critical patent/EP2007491A2/fr
Publication of EP2007491A2 publication Critical patent/EP2007491A2/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0426—Counter-current multistage extraction towers in a vertical or sloping position
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0446—Juxtaposition of mixers-settlers
    • B01D11/0457—Juxtaposition of mixers-settlers comprising rotating mechanisms, e.g. mixers, mixing pumps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
    • C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a process for the extractive separation of nickel (O) - complexes with phosphorus ligands and / or free phosphorus ligands, from a reaction of a hydrocyanation of unsaturated mononitriles to dinitriles, by extraction by means of a hydrocarbon, wherein a phase separation of the hydrocarbon and the nitrile-containing solution takes place in two phases and at least one polar additive is fed to the hydrocyanation discharge (feed stream) and / or the extraction stage.
  • nickel complexes of phosphorus ligands are suitable catalysts.
  • adiponitrile an important intermediate in nylon production, is prepared by double hydrocyanation of 1,3-butadiene.
  • 1,3-butadiene with hydrogen cyanide in the presence of nickel (O), which is stabilized with phosphorus ligands, converted to 3-pentenenitrile.
  • nickel (O) which is stabilized with phosphorus ligands, converted to 3-pentenenitrile.
  • 3-pentenenitrile is then reacted with hydrogen cyanide to give adiponitrile likewise on a nickel catalyst, but if appropriate with the addition of a Lewis acid and possibly a promoter.
  • Nickel (O) or Ni (O) means nickel in the oxidation state 0.
  • the nickel catalyst is usually separated off and recycled (catalyst circulation). Since the catalyst system in the second hydrocyanation, which is a mixture of complex and free ligand, is thermally less resilient, the separation of the high-boiling adiponitrile from the catalyst system can not be carried out by distillation. Therefore, the separation is generally carried out extractively with hydrocarbons as extractants.
  • the catalyst system remains - ideally completely, under real conditions at least partially - in the lighter hydrocarbon phase, while the heavier phase is more polar and contains crude adiponitrile, the vast majority of the unreacted pentenenitriles and the Lewis acid.
  • the extractant is separated after the phase separation usually by distillation under reduced pressure from the catalyst system, with pentenenitriles are added to the dilution. The boiling pressure of the extractant is significantly higher than that of the pentenenitriles.
  • US Pat. Nos. 3,773,809 and 5,932,772 describe the extraction of the catalyst complex and the ligands with paraffins and cycloparaffins, for example cyclohexane, hepane and octane, or alkylaromatics.
  • US Pat. No. 4,339,395 discloses a process for the extractive work-up of reaction effluents of hydrocyanations for catalyst systems with monodental ligands and a triarylborane promoter in which a small amount of ammonia is metered in to avoid lump formation.
  • WO 2004/062765 describes the extractive separation of a nickel-diphosphite catalyst from a mixture of mono- and dinitriles with alkanes or cycloalkanes as extractant, the mixture being mixed with a Lewis base, e.g. Organo amines or ammonia, is treated.
  • a Lewis base e.g. Organo amines or ammonia
  • US Pat. No. 5,847,191 discloses a process for the extractive work-up of reaction effluents of hydrocyanations, the chelate ligands carrying C.sub.1-C.sub.10-alkyl radicals.
  • U.S. Patent 4,990,645 discloses that the extractability of the nickel complex and the free ligand can be improved by separating the solid Ni (CN) 2 formed in the reaction prior to extraction in a decanter. For this purpose, a part of the pentenenitrile is previously evaporated in order to reduce the solubility of the catalyst and of the Ni (CN) 2.
  • a problem with this minimum conversion of 3-pentenenitrile is that a higher conversion of 3-pentenenitrile is associated with a poorer selectivity of adiponitrile with respect to 3-pentenenitrile and hydrogen cyanide.
  • a minimum conversion of 3-pentenenitrile of 60% leads to a shorter service life of the catalyst system.
  • the process according to the invention is used in the production of adiponitrile.
  • the process according to the invention is preferably intended for 3-pentenenitrile as mononitrile and adiponitrile as dinitrile.
  • the reaction effluent of the hydrocyanation is likewise preferably obtained by reacting 3-pentenenitrile with hydrogen cyanide in the presence of at least one nickel (0) complex with phosphorus-containing ligands, if appropriate in the presence of at least one Lewis acid (for example as promoter).
  • the process according to the invention is suitable for the extractive removal of Ni (O) complexes which contain phosphorus-containing ligands and / or free phosphorus-containing ligands from a reaction product which is obtained in a hydrocyanation of unsaturated mononitriles to give dinitriles.
  • Ni (O) complexes which contain phosphorus-containing ligands and / or free phosphorus-containing ligands from a reaction product which is obtained in a hydrocyanation of unsaturated mononitriles to give dinitriles.
  • the reaction product from which a part or all of the unreacted pentenenitriles have optionally been removed is extracted by means of a hydrocarbon with the addition of a polar additive;
  • a phase separation of the hydrocarbon and the reaction output occurs in two phases.
  • a first phase is formed, which is enriched with respect to the reaction effluent to said Ni (0) complexes or ligands, and a second phase, which is enriched against the reaction effluent to dinitriles.
  • the first phase is the lighter phase, ie the upper phase
  • the second phase is the heavier phase, ie the lower phase.
