EP1521737A1 - Procede de recuperation d'un acide de lewis - Google Patents

Procede de recuperation d'un acide de lewis

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Publication number
EP1521737A1
EP1521737A1 EP03763704A EP03763704A EP1521737A1 EP 1521737 A1 EP1521737 A1 EP 1521737A1 EP 03763704 A EP03763704 A EP 03763704A EP 03763704 A EP03763704 A EP 03763704A EP 1521737 A1 EP1521737 A1 EP 1521737A1
Authority
EP
European Patent Office
Prior art keywords
mixture
water
phase
lewis acid
compound
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.)
Withdrawn
Application number
EP03763704A
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German (de)
English (en)
Inventor
Tim Jungkamp
Jens Scheidel
Hermann Luyken
Michael Bartsch
Robert Baumann
Gerd Haderlein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from DE2002131292 external-priority patent/DE10231292A1/de
Priority claimed from DE2002140012 external-priority patent/DE10240012A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1521737A1 publication Critical patent/EP1521737A1/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Withdrawn legal-status Critical Current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
    • B01J31/16—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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/28—Regeneration or reactivation
    • B01J27/32—Regeneration or reactivation of catalysts comprising compounds of halogens
    • 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
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
    • C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
    • B01J2231/343—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones to prepare cyanhydrines, e.g. by adding HCN or TMSCN
    • 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 present invention relates to a process for the recovery of a Lewis acid from a reaction mixture (I) which has been obtained in the hydrocyanation of an olefinically unsaturated compound to give a nitrile which has a miscibility gap with water under certain quantity, pressure and temperature conditions Presence of a catalyst system containing a Lewis acid and a complex compound of a phosphorus-containing compound suitable as a ligand and a central atom suitable for this compound,
  • phase (III) which contains a higher proportion of water than said nitrile and a phase (IV) which contains a higher proportion contains said nitrile than water, phase (III) having a higher content of said Lewis acid than phase (IV),
  • cl does not form an azeotrope with water and whose boiling point is higher than that of under certain pressure conditions
  • step (V) is subjected to distillation under the pressure conditions mentioned in step cl) or c2) to obtain a mixture (VI) which contains a higher proportion of water than the diluent (V) and a mixture (VII) which comprises one contains a higher proportion of diluent (V) than water, mixture (VII) having a higher content of said ter Lewis acid has as mixture (VI), and
  • the present invention had for its object to provide a process which enables the recovery of the Lewis acid from such a reaction mixture in a form which permits the reuse of the Lewis acid in the said hydrocyanation in a technically simple and economical manner.
  • the process according to the invention also has the advantage that it separates the complex compound used as a component of the catalyst system from a phosphorus-containing compound suitable as a ligand and a central atom suitable for this compound in a form which enables the reuse of the Complex compound allowed in said hydrocyanation, as well as the separation of the product of value obtained in the hydrocyanation from the reaction mixture obtained in the hydrocyanation in a technically simple and economical manner.
  • step a) of the process according to the invention a reaction mixture (I) is used which was obtained in the hydrocyanation of an olefinically unsaturated compound to give a nitrile which has a miscibility gap with water under certain quantity, pressure and temperature conditions, in the presence of a catalyst system , containing a Lewis acid and a complex compound of a phosphorus-containing compound suitable as a ligand and a central atom suitable for this compound.
  • adiponitrile comes into consideration as the nitrile, which has a miscibility gap with water under certain quantity, pressure and temperature conditions.
