EP0489781A1 - Procede de production de sels alcalins d'acides carboxyliques d'ether - Google Patents

Procede de production de sels alcalins d'acides carboxyliques d'ether

Info

Publication number
EP0489781A1
EP0489781A1 EP90912729A EP90912729A EP0489781A1 EP 0489781 A1 EP0489781 A1 EP 0489781A1 EP 90912729 A EP90912729 A EP 90912729A EP 90912729 A EP90912729 A EP 90912729A EP 0489781 A1 EP0489781 A1 EP 0489781A1
Authority
EP
European Patent Office
Prior art keywords
ether
oxygen
oxidation
reactor
alkali metal
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Withdrawn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
EP90912729A
Other languages
German (de)
English (en)
Inventor
Wolf-Eckart Noack
Gerd GÖBEL
Holger Tesmann
Franz-Josef Carduck
Harald Liebs
Willi WÜST
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0489781A1 publication Critical patent/EP0489781A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part

Definitions

  • the invention relates to a process for the preparation of alkali metal salts of ether carboxylic acids of the general formula I.
  • R is an alkyl group with 1 to 22 carbon atoms, an aryl group or an aralkyl group,
  • n 2 and / or 3
  • n is a number in the range from 0 to 20 and
  • M is an alkali metal from the group formed by lithium, sodium and potassium
  • Alkali salts of ether carboxylic acids are compounds with interesting surface-active properties, which in the form of their aqueous solutions e.g. be used in cosmetic formulations.
  • Aqueous solutions of alkali salts of ether carboxylic acids foam too much when the water is removed by distillation.
  • the cost-effectiveness of the process is greatly reduced by the energy required for the separation of water by distillation.
  • the invention is directed to a process for the preparation of alkali salts of ether carboxylic acids of the type mentioned in the introduction, in which the above-mentioned disadvantages with regard to the increase in viscosity and the foaming of the reaction mixture are avoided and highly concentrated aqueous solutions of alkali salts of ether carboxylic acids, e.g. can be obtained with a concentration of 20 to 50 wt .-%, based on the total weight of the solution.
  • an aqueous Solution of alkali metal hydroxide solution in a thin layer on a solid support or in the form of fine particles or droplets in contact with oxygen or the gases containing oxygen as a continuous phase, the concentration of the ether alcohols in the aqueous phase in the range from at least 0.1, in particular from 0.5 to 15 wt .-%, based on the total weight of the aqueous phase. Below the specified range, the reaction rate is generally too slow, so that this range should only be undercut at the end of the reaction after the ether alcohol supply has ended.
  • the process of the invention can be used to prepare alkali metal salts of ether carboxylic acids of the general formula (I) in which the group R can be a straight-chain or branched alkyl group having 1 to 22 carbon atoms; typical examples of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and docosyl.
  • the group R can be a straight-chain or branched alkyl group having 1 to 22 carbon atoms
  • typical examples of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecy
  • the method of the invention is particularly suitable for the production of alkali salts of ether carboxylic acids, the remainder of which R is derived from C 2 -C 8 fatty alcohols or technical mixtures thereof, obtainable from animal and / or vegetable fats and oils.
  • the group R can also be an aryl radical be, for example a phenyl group, or an aralkyl radical, for example a phenylalkylene group having 1 to 3 carbon atoms in the alkylene radical.
  • the compound of the general formula II is an adduct of ethylene oxide or ethylene oxide and propylene oxide onto alcohols of the formula ROH, where in the case of the ethylene oxide / propylene oxide adducts of the formula II the propylene glycol residues are randomly distributed in the alkoxylate chain. or block distribution, but there is always an ethylene glycol residue at the end.
  • reaction solution is present in the form of thin layers on a solid support or in the form of fine particles in a continuous phase of gases containing oxygen or oxygen.
  • the oxidation is carried out at temperatures in the range from 40 to 130 ° C., in particular 60 to 85 ° C.
  • the reaction rate is too low below the specified range. You can work above the specified range, but only an insignificant increase in the reaction rate.
  • the oxidation is carried out at an oxygen partial pressure of 0.1 to 5 bar abs. out.
  • the foam formation is suppressed more and more as the system pressure increases and thus the effective gas throughput decreases.
  • the reaction rate may increase with increasing partial pressure of oxygen.
  • the oxidation is carried out with air.
  • Suitable catalysts for use in the process of the invention are the noble metal catalysts known from the prior art mentioned above, in particular based on platinum or palladium.
  • Palladium catalysts have proven particularly suitable for the process of the invention, for example palladium on carbon.
  • the catalyst is preferably introduced into the process in the form of a suspension in the aqueous solution of the ether alcohols.
  • activated carbon, graphite, diatomaceous earth, silica gel, spinels, aluminum oxide or ceramic materials can be used as carrier material.
  • the catalysts can also contain combinations of several noble metals, for example mixtures of Pd and Pt, and further suitable activators such as lead, bismuth or cadmium in the form of their metals or their compounds, including combinations thereof.
  • suitable catalysts are in the literature mentioned at the outset and in US Pat. No. 4,607,121.