  • the extraction preferably has an extraction coefficient-defined as the ratio of the mass content of said nickel (0) complexes or ligands in the upper phase to the mass content of said nickel (O) complexes or ligands in the lower phase for each theoretical extraction step, from 0.1 to 50, more preferably from 0.6 to 30.
  • the upper phase preferably contains between 50 and 99% by weight, particularly preferably between 60 and 97% by weight, in particular between 80 and 95% by weight, of the hydrocarbon used for the extraction.
  • the Lewis acid which is optionally contained in the feed stream of the extraction (namely in the second hydrocyanation mentioned in the introduction), preferably remains mostly and most preferably completely in the lower phase.
  • the residual concentration of the Lewis acid in the upper phase is preferably less than 1 wt .-%, more preferably less than 0.5 wt .-%, in particular less than 500 ppm by weight.
  • the hydrocarbon is the extractant. It preferably has a boiling point of at least 30, preferably at least 60, in particular at least 90 ° C, and preferably at most 140, more preferably at most 135, in particular at most 130 ° C, in each case at a pressure of 10 5 Pa absolute.
  • a hydrocarbon which in the context of the present invention is understood to mean a single hydrocarbon, as well as a mixture of such hydrocarbons, for the separation, in particular by extraction, of Ni (0) -containing catalyst and free ligand from a mixture containing adiponitrile , the Ni (O) -containing catalyst and free ligands are used, which has a boiling point in the range between 60 ° C and 135 ° C.
  • the catalyst can be advantageously obtained by distillative removal of the hydrocarbon, optionally with addition of a suitable solvent which is higher boiling than the hydrocarbon K (eg pentenenitrile), the use of a Hydrocarbon having a boiling point in the said range a particularly economical and technically simple separation by the possibility of condensing the distilled hydrocarbon with river water allowed.
  • a suitable solvent which is higher boiling than the hydrocarbon K (eg pentenenitrile)
  • the use of a Hydrocarbon having a boiling point in the said range a particularly economical and technically simple separation by the possibility of condensing the distilled hydrocarbon with river water allowed.
  • Suitable hydrocarbons are described, for example, in US Pat. No. 3,773,809, column 3, lines 50-62.
  • a hydrocarbon selected from cyclohexane, methylcyclohexane, cycloheptane, n-hexane, n-heptane, isomeric heptanes, n-octane, iso-octane, isomeric octanes such as 2,2,4-trimethylpentane, cis- and trans- decalin or mixtures thereof, in particular from cyclohexane, methylcyclohexane, n-heptane, isomeric heptanes, n-octane, isomeric octanes such as 2,2,4-trimethylpentane, or mixtures thereof, into consideration.
  • Cyclohexane, methylcyclohexane, n-heptane or n-octane are
  • Mulm is understood as meaning an area of incomplete phase separation between the upper and lower phases, usually a liquid / liquid mixture in which solids can also be dispersed. Excessive dew formation is undesirable because it hinders the extraction and may be obstructed. The extraction device can be flooded by Mulm, so they can no longer fulfill their separation task.
  • the hydrocarbon used is preferably anhydrous, wherein anhydrous one water content of less than 100, preferably less than 50, in particular less than 10 ppm by weight.
  • the hydrocarbon can be dried by suitable methods known to the person skilled in the art, for example by adsorption or azeotropic distillation. The drying can take place in a step preceding the process according to the invention.
  • the above-mentioned objects are achieved by a process for the extractive separation of nickel (0) complexes with phosphorus-containing ligands and / or free phosphorus-containing ligands, from a reaction effluent hydrocyanation of unsaturated mononitriles to dinitriles, by extraction by means of a hydrocarbon, wherein a phase separation of the hydrocarbon and of the reaction discharge takes place in two phases, achieved in that the addition of at least one polar additive for the hydrocyanation discharge reduces the formation of lumps and / or solids and increases the speed of the phase separation.
  • Polar additives are to be understood as meaning organic compounds which, by increasing the polarity of the dinitrile phase, bring about an accelerated phase separation and a reduced formation of mulching and solids.
  • polar additives especially saturated linear or branched aliphatic nitriles having two to ten carbon atoms and aromatic nitriles having seven to twelve carbon atoms are suitable.
  • acetonitrile examples include acetonitrile, propionitrile, butyronitrile, 2-methylbutanenitrile, pentanitrile, hexanenitrile, heptanenitrile and octanenitrile, cyclohexanenitrile, benzonitrile and alkyl- Benzonitrile such as 2-methylbenzonitrile and 2-ethylbenzonitrile or mixtures of these compounds.
  • sulfolane, alkyl ureas and pyrrolidones are suitable. Examples of these are dimethylurea, tetraethylurea, tetramethylurea, pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-hexylpyrrolidone or mixtures of these compounds.
  • the extraction of the nickel (0) complexes or ligands from the reaction effluent can be carried out in any suitable apparatus known to the person skilled in the art, preferably in countercurrent extraction columns, mixer-settler cascades or combinations of mixer-settler cascades with columns , Particularly preferred is the use of countercurrent extraction columns, which are equipped in particular with sheet metal packings as dispersing elements.
  • the extraction is carried out in countercurrent in a compartmented, stirred extraction column (eg a rotating disc contactor (RDC), Kühni column, Scheibel column, QVF column).