  • 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, Znl, ZnCl, ZnS0, CuCl 2 , CuCl, Cu (0 3 SCF 3 ) 2 , CoCl 2 , CoI 2 , Fel 2 , FeCl 3 , FeCl 2 , FeCl 2 (THF) 2 , TiCl 4 (THF ) 2 , TiCl 4 , TiCl 3 , ClTi (0-i-propyl) 3- MnCl 2 , SCCI 3 , AICI 3 , (CsH ⁇ ) A1C1, (C 8 H ⁇ ) 2 A1C1, (i-CH 9 ) 2 AlCl, (C 6 H 5 ) 2 A1C1, (C 6 H 5 ) A1C1 2 , ReCl 5 , ZrCl 4 / NbCl 5 , VCI 3 , CrCl 2 , M0CI 5 , YCI3, CdCl 2 , LaCl 3 , Er (0 3 SCF 3
  • 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, can also be used as a promoter , Chromium, molybdenum, tungsten, manganese, rhenium, palladium, thorium, iron and cobalt, preferably zinc, cadmium, titanium, tin, chromium, iron and cobalt, can be used, and the anionic part of the compound can be selected from the group consisting of from 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 P0 2- , CF 3 COO-, ' C 7 H 15 OSO 2 - or SO 4
  • halides such
  • borohydrides, 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 with between 6 and 18 carbon atoms. Atoms, aryl radicals substituted with alkyl groups with 1 to 7 carbon atoms and aryl radicals substituted with cyano-substituted alkyl groups with 1 to 7 carbon atoms, advantageously called riphenylboron.
  • riphenylboron advantageously called riphenylboron.
  • synergistically effective combinations of Lewis acids can be used to increase the activity of the catalyst system.
  • Lewis acid also includes the promoters mentioned in US 3,496,217, US 3,496,218, US 4,774,353, US 4,874,884, US 6,127,567, US 6,171,996 and US 6,380,421.
  • Lewis acids include, in particular, metal salts, particularly preferably metal halides, such as fluorides, chlorides, bromides, iodides, in particular chlorides, of which zinc chloride, iron (II) chloride and iron (III) chloride are particularly preferred.
  • metal salts particularly preferably metal halides, such as fluorides, chlorides, bromides, iodides, in particular chlorides, of which zinc chloride, iron (II) chloride and iron (III) chloride are particularly preferred.
  • reaction mixtures (I) are known per se, for example from US 3,496,217, US 3,496,218, US 4,774,353, US 4,874,884, US 6,127,567, US 6,171,996 and US 6,380,421.
  • step a) of the process according to the invention said complex compound is separated from mixture (I) to obtain a mixture (II).
  • This separation can be carried out in a manner known per se, preferably by extraction, as described, for example, in US Pat. No. 3,773,809.
  • Preferred extraction agents are alkanes or cycloalkanes.
  • Alkanes which can advantageously be used are n-pentane, n-hexane, n-heptane, n-octane and their branched isomers, or mixtures thereof, in particular those having a boiling point in the range from about 30 to about 135 ° C.
  • Suitable cycloalkanes are advantageously cyclopentane, cyclohexane, cycloheptane and alkyl-substituted cycloalkanes, or mixtures thereof, in particular those having a boiling point in the range from about 30 to about 135 ° C., such as methylcyclohexane.
  • the extraction can advantageously be carried out at a temperature in the range from approximately 0 to approximately 100 ° C.
  • the extraction can be carried out batchwise or continuously, a continuous countercurrent procedure having proven to be advantageous.
  • the weight ratio of phosphorus compound suitable as a ligand to the nitrile to be extracted should be in the range from 1: 1000 to 90: 100.
  • the weight ratio between extractant and phosphorus compound suitable as ligand should advantageously be in the range from 2: 1 to 100: 1.
  • the extraction can be carried out under ambient pressure or under increased pressure to avoid evaporation of the extractant.
  • the complex compound can be obtained from the extract by removing the extractant, for example by evaporating the extractant, and, if desired, can be returned to the hydrocyanation, as described in US Pat. No. 3,773,809.
  • the mixture (II) obtained in step a) contains the nitrile obtained by hydrocyanation of an olefinically unsaturated compound which, under certain quantity, pressure and temperature conditions, has a miscibility gap with water which is part of that used for the hydrocyanation
  • the content of the complex compound used as a component of the catalyst system used for hydrocyanation, comprising a phosphorus-containing compound suitable as a ligand and a central atom suitable for this compound, is preferably 0 to 60% by weight, in particular 0 to 50% by weight, based on the total weight of the mixture (I).
  • mixture (II) contains undissolved constituents
  • the optimal equipment and process conditions for such a separation can easily be determined by a few simple preliminary tests.
