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WO1999047484A1 - Procede de realisation d'une reaction d'equilibre - Google Patents

Procede de realisation d'une reaction d'equilibre Download PDF

Info

Publication number
WO1999047484A1
WO1999047484A1 PCT/EP1999/001451 EP9901451W WO9947484A1 WO 1999047484 A1 WO1999047484 A1 WO 1999047484A1 EP 9901451 W EP9901451 W EP 9901451W WO 9947484 A1 WO9947484 A1 WO 9947484A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
educt
carbon atoms
optionally
boiling
Prior art date
Application number
PCT/EP1999/001451
Other languages
German (de)
English (en)
Inventor
Stephan Blum
Jürgen FALKOWSKI
Jens-Joachim Vier
Bernhard Gutsche
Rolf Kawa
Holger Tesmann
Original Assignee
Cognis Deutschland Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Priority to EP99913234A priority Critical patent/EP1064248A1/fr
Publication of WO1999047484A1 publication Critical patent/WO1999047484A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention is in the field of steam permeation and relates to the esterification of substituted carboxylic acids or the conversion of aldehydes or ketones into acetals or ketals.
  • Carbonyl compounds are interesting starting materials for the production of products for a large number of applications.
  • fatty acids or other substituted carboxylic acids can be converted into esters by reaction with lower alcohols, which are of interest, for example, as lubricants, finishing agents or oil bodies for cosmetic or pharmaceutical applications.
  • Aldehydes or ketones can be acetalized or ketalized with alcohols or then find similar fields of application.
  • European patent EP 0535073 B1 also discloses a method for carrying out an equilibrium reaction using vapor permeation, in which gaseous isopropyl alcohol is passed through myristic acid in a bubble reactor, unreacted alcohol and condensate water are separated in a membrane module and the recovered alcohol is in leads the reaction back.
  • gaseous isopropyl alcohol is passed through myristic acid in a bubble reactor, unreacted alcohol and condensate water are separated in a membrane module and the recovered alcohol is in leads the reaction back.
  • the practically complete implementation of linear fatty acids with lower alcohols is due to the lack of steric hindrance is not a technically demanding problem and therefore has no relation to the subject of the invention.
  • the complex object of the invention was to provide a process for the implementation of carbonyl compounds which are usually difficult to derivatize, i.e. to provide substituted carboxylic acids, aldehydes and ketones with lower alcohols to the corresponding esters, acetals and ketals, which is free from the disadvantages described.
  • high sales should be achieved within a short period of time and products that were as light as possible should be obtained.
  • the invention relates to a method for carrying out an equilibrium reaction, in which
  • B represents an optionally hydroxy- and / or carboxysu substituted and optionally interrupted by an ether oxygen alk (en) ylene radical having 1 to 12 carbon atoms, represents a phenyl radical or a carbonyl group
  • R 1 and R 2 independently of one another are hydrogen, represent a hydroxyl or alkyl radical having 1 to 12 carbon atoms or, together with at least one carbonyl group, form a saturated or unsaturated, optionally C 1 -C 4 -alkyl and / or hydroxy-substituted aliphatic Cs or C ⁇ ring
  • the sum of either n1 and n2 represents 1 or 2 and m represents 0 or 1
  • E2 uses aliphatic alcohols having 2 to 8 carbon atoms.
  • the equilibrium reaction can be an esterification.
  • carboxyl compounds which are selected from the group formed by aliphatic or aromatic di-, tri- or tetracarboxylic acids, mono- or polyhydric hydroxycarboxylic acids, aldehyde carboxylic acids, ketocarboxylic acids and ether carboxylic acids, preferably those, which have 2 to 20 and preferably 4 to 10 carbon atoms.
  • Typical examples are oxalic acid, succinic acid, maleic acid, itaconic acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1, 12-dodecanedioic acid, lactic acid, tartaric acid, malic acid, citric acid, glyoxylic acid, mesoxalic acid, pyruvic acid, and acetoacetic acid, diglytic acid, digly.
  • the equilibrium reaction can be acetalization or ketalization.
  • mono- or dialdehydes, open-chain or branched ketones, diketones or ⁇ -diketones are used as heavy-boiling feedstocks, preferably those which have 2 to 20 and preferably 4 to 10 carbon atoms.
  • Typical examples are glyoxal, diethyl ketone, diisopropyl ketone, methyl tert-butyl ketone (pinacoline), methyl isobutyl ketone, caprinone, stearone, cyclopentanone, cyciohexanone, menthone, dimedone and the like.
  • Low alcohols such as ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, heptanol, n-octanol and 2-ethylhexanol, are suitable as low boilers. Also suitable are 1, 2- or 1, 3-diols with 1 to 6 carbon atoms, such as 1, 3-propylene glycol, 1, 2-butanediol, 2,3-butanediol and the like.
  • the boiling point difference between the starting materials E1 and E2 is preferably 5 to 25 and in particular 10 to 20 ° C.