  • a compartmented, stirred extraction column eg a rotating disc contactor (RDC), kuhni column, Scheibel column, QVF column.
  • the hydrocarbon is used as the continuous phase and the reaction effluent of the hydrocyanation as the disperse phase.
  • the extractant, the polar additive and the feed stream may be fed to the extraction device separately or together.
  • a phase ratio of preferably 0.1 to 10, particularly preferably 0.4 to 3, in particular 0.75 to 1.5, in each case calculated as the ratio of the mass of the supplied hydrocarbon to the mass of the mixture to be extracted, is used .
  • the mass of polar additive is 1 to 50 wt .-%, preferably 2 to 45 wt .-%, particularly preferably 3 to 40 wt .-%, based on the mass of the feed stream
  • the absolute pressure during the extraction is preferably 10 kPa to 1 MPa, more preferably 50 kPa to 0.5 MPa, especially 75 kPa to 0.25 MPa (absolute).
  • the extraction is preferably carried out at a temperature of -15 to 120, in particular 20 to 100 and particularly preferably 30 to 80 ° C. It has been found that at a higher extraction temperature, the lump formation is lower.
  • the extraction is operated with a temperature profile.
  • a temperature profile In particular, working in this case at an extraction temperature of at least 30, preferably 30 to 95 and particularly preferably at least 40 ° C.
  • the temperature profile is preferably such that in that region of the extraction where the content of nickel (0) complexes with phosphorus-containing ligands and / or free phosphorus-containing ligands is higher than in the other region, the temperature is lower than in the other region , In this way, the temperature-labile Ni (0) complexes are thermally less stressed and their decay reduced.
  • phase separation can be considered spatially and temporally depending on the apparatus design as the last part of the extraction.
  • phase separation it is usually possible to select a further range of pressure, concentration and temperature, wherein the optimum parameters for the particular composition of the reaction mixture can easily be determined by a few simple preliminary tests.
  • the temperature T in the phase separation is usually at least 0, preferably at least 10, more preferably at least 20 ° C. Usually, it is at most 80, preferably at most 70, more preferably at most 60 ° C.
  • the phase separation is carried out at 10 to 80, preferably 20 to
  • the pressure during the phase separation is generally at least 1 kPa, preferably at least 10 kPa, particularly preferably 20 kPa. In general, it is at most 2 MPa, preferably at most 1 MPa, more preferably at most 0.5 MPa absolute.
  • the phase separation may be carried out in one or more devices known to those skilled in the art for such phase separation. In an advantageous embodiment, it is possible to carry out the phase separation in the extraction apparatus, for example in one or more mixer-settler combinations or by equipping an extraction column with a settling zone.
  • a gravity separator with internals as coalescing aids eg lamellas, fabric or sheet metal packings
  • a cyclone separator or in extreme cases that the heavy phase is to be completely retained can be a mechanically driven centrifugal separator (eg plate separator).
  • the Mulmphase can be selectively withdrawn from the Settlement.
  • the setting of a certain, targeted coating of the continuous phase is sufficient together with the disperse phase.
  • phase separation two liquid phases are obtained, one of which has a higher proportion of the nickel (0) complex with phosphorus-containing ligands and / or free phosphorus ligands, based on the total weight of this phase, than the other phase or phases ,
  • phase containing the higher proportion of Ni (0) complexes and phosphorus ligands may optionally be recycled to the hydrocyanation stage after regeneration of the catalyst and removal of the extractant.
  • the predominantly dinitrile, unreacted mononitrile and polar additive containing phase can be separated by distillation.
  • the polar additive has the lowest boiling point of the compounds present, it can be separated off in a first column as top product, mononitrile and dinitrile as bottom product. In a second column, the bottom product of the first column can be separated, the mononitrile can be separated overhead and the dinitrile over the bottom. But it is also possible to carry out the separation in only one column and thereby remove the polar additive overhead, mononitrile via a side draw and dinitrile through the bottom. If the mononitrile has the lowest boiling point, it can be separated off via the top, the polar additive via side draw or, in the case of two-stage distillation, together with dinitrile via the bottom.
  • the valuable product dinitrile can be discharged from the process, mononitrile can be recycled to the hydrocyanation and polar additive to the extraction.
  • the amount of polar additive is generally 1 to 50 wt .-%, preferably 2 to 45 wt .-%, based on the amount of the feed stream.
  • the reaction effluent of the hydrocyanation is treated before or during the extraction with ammonia or a primary, secondary or tertiary aromatic or aliphatic amine.
  • Aromatic includes alkylaromatic, and aliphatic includes cycloaliphatic.
  • a treatment of the reaction onsaustrags with ammonia or an amine is preceded or carried out during the extraction.
  • the treatment during the extraction is less preferred.
  • the amines used are monomines, diamines, triamines or higher-performance amines (polyamines).
  • the monoamines usually have alkyl radicals, aryl radicals or arylalkyl radicals having 1 to 30 carbon atoms; suitable monoamines are, for example, primary amines, for example monoalkylamines, secondary or tertiary amines, for example dialkylamines.
  • suitable primary monoamines are, for example, butylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, benzylamine, tetrahydrofurfurylamine and furfurylamine.
  • Suitable secondary monoamines are, for example, diethylamine, dibutylamine, di-n-propylamine and N-methylbenzylamine.