  • step b) mixture (II) is mixed with water and the system is brought into pressure and temperature conditions such that a phase (II) which contains a higher proportion of water than said nitrile and a phase (IV) which contains a higher proportion of said nitrile than water, phase (III) having a higher content of said Lewis acid than phase (IV).
  • the ratio of water to mixture (II) is not critical per se. With increasing ratio of Lewis acid to be recovered in mixture (II) to water, the viscosity of phase (III) increases significantly, so that the handling of the system of phase (IV) and phase (III) becomes increasingly complex.
  • a proportion of the Lewis acid in the total weight of phase (III) is in the range of at least 0.01% by weight, preferably at least 0.1% by weight, particularly preferably at least 0.25% by weight, particularly preferably at least 0.5% by weight.
  • Such an amount of water has proven to be advantageous that a proportion of the Lewis acid in the total weight of phase (III) is in the range of at most 60% by weight, preferably at most 35% by weight, particularly preferably at most 30% by weight. % sets. If the amount of water used to extract the Lewis acid from the mixture (II) is such that the mixture (III) has a concentration of Lewis acid which is less than that of the fresh feed solution, the Concentration of the Lewis acid by concentration in a manner known per se, such as being increased by pre-evaporation with the deduction of "a portion of the water from mixture (III), preferably to the concentration of Lewis acid which prevails in the freshly used solution at most 60% by weight, preferably at most 35% by weight, particularly preferably at most 32% by weight, particularly preferably at most 30% by weight, further advantageously at least 1% by weight, preferably at least 15% by weight, particularly preferably at least 25% by weight, based in each case on the proportion by weight of Lewis acid in mixture (III).
  • step) b can be employed pure 'water.
  • the water can contain further constituents, such as ionic or nonionic, organic or inorganic compounds, in particular those which are homogeneously miscible with water in a single phase or dissolved in water.
  • the addition of an inorganic or organic acid can be considered.
  • Those acids which do not form an azeotrope with water and which have a boiling point under the distillation conditions according to step d) of the process according to the invention which is lower than that of the liquid diluent (V) or under the distillation conditions according to step d) of the invention can preferably be used Process forms an azeotrope or heteroazeotrope with water.
  • Hydrogen halides such as HF, HC1, HBr, HJ, in particular HC1, are particularly preferred.
  • the amount of acid can advantageously be chosen so that the pH of the water used in step b) is less than 7.
  • the amount of acid can advantageously be chosen such that the pH of the water used in step b) is greater than or equal to 0, preferably greater than or equal to 1.
  • phase separation can be carried out in a manner known per se in apparatuses described for such purposes, as described, for example, in: Ullmann's Encyclopedia of Industrial Chemistry, Vol. B3, 5th Ed., VCH Verlagsgesellschaft, 'Weinheim, 1988, pages 6-14 to 6 -22 are known.
  • reaction according to step b) can be carried out batchwise or preferably continuously, with a continuous countercurrent procedure, particularly in a multistage extraction column ⁇ gene or a single-stage or multi-stage mixer-settler apparatus, as has been found advantageous.
  • Phase (IV) which contains the majority of the nitrile obtained in the hydrocyanation, can advantageously be fed to the production of this nitrile.
  • step (c) phase (III) is mixed with a liquid diluent (V) which
  • cl does not form an azeotrope with water and whose boiling point is higher than that of water or under certain pressure conditions
  • c2 forms an azeotrope or heteroazeotrope with water under certain pressure conditions.
  • Diluent (V) should advantageously be chosen so that said Lewis acid in diluent (V) under the distillation conditions according to step d) has a solubility of at least 0.1% by weight, based on diluent (V).
  • Diluents (V) include, for example, amides, in particular dialkylamides, such as diethylformamide, dimethylacetamide, N, N, -dimethylethyleneurea (DMEU), N, N-dimethylpropyleneurea (DMPU), hexamethylenephosphoric triamide (HMPT), ketones, sulfur-oxygen- Compounds such as dimethyl sulfoxide, tetra hydrothiophene-1,1-dioxide, nitroaromatics, such as nitrobenzene, nitroalkanes, such as nitromethane, nitroethane, ethers, such as diether of diethylene glycol, for example diethylene glycol dimethyl ether, alkylene carbonates, such as ethylene carbonate, nitriles, such as acetonitrile, propionitrile, n-butyronitrile Valeronitrile, cyanocyclopropane, acrylonitrile, crotonitrile,