  • those starting materials are preferred which form an azeotrope with water or in which water is soluble in small amounts. It has also proven advantageous that React reactants E1 and E2 in a stoichiometric ratio, ie in molar ratios of 1: 0.9 to 1: 1, 1. Alcohol component and membrane must match each other so that the permeate - usually the condensate water - can pass through, while the alcohol is largely retained from retentate. The person skilled in the art can set this within the framework of customary optimization, without having to be inventive.
  • the membrane module and / or its feed line from the reactor be heated or cooled in accordance with the desired membrane temperature.
  • evaporative cooling blowing in liquid alcohol
  • this measure leads to a decrease in the partial pressure of the preferably permeating component and thus to a reduction in the driving force.
  • the reactor is designed as a bubble reactor in which the higher-boiling component E1 is brought to the necessary reaction temperature.
  • the alcohol component E2 is pumped into the reactor in liquid form, close to the boiling point (ie 1 to 5 ° C. below the boiling point).
  • reaction temperature is usually significantly higher, ie at least 10 ° C above the boiling point of the alcohol
  • E2 evaporates suddenly when it enters the hot component E1, bubbles in bubble form through the reaction volume and thus ensures thorough mixing.
  • the water generated by the reaction escapes with the unreacted alcohol as an overheated steam mixture into the steam room.
  • the steam mixture is fed to a membrane module, which serves as a receptacle for the membrane.
  • the water is removed from this vaporous alcohol / water mixture by the vacuum applied to the membrane permeate side.
  • the retentate remaining from unreacted alcohol and small amounts of water not separated off is preferably condensed outside the module and returned to the reaction mixture.
  • the retentate is passed into the reactor together with the lower-boiling educt in the liquid state.
  • the retentate is passed into the reactor together with the lower-boiling educt in the gaseous state.
  • the steam stream emerging from the reactor is conducted through the membrane module analogously to the reaction procedure described above and then sucked in again. As a result of this circulation, the energy-consuming evaporation and thus the subsequent condensation of the retentate can be dispensed with.
  • small amounts of membrane-damaging educt or product e.g. B.
  • the vapors a device, z. B. a droplet separator, upstream for the separation of entrained liquid.
  • the reaction can take place in one preferred embodiment of the invention can also be carried out under pressure, ie in the range from 1 to 5 bar.
  • the educt E1 was metered in at 120.degree. C., heated to 170.degree. C., 1% by weight of isobutyl titanate was added as a catalyst and then E2 was pumped into the hot E1 in liquid form at approx. 85.degree.
  • the amount of E2 used was in a stoichiometric molar ratio (1: 1) to the E1 used.
  • the operating pressure was 4 bar, the retentate circulation 4 kg / h and the permeate pressure 50 mbar.
  • Table 1 gives an overview of the starting materials used.
  • Table 2 shows the progress of the reaction using the amount of condensate water discharged as permeate.
  • Residues form an aliphatic Ce ring with the carbonyl group, which is substituted in the 3-position with 2 methyl groups and in the 5-position with a hydroxyl group and has a double bond in the 4,5-position.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé permettant de réaliser une réaction d'équilibre, selon lequel: (a) on fait passer, dans un réacteur à bulles, un éduit (E2) à bas point d'ébullition, présent sous forme gazeuse dans des conditions de réaction, à travers un éduit (E2) liquide, séparé, dont le point d'ébullition est plus élevé; (b) on conduit l'éduit (E2) n'ayant pas réagi et le produit (P1) à séparer, également présent sous forme de gaz, en tant que charge, à un module membranaire adapté pour être traversé par des vapeurs, dans lequel (P1) est séparé en tant que perméat, tandis que l'éduit (E2) est récupéré en tant que rétentat et remis en circulation dans le réacteur jusqu'à ce que l'éduit (E1) ait été transformé, dans la proportion souhaitée, en produit cible. Ledit procédé se caractérise en ce que: l'on utilise comme éduit E1 des composés carbonylés de la formule (I) R1-(CO)¿n1?-(B)m-(CO)n2-R?2¿, dans laquelle B représente un reste alkyle ou alcényle C¿1?-C12 éventuellement substitué par hydroxy et/ou carboxy et éventuellement interrompu par un oxygène d'éther, un reste phényle ou un groupe carbonyle, R?1 et R2¿ représentent, indépendamment l'un de l'autre, hydrogène, un reste hydroxyle ou alkyle C¿1?-C12, ou bien forment, avec au moins un groupe carbonyle, un cycle C5 ou C6 aliphatique, saturé ou insaturé, éventuellement substitué par alkyle C1-C4 et/ou hydroxy, la somme de n1 et n2 étant égale à 1 ou 2, et m valant 0 ou 1; et l'on utilise comme éduit (E2) des alcools aliphatiques comportant 2 à 8 atomes de carbone.
PCT/EP1999/001451 1998-03-17 1999-03-06 Procede de realisation d'une reaction d'equilibre WO1999047484A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99913234A EP1064248A1 (fr) 1998-03-17 1999-03-06 Procede de realisation d'une reaction d'equilibre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19811451A DE19811451C1 (de) 1998-03-17 1998-03-17 Verfahren zur Acetalisierung bzw. Ketalisierung
DE19811451.6 1998-03-17