  • tertiary amines For example, trialkylamines having Ci-10-alkyl radicals, such as trimethylamine, triethylamine or tributylamine are suitable.
  • Suitable diamines are, for example, those of the formula R 1 -NH-R 2 -NH-R 3 , where R 1 , R 2 and R 3 independently of one another are hydrogen or an alkyl radical, aryl radical or arylalkyl radical having 1 to 20 C atoms.
  • the alkyl radical can also be cyclic, in particular linearly or in particular for R 2 .
  • Suitable diamines are, for example, ethylenediamine, the propylenediamines (1,2-diaminopropane and 1,3-diaminopropane), N-methylethylenediamine, piperazine, tetramethylenediamine (1,4-diaminobutane), N, N'-dimethylethylenediamine, N-ethylethylenediamine, 1, 5-diaminopentane, 1, 3-diamino-2,2-diethylpropane, 1, 3-bis (methylamino) propane, hexamethylenediamine (1,6-diaminohexane), 1, 5-diamino-2- methylpentane, 3- (propylamino) propylamine, N, N'-bis (3-aminopropyl) piperazine, N 1 N'-bis (3-aminopropyl) piperazine, and isophoronediamine (IPDA).
  • IPDA isophoronedia
  • triamines, tetramines or higher-functional amines examples include tris (2-aminoethyl) amine, tris (2-aminopropyl) amine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), isopropyltriamine, dipropylenetriamine and N, 1 N'-bis (3-aminopropyl-ethylenediamine).
  • Aminobenzylamines and aminohydrazides having 2 or more amino groups are also suitable.
  • ammonia or aliphatic amines in particular trialkylamines having 1 to 10 C atoms in the alkyl radical, e.g. Trimethylamine, triethylamine or tributylamine, and diamines such as ethylenediamine, Hexamehtylendiamin or 1, 5-diamino-2-methylpentane.
  • ammonia alone, i. It is particularly preferable to use no amine in addition to ammonia.
  • Anhydrous ammonia is most preferred; anhydrous means a water content below 1 wt .-%, preferably below 1000 and in particular below 100 ppm by weight.
  • the molar ratio of amine to ammonia can be varied within wide limits, is usually at 10000: 1 to 1: 10000.
  • the amount of ammonia or amine used depends i.a. the type and amount of nickel (0) catalyst and / or ligands, and - if used - on the type and amount of Lewis acid, which is used in the hydrocyanation as a promoter.
  • Lewis acid at least 1: 1.
  • the upper limit of this molar ratio is generally not critical and is for example 100: 1; the excess of ammonia or amine However, it should not be so large that the Ni (0) complex or its ligands decompose.
  • the molar ratio of ammonia or amine to Lewis acid is preferably 1: 1 to 10: 1, more preferably 1: 5: 1 to 5: 1, and in particular about 2.0: 1, if a mixture of ammonia and amine is used , these MoI ratios apply to the sum of ammonia and amine.
  • the temperature in the treatment with ammonia or amine is usually not critical and is for example 10 to 140, preferably 20 to 100 and in particular 20 to 90 ° C.
  • the pressure is usually not critical.
  • the ammonia or the amine can be added to the reaction effluent in gaseous form, liquid (under pressure) or dissolved in a solvent.
  • Suitable solvents are e.g. Nitriles, in particular those which are present in the hydrocyanation, and furthermore aliphatic, cycloaliphatic or aromatic Kohlenwasserstof- fe, as used in the inventive method as an extraction agent, for example cyclohexane, methylcyclohexane, n-heptane or n-octane.
  • ammonia or amine addition is carried out in conventional devices, for example those for gas introduction or in liquid mixers.
  • the solid which precipitates in many cases can either remain in the reaction effluent, i. the extraction is fed to a suspension or separated as described below.
  • the solids present in the reaction effluent are at least partially separated off prior to extraction.
  • the extraction performance of the method according to the invention can be further improved in many cases. It is believed that high solids content hinders mass transfer during extraction, requiring larger and therefore more expensive extraction equipment. In addition, it has been found that solids separation prior to extraction often significantly reduces undesirable scum formation.
  • the solids separation is preferably designed such that solid particles having a hydraulic diameter greater than 5 .mu.m, in particular greater than 1 .mu.m and particularly preferably greater than 100 nm, are separated off.
  • Solids separation it is possible to use customary processes, for example filtration, crossflow filtration, centrifugation, sedimentation, classification or, preferably, decanting, for which conventional devices such as filters, centrifuges or decanters can be used.
  • Temperature and pressure during solids separation are usually not critical. For example, one can work in the aforementioned temperature or pressure ranges.
  • the solids separation can be carried out before, during or after the - optional - treatment of the reaction output with ammonia or amine.
  • the separation during or after the ammonia or amine treatment is preferred, and thereafter particularly preferred.
  • the solids are usually compounds of ammonia or amine which are sparingly soluble in the reaction effluent with the Lewis acid or the promoter used. If ZnCb is used, for example, substantially sparingly soluble ZnCb * 2 NH3 precipitates during the ammonia treatment.
  • the solids are generally nickel compounds of the oxidation state + II, for example nickel (II) cyanide or similar cyanide-containing nickel ( ll) compounds.
  • Ni (0) complexes which contain phosphorus-containing ligands and / or free phosphorus-containing ligands are preferably homogeneously dissolved nickel (0) complexes.