  • Such diluents can be used alone or as a mixture.
  • Such aprotic, polar diluents can contain further diluents, preferably aromatics, such as benzene, toluene, o-xylene, m-xylene, p-xylene, aliphatics, in particular cycloaliphatics, such as cyclohexane, methylcyclohexane, or mixtures thereof.
  • aromatics such as benzene, toluene, o-xylene, m-xylene, p-xylene, aliphatics, in particular cycloaliphatics, such as cyclohexane, methylcyclohexane, or mixtures thereof.
  • diluents (V) can be used which form an azeotrope or heteroazeotrope with water.
  • the amount of diluent (V) compared to the amount of water in phase (III) is not critical per se. It is advantageous to use more liquid diluent (V) than the amounts to be distilled off by the azeotropes in step d), so that excess diluent (V) remains as the bottom product. .
  • the amount of diluent per se is not critical to the amount of water in phase (III).
  • the diluent should have a boiling point under the pressure and temperature conditions of the distillation in step d), which is preferably at least 5 ° C., in particular at least 20 ° C., and preferably at most 200 ° C., in particular at most 100 ° C above that of water under these distillation conditions.
  • Organic diluents are advantageous, preferably those with at least one nitrile group, in particular one nitrile group.
  • an aliphatic, saturated or an aliphatic, olefinically unsaturated nitrile can be used as the nitrile.
  • nitriles with 3, 4, 5, 6, 7, 8, 9, 10, in particular 4 carbon atoms, calculated without the nitrile groups, preferably nitrile groups, are suitable.
  • a diluent (V) is suitable which partially or completely contains the compound to be cyanated according to step e), in particular consists of it.
  • an aliphatic, olefinically unsaturated mononitrile selected from the group consisting of 2-cis-pentenenitrile, 2-trans-pentenenitrile, 3-cis-pentenenitrile, 3-trans-pentenenitrile can be used as the diluent.
  • 2-cis-pentenenitrile, 2-trans-pentenenirile, 3-cis-pentenenitrile, 3-trans-pentenenitrile, 4-pentenenitrile, E-2-methyl-2-butenenitrile, Z-2-methyl-2-butenenitrile, 2- Methyl-3-butenenitrile or mixtures thereof are known and can be obtained by processes known per se, such as by hydrocyanation of butadiene in the presence of catalysts, for example according to US Pat. No. 3,496,215 or the linear pentenenitriles by isomerization of 2-methyl-3-butenenitrile according to WO 97/23446 and methods described therein.
  • This product can advantageously be used for further hydrocyanation in the presence of a catalyst to give adiponitrile.
  • a depletion of 2-cis-pentenenitrile, 2-trans-pentenenitrile, E-2-methyl-2-butenenitrile, Z-2-methyl-2-butenenitrile, 2-methyl-3-butenenitrile is advantageous in so far as this two compounds of the hydrocyanation mentioned considerably are less accessible than 3-cis-pentenenitrile, 3-trans-pentenonitrile, 4-pentenenitrile or mixtures thereof.
  • the ratio of pentenenitrile to said Lewis acid has at least 0.5 mol / mol, preferably at least 5 mol / mol, particularly preferably at least 15 mol / mol proved to be advantageous.
  • the quantitative ratios of pentenenitrile to said Lewis acid have at most 10,000 mol / mol, preferably at most 5000 mol / mol, particularly preferably at most 2000 mol / mol proven to be advantageous.
  • Such pentenenitriles can advantageously be hydrocyanated to adiponitrile in step e).
  • step d) the mixture of phase (III) and liquid diluent (V) is subjected to a distillation under the pressure conditions mentioned in step cl) or c2) to obtain a mixture (VI) which has a higher proportion of water than of diluent ( V) and a mixture (VII) which contains a higher proportion of diluent (V) than water, mixture (VII) having a higher content of said Lewis acid than mixture (VI).
  • the pressure conditions for the distillation are not critical per se. Pressures of at least 10 -4 MPa, preferably at least 10 -3 MPa, in particular at least 5 * 10 -3 MPa, have proven to be advantageous.
  • the distillation temperature is then set depending on the pressure conditions and the composition of the mixture to be distilled.
  • the distillation can advantageously be carried out at a pressure of at most 200 kPa, preferably at most 100 kPa, in particular at most 50 kPa.
  • the distillation can advantageously be carried out at a pressure of at least 1 kPa, preferably at least 5 kPa, particularly preferably at 10 kPa.