Publications (1)

Publication Number Publication Date
WO1999047484A1 true WO1999047484A1 (fr) 1999-09-23

Family

ID=7861123

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/001451 WO1999047484A1 (fr) 1998-03-17 1999-03-06 Procede de realisation d'une reaction d'equilibre

Country Status (3)

Country Link
EP (1) EP1064248A1 (fr)
DE (1) DE19811451C1 (fr)
WO (1) WO1999047484A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1167333A2 (fr) * 2000-06-26 2002-01-02 F. Hoffmann-La Roche Ag Pocédé et dispositif pour la préparation d'acétals et de kétals
US6528025B1 (en) 2000-06-26 2003-03-04 Roche Vitamins Inc. Process of manufacturing equipment for preparing acetals and ketals
EP1357102A1 (fr) * 2002-04-27 2003-10-29 Degussa AG Procédé pour la préparation d'acetals et de cétals à l'aide de la pervaporation ou de la perméation de vapeur en plusieurs étapes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991019559A1 (fr) * 1990-06-15 1991-12-26 Henkel Kommanditgesellschaft Auf Aktien Procede d'execution d'une reaction d'equilibre avec application d'une permeation de vapeur
EP0691324A1 (fr) * 1994-07-04 1996-01-10 Bayer Ag Procédé de préparation d'esters dialkyliques d'acide maléique
EP0835860A1 (fr) * 1996-10-14 1998-04-15 Bayer Ag Séparation d'eau de mélanges réactionnels

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2956070A (en) * 1958-04-29 1960-10-11 American Oil Co Organic chemical reactions involving liberation of water
GB8518575D0 (en) * 1985-07-23 1985-08-29 Bp Chem Int Ltd Esterification process
JPH069645B2 (ja) * 1986-12-25 1994-02-09 リグナイト株式会社 混合溶液の分離方法
US4894163A (en) * 1987-06-12 1990-01-16 Kuraray Co., Ltd. Separation of liquid mixtures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991019559A1 (fr) * 1990-06-15 1991-12-26 Henkel Kommanditgesellschaft Auf Aktien Procede d'execution d'une reaction d'equilibre avec application d'une permeation de vapeur
EP0535073A1 (fr) * 1990-06-15 1993-04-07 Henkel Kgaa Procede d'execution d'une reaction d'equilibre avec application d'une permeation de vapeur.
EP0691324A1 (fr) * 1994-07-04 1996-01-10 Bayer Ag Procédé de préparation d'esters dialkyliques d'acide maléique
EP0835860A1 (fr) * 1996-10-14 1998-04-15 Bayer Ag Séparation d'eau de mélanges réactionnels

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1167333A2 (fr) * 2000-06-26 2002-01-02 F. Hoffmann-La Roche Ag Pocédé et dispositif pour la préparation d'acétals et de kétals
EP1167333A3 (fr) * 2000-06-26 2002-07-31 F. Hoffmann-La Roche Ag Pocédé et dispositif pour la préparation d'acétals et de kétals
US6528025B1 (en) 2000-06-26 2003-03-04 Roche Vitamins Inc. Process of manufacturing equipment for preparing acetals and ketals
US6806392B2 (en) 2000-06-26 2004-10-19 Dsm Ip Assets B.V. Process and manufacturing equipment for preparing acetals and ketals
EP1357102A1 (fr) * 2002-04-27 2003-10-29 Degussa AG Procédé pour la préparation d'acetals et de cétals à l'aide de la pervaporation ou de la perméation de vapeur en plusieurs étapes

Also Published As

Publication number Publication date
DE19811451C1 (de) 1999-10-14
EP1064248A1 (fr) 2001-01-03

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