  • the phosphorus-containing ligands of the nickel (0) complexes and the free phosphorus-containing ligands which are removed by extraction according to the invention are preferably selected from mono- or bidentate phosphines, phosphites, phosphinites and phosphonites.
  • These phosphorus-containing ligands preferably have the formula I:
  • compound I is understood to be a single compound or a mixture of different compounds of the aforementioned formula.
  • X 1 , X 2 , X 3 are independently oxygen or single binder fertil. If all of the groups X 1, X are single bonds 2 and X 3, compound I is a phosphine of the formula P (R 1 R 2 R 3) with the definitions of R 1, R 2 and R 3 in this description represents , If two of the groups X 1, X 2 and X 3 are single bonds and one for oxygen, compound I is a phosphinite of formula P (OR 1) (R 2) (R 3) or P (R 1) (OR 2 ) (R 3 ) or P (R 1 ) (R 2 ) (OR 3 ) with the meanings given below for R 1 , R 2 and R 3 .
  • compound I is a phosphonite of formula P (OR 1 XOR 2 XR 3) or P (R 1) (OR 2) (OR 3 ) or P (OR 1 ) (R 2 ) (OR 3 ) with the meanings given for R 1 , R 2 and R 3 in this description.
  • all of the groups X 1, X is oxygen 2 and X 3 should give compound I is advantageously a phosphite of the formula P (OR 1) (OR 2) (OR 3) with the definitions of R 1, R 2 and R 3 represents the meanings mentioned below.
  • R 1 , R 2 , R 3 independently of one another represent identical or different organic radicals.
  • R 1 , R 2 and R 3 independently of one another are alkyl radicals, preferably having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, Aryl groups, such as phenyl, o-tolyl, m-tolyl, p-ToIyI, 1-naphthyl, 2-naphthyl, or hydrocarbyl, preferably having 1 to 20 carbon atoms, such as 1, 1 'biphenol, 1, 1' - Binaphthol into consideration.
  • the groups R 1 , R 2 and R 3 may be connected to each other directly, ie not solely via the central phosphorus atom.
  • the groups R 1 , R 2 and R 3 are not directly connected
  • groups R 1 , R 2 and R 3 are radicals selected from the group consisting of phenyl, o-tolyl, m-tolyl and p-tolyl. In a particularly preferred embodiment, a maximum of two of the groups R 1 , R 2 and R 3 should be phenyl groups.
  • two of the groups R 1, R 2 and R 3 should in this case be o-tolyl groups maximal.
  • Such compounds I a are, for example, (p-tolyl-O -) (phenyl-O-) 2 P, (m-tolyl-O -) (phenyl-O) 2 P, (o-tolyl-O-) (phenyl-) O-) 2 P, (p-tolyl-O-) 2 (phenyl-O-) P, (m-tolyl-O-) 2 (phenyl-O-) P, (o-tolyl-O-) 2 ( Phenyl-O-) P, (m-tolyl-O -) (p-tolyl-O) (phenyl-O-) P, (o-tolyl-O -) (p-tolyl-O -) (phenyl-O -) P, (o-tolyl-O -) (p-tolyl-O -) (phenyl-O -) P, (o-tolyl-O-) (p-tolyl-O
  • Mixtures containing (m-tolyl-O-) 3 P, (m -olyl-O-) 2 (p-tolyl-O-) P, (m-tolyl-O -) (p-tolyl-O) 2 P and (P-ToIyI-O) 3 P can be obtained, for example, by reacting a mixture containing m-cresol and p-cresol, in particular in a molar ratio of 2: 1, as obtained in the distillative workup of petroleum, with a phosphorus trihalide such as phosphorus trichloride ,
  • the phosphites of the formula Ib which are described in more detail in DE-A 199 53 058 are suitable as phosphorus-containing ligands:
  • R 1 aromatic radical having a Ci-Cis-alkyl substituent in the o-position to the
  • R 2 aromatic radical having a Ci-Cis-alkyl substituent in the m-position to the oxygen atom which connects the phosphorus atom with the aromatic system, or with an aromatic substituent in m-position to the oxygen atom which connects the phosphorus atom with the aromatic system , or with an aromatic system fused in m-position to the oxygen atom connecting the phosphorus atom to the aromatic system, wherein the aromatic radical in o-position to the oxygen atom connecting the phosphorus atom to the aromatic system, a hydrogen atom wearing,
  • R 3 aromatic radical having a Ci-Cis-alkyl substituent in p-position to the oxygen atom which connects the phosphorus atom with the aromatic system, or with an aromatic substituent in p-position to the oxygen atom which connects the phosphorus atom with the aromatic system , Where- wherein the aromatic radical in the position ortho to the oxygen atom which links the phosphorus atom to the aromatic system bears a hydrogen atom,
  • R 4 aromatic radical which carries in the o, m and p position to the oxygen atom which connects the phosphorus atom to the aromatic system, other than the substituents defined for R 1 , R 2 and R 3 , wherein the aromatic radical in the position ortho to the oxygen atom connecting the phosphorus atom to the aromatic system carries a hydrogen atom,
  • Preferred phosphites of the formula I b can be found in DE-A 199 53 058.
  • radical R 1 are advantageously o-tolyl, o-ethyl-phenyl, on-propyl-phenyl, o-isopropyl-phenyl, on-butyl-phenyl, o-sec-butyl-phenyl, o- tert-butyl-phenyl, (o-phenyl) -phenyl or 1-naphthyl groups into consideration.