  • the distillation can advantageously be carried out by single-stage evaporation, preferably by fractional distillation in one or more, such as 2 or 3, distillation apparatuses.
  • Equipment suitable for distillation for this purpose such as those described, for example, in: Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 7, John Wiley & Sons, New York, 1979, pages 870-881 , such as sieve tray columns, bubble tray trays, packed columns, packed columns, columns with side take-off or dividing wall columns.
  • the distillation can be carried out batchwise. i The distillation can be carried out continuously.
  • mixture (VI) is usually obtained overhead.
  • Mixture (VI) can advantageously be wholly or partly recycled in step b) and can be reacted there according to the invention as water or in a mixture with water with mixture (II).
  • mixture (VI) is single-phase, mixture (VI) can be partly or completely recycled.
  • mixture (VI) is two-phase, partial or complete recycling of the phase having the greater water mass content is advantageous.
  • Mixture (VII) is usually obtained as the bottom product in the distillation in step b).
  • Mixture (VII) contains the recovered proportion of said Lewis acid and diluent (V); the water content of mixture (VII) should preferably be in the range from 0 to 0.5% by weight, in particular in the range from 0 to 50 ppm by weight, based on the total weight of mixture (VII).
  • step e) mixture (VII) of a hydrocyanation of an olefinically unsaturated compound to give a nitrile which has a miscibility gap with water under certain quantity, pressure and temperature conditions, in the presence of a catalyst system comprising a Lewis acid and a complex compound from a phosphorus-containing compound suitable as a ligand and a central atom suitable for this compound.
  • a catalyst system comprising a Lewis acid and a complex compound from a phosphorus-containing compound suitable as a ligand and a central atom suitable for this compound.
  • the complex compound separated off in step a) can advantageously be used as the complex compound.
  • the olefinically unsaturated compound to be hydrocyanated is preferably diluent (V).
  • the content of Zn or zinc chloride was determined by means of atomic emission spectrometry.
  • the chlorine content was determined by the Schoeniger method.
  • the concentrations of water were determined potentiometrically by titration according to the Karl Fischer method.
  • the upper phase consisting essentially of trans-3-pentenenitrile
  • the lower phase consisted essentially of water and was continuously pumped out of the phase separation vessel.
  • a homogeneous solution of ZnCl 2 in trans-3-pentenenitrile at 348 K was separated off at the bottom.
  • Example 2 4 kg of the bottom discharge obtained in Example 1 were mixed with 1 kg of trans-3-pentonitrile and 500 g of water. The homogeneous mixture was metered into the distillation column operated as in Example 1 at a metering rate of 206 g / h.
  • the bottom discharge contained 350 ppm by weight of water, 16.9% by weight of chlorine, calculated as Cl and 15.5% by weight of Zn, in each case based on the total weight of the solution; this leads to an experimentally found Cl.Zn ratio of 2.01.
  • the zinc chloride solution in 3-pentenenitrile obtained in this way can be used in the hydrocyanation of 3-pentenenitrile in the presence of nickel (0) phosphite catalysts and shows no activity difference to a solution freshly prepared from 3-pentenenitrile and anhydrous zinc chloride.
  • a continuously operated mixer-settler apparatus consisting of a container with 2 1 volume operated at room temperature, equipped with an inclined blade stirrer operated at 700 rpm and a hydrostatic overflow into a subsequent switched phase separator with a volume of 0.5 l, 320 g / h of a solution of 0.52% by weight of ZnCl 2 in a mixture of 20% by weight of trans-3-pentenenitrile and the rest of adiponitrile, and 100 g / h of water were metered in.
  • the organic phase with 30 ppm of Zn was obtained via the phase separator, and the separated aqueous phase contained 0.75% by weight of Zn.
  • an accumulation of solid was observed in the phase separator, which accumulated at the phase interface.
  • the solid consisted of ZnCl 2 -4Zn (0H) 2 -2HO.
  • 320 g / h of trans-3-pentenenitrile were metered into the distillation column with a second pump. After 9.5 hours of continuous distillation, 310 ppm by weight of water and 0.10% by weight of Zn (corresponding to 0.20% by weight of ZnCl 2 ) were analyzed in the bottom discharge.
  • the solution of ZnCl in trans-3-pentenenitrile obtained via the bottom can be hydrocyanated to adiponitrile in the presence of Ni (O) phosphite catalysts.