  • radical R 2 are m-tolyl, m-ethyl-phenyl, mn-propyl-phenyl, m-isopropyl-phenyl, mn-butyl-phenyl, m-sec-butyl-phenyl, m-tert Butyl-phenyl, (m-phenyl) -phenyl or 2-naphthyl groups are preferred.
  • radical R 3 are advantageously p-tolyl, p-ethyl-phenyl, pn-propyl-phenyl, p-isopropyl-phenyl, pn-butyl-phenyl, p-sec-butyl-phenyl, p- tert-butyl-phenyl or (p-phenyl) -phenyl groups into consideration.
  • Radical R 4 is preferably phenyl.
  • p is equal to zero.
  • Preferred phosphites of the formula I b are those in which p is zero and R 1 , R 2 and R 3 are independently selected from o-isopropyl-phenyl, m-tolyl and p-tolyl, and R 4 is phenyl.
  • Particularly preferred phosphites of the formula Ib are those in which R 1 is the o-isopropylphenyl radical, R 2 is the m-tolyl radical and R 3 is the p-tolyl radical having the indices mentioned in the table above; also those in which R 1 is the o-tolyl radical, R 2 is the m-tolyl radical and R 3 is the p-tolyl radical having the indices mentioned in the table; furthermore those in which R 1 is the 1-naphthyl radical, R 2 is the m-tolyl radical and R 3 is the p-tolyl radical having the indices mentioned in the table; also those in which R 1 is the o-tolyl radical, R 2 is the 2-naphthyl radical and R 3 is the p-tolyl radical having the indices mentioned in the table; and finally those in which R 1 is the o-isopropyl-phenyl radical, R 2 is the 2-naphthy
  • Phosphites of the formula I b can be obtained by
  • reaction can be carried out in three separate steps. Likewise, two of the three steps can be combined, ie a) with b) or b) with c). Alternatively, all of steps a), b) and c) can be combined with each other.
  • phosphorus trihalogenide are basically all phosphorus trihalides, preferably those in which as the halide Cl, Br, I, in particular Cl, is used, and mixtures thereof. It can also be mixtures of the same or the same different halogen-substituted phosphines are used as phosphorus trihalide. Particularly preferred is PCb. Further details on the reaction conditions in the preparation of phosphites I b and for workup can be found in DE-A 199 53 058.
  • the phosphites I b can also be used in the form of a mixture of different phosphites I b as a ligand. Such a mixture can be obtained, for example, in the preparation of phosphites I b.
  • the phosphorus-containing ligand is polydentate, in particular bidentate. Therefore, the ligand used preferably has the formula II
  • X 11 , X 12 , X 13 , X 21 , X 22 , X 23 are independently oxygen or single bond
  • R 11 , R 12 are independently identical or different, single or bridged organic radicals
  • R 21 , R 22 independently of one another are identical or different, individual or bridged organic radicals,
  • compound II is understood to be a single compound or a mixture of different compounds of the aforementioned formula.
  • X 11 , X 12 , X 13 , X 21 , X 22 , X 23 may be oxygen.
  • the bridging group Y is linked to phosphite groups.
  • X 11 and X 12 can be oxygen and X 13 is a single bond or X 11 and X 13 is oxygen and X 12 is a single bond such that the phosphorus atom surrounded by X 11 , X 12 and X 13 is the central atom of a phosphonite.
  • X 21 , X 22 and X 23 may be oxygen or X 21 and X 22 is oxygen and X 23 is a single bond or X 21 and X 23 are oxygen and X 22 is one Single bond or X 23 oxygen and X 21 and X 22 represent a single bond or X 21 oxygen and X 22 and X 23 represent a single bond or X 21 , X 22 and X 23 represent a single bond, so that with X 21 , X 22 and X 23 surrounding phosphorus atom may be central atom of a phosphite, phosphonite, phosphinite or phosphine, preferably a phosphonite.
  • X 13 may be oxygen and X 11 and X 12 may be a single bond or X 11 oxygen and X 12 and X 13 may be a single bond such that the phosphorous atom surrounded by X 11 , X 12 and X 13 is the central atom of a phosphonite.
  • X 21 , X 22 and X 23 may be oxygen or X 23
  • Oxygen and X 21 and X 22 represent a single bond or X 21 oxygen and X 22 and X 23 represent a single bond or X 21 , X 22 and X 23 represent a single bond, so that the phosphorus atom surrounded by X 21 , X 22 and X 23 central atom of a Phosphites, phosphinites or phosphines, preferably a phosphinite.
  • X 11 , X 12 and X 13 may represent a single bond such that the phosphorus atom surrounded by X 11 , X 12 and X 13 is the central atom of a phosphine.
  • X 21 , X 22 and X 23 oxygen or X 21 , X 22 and X 23 may represent a single bond such that the phosphorus atom surrounded by X 21 , X 22 and X 23 is the central atom of a phosphite or phosphine, preferably a phosphine , can be.
  • Bridging group Y is preferably substituted, for example, with C 1 -C 4 -alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups, preferably those having 6 to 20 carbon atoms in the aromatic system , in particular pyrocatechol, bis (phenol) or bis (naphthol).
  • halogen such as fluorine, chlorine, bromine
  • halogenated alkyl such as trifluoromethyl
  • aryl such as phenyl
  • unsubstituted aryl groups preferably those having 6 to 20 carbon atoms in the aromatic system , in particular pyrocatechol, bis (phenol) or bis (naphthol).
  • radicals R 11 and R 12 may independently of one another represent identical or different organic radicals.
  • Advantageously suitable radicals R 11 and R 12 are aryl radicals, preferably those having 6 to 10 carbon atoms, which may be unsubstituted or mono- or polysubstituted, in particular by C 1 -C 4 -alkyl, halogen, such as fluorine, chlorine, bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups.
  • the radicals R 21 and R 22 may independently represent identical or different organic radicals.
  • Advantageously suitable radicals R 21 and R 22 are aryl radicals, preferably those having 6 to 10 carbon atoms, which may be unsubstituted or monosubstituted or polysubstituted, in particular by C 1 -C 4 -alkyls, halides, such as fluorine, chlorine, Bromine, halogenated alkyl, such as trifluoromethyl, aryl, such as phenyl, or unsubstituted aryl groups.
  • the radicals R 11 and R 12 may be singly or bridged.
  • the radicals R 21 and R 22 may also be singly or bridged.
  • the radicals R 11 , R 12 , R 21 and R 22 may all be individually bridged and two individually or all four bridged in the manner described.
  • the compounds of the formula I, II, III, IV and V mentioned in US Pat. No. 5,723,641 are suitable.
  • the compounds of the formula I, II, IV, V, VI and VII mentioned in US Pat. No. 5,512,696, in particular the compounds used there in Examples 1 to 31, come into consideration.
  • the compounds of the formula I, M, III, IV, V and VI mentioned in US Pat. No. 5,512,695, in particular the compounds used there in Examples 1 to 6, are suitable.
  • the compounds of the formula I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII and XIV mentioned in US Pat. No. 5,981,772, in particular those in the examples thereof, are used 1 to 66 compounds used, into consideration.
  • the compounds mentioned in US Pat. No. 6,127,567 and compounds used there in Examples 1 to 29 are suitable.
  • the compounds of the formula I, M, III, IV, V, VI, VII, VIII, IX and X mentioned in US Pat. No. 6,020,516, in particular the compounds used there in Examples 1 to 33 are suitable.
  • the compounds mentioned in US Pat. No. 5,959,135 and compounds used there in Examples 1 to 13 are suitable.
  • the compounds of the formula I, II and III mentioned in US Pat. No. 5,847,191 are suitable.
  • the compounds mentioned in WO 01/14392 preferably those in formula V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XXI, XXII, XXIII compounds, into consideration.
  • the compounds mentioned in WO 98/27054 come into consideration.
  • the compounds mentioned in WO 99/13983 come into consideration.
  • the compounds mentioned in WO 99/64155 come into consideration.
  • the compounds mentioned in the German patent application DE 100 380 37 come into consideration.
  • the compounds mentioned in the German patent application DE 100 460 25 come into consideration.
  • the compounds mentioned in German Patent Application DE 101 502 85 come into consideration.
  • the compounds mentioned in German Patent Application DE 101 502 86 come into consideration.
  • the compounds mentioned in German Patent Application DE 102 071 65 come into consideration.
  • the phosphorus-containing chelate ligands mentioned in US 2003/0100442 A1 come into consideration.
  • the compounds I, I a, I b and II described and their preparation are known per se.
  • the phosphorus-containing ligand it is also possible to use mixtures containing at least two of the compounds I, Ia, Ib and II.
  • the phosphorus-containing ligand of the nickel (0) complex and / or the free phosphorus-containing ligand is selected from tritolyl phosphite, bidentate phosphorus-containing chelate ligands, and the phosphites of the formula I b
  • a Lewis acid is understood as meaning a single Lewis acid, as well as a mixture of several, such as two, three or four Lewis acids.
  • Suitable Lewis acids are inorganic or organic metal compounds in which the cation is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, Yttrium, zirconium, niobium, molybdenum, cadmium, rhenium and tin.
  • Examples include ZnBr 2 , ZnI 2 , ZnCl 2 , ZnSO 4 , CuCl 2 , CuCl, Cu (O 3 SCFa) 2 , CoCl 2 , CoI 2 , FeI 2 , FeCl 3 , FeCl 2 , FeCl 2 (THF) 2 , TiCl 4 (THF) 2 , TiCl 4 , TiCl 3 , CITi (Oi-propyl) 3 , MnCl 2 , ScCl 3 , AICI 3 , Al-alkyls such as Me 3 Al, Et 3 Al, Pr 3 Al, Bu 3 Al, Et 2 AICN, EtAl (CN) 2 (C 8 Hi 7 ) AICI 2 , (C 8 HiZ) 2 AICI, (JC 4 Hg) 2 AICI, (C 6 Hs) 2 AICI, (C 6 H 5 ) AICI 2 , ReCl 5 , ZrCl 4 , NbCl 5 , V
  • metal salts such as ZnCl 2 , CoI 2 and SnCl 2 and organometallic compounds such as RAICl 2 , R 2 AICI, RSnO 3 SCF 3 and R 3 B, where R is an alkyl or aryl group, such as for example, in US 3,496,217, US 3,496,218 and US 4,774,353.