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de récupération d'un acide de Lewis contenu dans un mélange réactionnel (I), qui est obtenu lors de l'hydrocyanation d'un composé oléfiniquement insaturé en un nitrile, présentant une lacune de miscibilité avec l'eau dans certaines conditions de quantité, de pression et de température, en présence d'un système catalyseur contenant un acide de Lewis et un composé complexe constitué d'un composé phosphoré, approprié pour être utilisé comme ligand, et d'un atome central approprié pour ce composé. Ledit procédé se caractérise en ce qu'il consiste a) à séparer du mélange (I) le composé complexe susmentionné jusqu'à l'obtention d'un mélange (II), b) à mélanger ce mélange (II) avec de l'eau et à transformer ce mélange dans certaines conditions de pression et de température, de façon à obtenir une phase (III), présentant davantage d'eau que de nitrile susmentionné, et une phase (IV), présentant davantage de nitrile susmentionné que d'eau, laquelle phase (III) présente une teneur en acide de Lewis susmentionné supérieure à celle de la phase (IV), c) à mélanger la phase (III) avec un agent de dilution liquide (V), c1) qui ne forme aucun azéotrope avec l'eau et dont le point d'ébullition est supérieur à celui de l'eau dans certaines conditions de pression ou c2) qui forme un azéotrope ou hétéroazéotrope avec l'eau dans certaines conditions de pression, d) à soumettre le mélange constitué de la phase (III) et de l'agent de dilution liquide (V) à une distillation dans les conditions de pression mentionnées à l'étape cl) ou c2) jusqu'à l'obtention d'un mélange (VI), contenant davantage d'eau que d'agent de dilution (V), et d'un mélange (VII), contenant davantage d'agent de dilution (V) que d'eau, lequel mélange (VII) présente une teneur en acide de Lewis susmentionné supérieure à celle du mélange (VI), puis e) à amener le mélange (VII) à une hydrocyanation d'un composé oléfiniquement insaturé en un nitrile, présentant une lacune de miscibilité avec l'eau dans certaines conditions de quantité, de pression et de température, en présence d'un système catalyseur, contenant un acide de Lewis et un composé complexe constitué d'un composé phosphoré, approprié pour être utilisé comme ligand, et d'un atome central approprié pour ce composé.
EP03763704A 2002-07-10 2003-07-04 Procede de recuperation d'un acide de lewis Withdrawn EP1521737A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE2002131292 DE10231292A1 (de) 2002-07-10 2002-07-10 Verfahren zur Rückführung einer Lewis-Säure
DE10231292 2002-07-10
DE2002140012 DE10240012A1 (de) 2002-08-27 2002-08-27 Verfahren zur Rückführung einer Lewis-Säure
DE10240012 2002-08-27
PCT/EP2003/007150 WO2004007431A1 (fr) 2002-07-10 2003-07-04 Procede de recuperation d'un acide de lewis