  • a metal in cationic form selected from the group consisting of zinc, cadmium, beryllium, aluminum, gallium, indium, thallium, titanium, zirconium, hafnium, erbium, germanium, tin, vanadium, niobium , Scandium, chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, iron and cobalt, preferably zinc, cadmium, titanium, tin, chromium, iron and cobalt, wherein the anionic part of the compound may be selected from A group consisting of halides such as fluoride, chloride, bromide and iodide, anions of lower fatty acids having from 2 to 7 carbon atoms, HPO 3 2 ", H 3 PO 2 -, CF 3 COO-, C 7 Hi 5 OSO 2 - or SO 4 2 " .
  • halides such as fluoride, chloride, bromide
  • boron hydrides, organoborohydrides and boric acid esters of the formula R 3 B and B (OR) 3 where R is selected from the group consisting of hydrogen, aryl radicals having between 6 and 18 carbon atoms, with alkyl, are suitable promoters from US Pat. No. 3,773,809 Groups with 1 to 7 carbon atoms substituted aryl radicals and with cyano-substituted alkyl groups having 1 to 7 carbon atoms substituted aryl radicals, preferably triphenylboron called.
  • Suitable promoters may, for example, be selected from the group consisting of CdCl 2 , FeCl 2 , ZnCl 2 , B (C 6 Hs) 3 and (C 6 Hs) 3 SnX, with X being CF 3 SO 3 , CH 3 C 6 H 4 SO 3 or (C 6 Hs) 3 BCN, wherein the ratio of promoter to nickel is in the range of preferably from about 1:16 to about 50: 1.
  • Lewis acid also encompasses the promoters mentioned in US Pat. Nos. 3,496,217, 3,496,218, 4,774,353, 4,874,884, 6,127,567, 6,171, 996 and 6,380,421.
  • Particularly preferred Lewis acids are among the metal salts mentioned, in particular metal halides, particularly preferably metal halides, such as fluorides, chlorides, bromides, iodides, in particular chlorides, of which in turn zinc chloride, iron (II) chloride and iron (III) chloride are particularly preferred.
  • the hydrocyanation of 3-pentenenitrile is possible with a low degree of conversion, without the need to pre-evaporate 3-pentenenitrile or adiponitrile must be added to the dilution to allow the phase separation in the proposed extractive separation of the catalyst system.
  • the enabled mode of operation of the hydrocyanation with a lower degree of conversion of 3-pentenenitrile is associated with a better selectivity of adiponitrile with respect to 3-pentenenitrile and hydrogen cyanide.
  • the enabled mode of operation of the hydrocyanation with lower conversion of 3-pentenenitrile is also associated with a higher stability of the catalyst system.
  • Example 1 shows that the rate of phase separation is influenced by polar additives and the temperature.
  • the hydrocyanation reaction used for the experiments was from a continuous hydrocyanation of 3-pentenenitrile (3-PN) with hydrogen cyanide to adiponitrile (ADN) in the presence of nickel (0) complexes with chelated phosphonites of formula A and tritolyl phosphites of formula B.
  • Table 2 and Figure 1 show that even 1% acetonitrile and reinforced 10% acetonitrile between 20 and 70 ° C cause a significant acceleration of the phase separation. This effect is less pronounced with 1% DMSO, DMEU or sulfolane. For this, the phase boundaries become more visible, which also facilitates the phase separation.
  • Example 2 shows the effects of increasing amounts of acetonitrile at temperatures between 20 and 70 ° C.
  • Example 2 For the experiments, the same batch of hydrocyanation effluent as used in Example 1 was used. Based on 3 ml Hydrocyantechniksaustrag but 6 ml of n-heptane were used. The procedure was carried out as described in Example 1. The test results are summarized in Table 3 and Figure 2.
  • Table 3 and Figure 2 show that the rate of phase separation increases significantly as the amount of acetonitrile increases and the temperature increases.

Abstract

L'invention concerne un procédé de séparation extractive de complexes de nickel(0) et de ligands contenant du phosphore à partir d'un produit de réaction d'hydrocyanuration de mononitriles insaturés en dinitriles, par extraction au moyen d'un hydrocarbure. Une séparation de phases est réalisée afin de séparer l'hydrocarbure et la solution contenant des nitriles en deux phases par addition d'au moins un additif polaire au produit d'hydrocyanuration (flux d'alimentation) et/ou à l'étape d'extraction.
EP07727428A 2006-04-07 2007-03-28 Procédé de séparation de complexes de nickel(0) et de ligands contenant du phosphore à partir de mélanges de nitriles Withdrawn EP2007491A2 (fr)

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US9051242B2 (en) 2010-07-07 2015-06-09 Invista North America S.A.R.L. Process for making nitriles
US9133108B2 (en) 2010-07-07 2015-09-15 Invista North America S.A.R.L. Process for making nitriles
US9133107B2 (en) 2010-07-07 2015-09-15 Invista North America S.A.R.L. Process for making nitriles
US9169197B2 (en) 2010-07-07 2015-10-27 Invista North America S.A. R.L. Process for making nitriles

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US20090270645A1 (en) 2009-10-29
KR20090006177A (ko) 2009-01-14
WO2007115936A2 (fr) 2007-10-18
CN101460229A (zh) 2009-06-17
JP2009532419A (ja) 2009-09-10
WO2007115936A3 (fr) 2007-11-29

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