Publications (1)

Publication Number Publication Date
EP1521737A1 true EP1521737A1 (fr) 2005-04-13

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EP03763704A Withdrawn EP1521737A1 (fr) 2002-07-10 2003-07-04 Procede de recuperation d'un acide de lewis

Country Status (12)

Country Link
US (1) US7084294B2 (fr)
EP (1) EP1521737A1 (fr)
JP (1) JP2005538075A (fr)
CN (1) CN1274671C (fr)
AR (1) AR039736A1 (fr)
AU (1) AU2003246375A1 (fr)
BR (1) BR0311982A (fr)
CA (1) CA2491240A1 (fr)
MX (1) MXPA04012030A (fr)
MY (1) MY134370A (fr)
TW (1) TW200401764A (fr)
WO (1) WO2004007431A1 (fr)

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US7880028B2 (en) 2006-07-14 2011-02-01 Invista North America S.A R.L. Process for making 3-pentenenitrile by hydrocyanation of butadiene
US7897801B2 (en) 2003-05-12 2011-03-01 Invista North America S.A R.L. Process for the preparation of dinitriles
US7919646B2 (en) 2006-07-14 2011-04-05 Invista North America S.A R.L. Hydrocyanation of 2-pentenenitrile
US7973174B2 (en) 2005-10-18 2011-07-05 Invista North America S.A.R.L. Process of making 3-aminopentanenitrile
US7977502B2 (en) 2008-01-15 2011-07-12 Invista North America S.A R.L. Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile
US8088943B2 (en) 2008-01-15 2012-01-03 Invista North America S.A R.L. Hydrocyanation of pentenenitriles
US8101790B2 (en) 2007-06-13 2012-01-24 Invista North America S.A.R.L. Process for improving adiponitrile quality
US8178711B2 (en) 2006-03-17 2012-05-15 Invista North America S.A R.L. Method for the purification of triorganophosphites by treatment with a basic additive
US8338636B2 (en) 2009-08-07 2012-12-25 Invista North America S.A R.L. Hydrogenation and esterification to form diesters
US8373001B2 (en) 2003-02-10 2013-02-12 Invista North America S.A R.L. Method of producing dinitrile compounds

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DE10231296A1 (de) * 2002-07-10 2004-01-22 Basf Ag Verfahren zur Entfernung von Wasser aus einer Mischung, die Wasser und Zinkchlorid enthält
CN101687658B (zh) 2007-05-14 2013-07-24 因温斯特技术公司 高效反应器和方法
EP2334624B1 (fr) 2008-10-14 2014-10-01 Invista Technologies S.à.r.l. Procédé de fabrication de 2-alkyl secondaire-4,5-di-(alkyl normal)phénols
WO2012005918A1 (fr) 2010-07-07 2012-01-12 Invista Technologies S.A.R.L. Méthode de production de nitriles
CN104039412B (zh) 2011-12-21 2016-08-24 因温斯特技术公司 用于减少稳定乳液的萃取溶剂控制
EP2794048B1 (fr) 2011-12-21 2022-01-05 INVISTA Textiles (U.K.) Limited Contrôle de solvant d'extraction pour réduire des emulsions stables
KR20140127218A (ko) 2011-12-21 2014-11-03 인비스타 테크놀러지스 에스.에이 알.엘. 안정한 에멀젼을 감소시키기 위한 추출 용매 제어

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Publication number Priority date Publication date Assignee Title
US8373001B2 (en) 2003-02-10 2013-02-12 Invista North America S.A R.L. Method of producing dinitrile compounds
US7897801B2 (en) 2003-05-12 2011-03-01 Invista North America S.A R.L. Process for the preparation of dinitriles
US7973174B2 (en) 2005-10-18 2011-07-05 Invista North America S.A.R.L. Process of making 3-aminopentanenitrile
US8178711B2 (en) 2006-03-17 2012-05-15 Invista North America S.A R.L. Method for the purification of triorganophosphites by treatment with a basic additive
US7880028B2 (en) 2006-07-14 2011-02-01 Invista North America S.A R.L. Process for making 3-pentenenitrile by hydrocyanation of butadiene
US7919646B2 (en) 2006-07-14 2011-04-05 Invista North America S.A R.L. Hydrocyanation of 2-pentenenitrile
US8394981B2 (en) 2006-07-14 2013-03-12 Invista North America S.A R.L. Hydrocyanation of 2-pentenenitrile
US8101790B2 (en) 2007-06-13 2012-01-24 Invista North America S.A.R.L. Process for improving adiponitrile quality
US7977502B2 (en) 2008-01-15 2011-07-12 Invista North America S.A R.L. Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile
US8088943B2 (en) 2008-01-15 2012-01-03 Invista North America S.A R.L. Hydrocyanation of pentenenitriles
US8338636B2 (en) 2009-08-07 2012-12-25 Invista North America S.A R.L. Hydrogenation and esterification to form diesters

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MY134370A (en) 2007-12-31
CN1274671C (zh) 2006-09-13
AR039736A1 (es) 2005-03-09
CN1665776A (zh) 2005-09-07
MXPA04012030A (es) 2005-03-07
US20050247624A1 (en) 2005-11-10
WO2004007431A1 (fr) 2004-01-22
AU2003246375A1 (en) 2004-02-02
JP2005538075A (ja) 2005-12-15
TW200401764A (en) 2004-02-01
US7084294B2 (en) 2006-08-01
BR0311982A (pt) 2005-04-26
CA2491240A1 (fr) 2004-01-22

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