  • the catalyst in suspension form is used in a concentration of 0.2 to 3% by weight, based on the total weight of the suspension containing the ether alcohols and water.
  • the process of the invention is carried out at pH values of at least 8. PH values of at least 9, in particular in the range from 9 to 11, are particularly advantageous.
  • the oxidation of the ether alcohols is carried out in a reactor in which the oxygen or the gases containing oxygen and the ether phase, alkali metal hydroxide solution and, if appropriate, the aqueous phase containing the catalyst are added to the upper part of the reactor, the ether carboxylic acid salt, unreacted ether alcohol and, if appropriate, the reaction mixture containing the catalyst are removed at the lower part of the reactor and the reaction mixture is recycled to the upper part of the reactor for the further oxidation of unreacted ether alcohol.
  • reaction mixture withdrawn from the lower part of the reactor is continuously subjected to alkali metal hydroxide to maintain the pH of at least 9, in particular 9 to 11, and ether alcohol to maintain the ether alcohol concentration before being returned to the upper part of at least 0.1, in particular from 0.5 to 15% by weight in the reaction mixture.
  • packed columns of conventional design such as are used, for example, in Ullmann, Encyclopedia of Industrial Chemistry, 4th Edition, Volume 3, pp. 390 to 392 (1973), Verlag Chemie, Weinheim, are described as direct current packed columns.
  • the packing to be used in the packed columns expediently have a large intermediate volume so that the gas velocity and the rate of foam formation do not become too high.
  • suitable fillers are known from Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 2, page 529 (1972) and 5th edition, volume B3, pages 4-82 to 4-83 (1988); the use of Pall rings, Novalox saddles, Berl saddles, Intralox saddles and Interpack bodies is particularly preferred.
  • Ordered packs as described in Volume 2 of the 4th edition of the aforementioned encyclopedia, pages 533-534, can also be used, e.g. of the Sulzer packing type.
  • catalyst beds or fixed catalyst beds instead of a packed bed. Ordered catalyst packs, e.g. in honeycomb form, can be used.
  • the reaction mixture withdrawn at the lower end of the column, after adjustment of the pH and the ether alcohol concentration, is returned to the upper part of the column for renewed reaction until the ether carboxylic acid salt has a concentration of 20 to 50% by weight .-%, based on the total weight of the solution, and the metered ether alcohol is converted.
  • the system comprises a packed column 1, which is provided at its upper end with a supply line for oxygen or gases containing oxygen, in particular air.
  • a line 3 is used to supply the water / ether alcohol mixture which may contain the suspended catalyst.
  • a line 4 for removing the oxidized reaction mixture is arranged at the lower end of the packed column; the reaction mixture can be returned to the top of the packed column via a circulation pump 5, a valve 6 which is open during the reaction and is only closed in the filtration discussed below, and a heat exchanger 7 and via line 3.
  • Aqueous sodium hydroxide solution is supplied via a line 8 and a metering pump 9, that of the ether alcohol to be oxidized via a line 10 and a metering pump 11.
  • the exhaust air flowing from the packed column 1 is removed laterally via a line 12 and fed to an exhaust gas heater 13.
  • the foam that arises, for example, when the system is operated incorrectly and carried along with the exhaust air can be destroyed and returned to the reactor as a liquid via a line 14.
  • the air freed from the foam is fed to a cooler 16 via a line 15 and removed from the system via a valve 17 and a line 18; Any liquid droplets that are entrained or condensate are also returned to the reactor via a line 19.
  • the aqueous suspension containing the end product is removed via a line 20 and a valve 21 and fed to a filter system 22, where the separation between the aqueous solution of the process products and the suspended catalyst takes place, which are carried away via lines 23 and 24, respectively.
  • the catalyst is placed in a line 4, which is not shown.
  • the system shown in Fig. 1 is operated as follows:
  • the suspension of the powdered noble metal catalyst in water is recirculated from the bottom of the reactor to the top thereof by means of the circulation pump 5.
  • a small amount of ether alcohol and sodium hydroxide solution in the form of an aqueous solution is metered into the circuit suspension by means of the metering pumps 9, 10.
  • the nitrogen is then displaced by oxygen or a gas containing oxygen, and immediately after the desired pressure has been reached, the gas throughput required for the oxidation and the addition of sodium hydroxide solution and alcohol are adjusted via the metering pumps 9 and 11.
  • Alcohol and aqueous sodium hydroxide solution are continuously metered in during the reaction, which can be recognized by an oxygen uptake.
  • the metering rate is adjusted or varied and adapted to the reaction rate so that a low amount of unreacted ether alcohol and thus a low viscosity is ensured in the solution during the entire course of the reaction.
  • the gas supply is interrupted and the catalyst is separated from the solution by filtration.
  • a conventional packed column with an inner diameter of 50 mm and a height was used for this exemplary embodiment the packing of 1000 mm used; the column was filled with Interpack 15/40. loaded.
  • the starting material was a commercially available fatty alcohol ethoxylate (adduct of approx. 4 mol of ethylene oxide with a technical fatty alcohol of chain length C 2 -C 4, molecular weight: 369).
  • a palladium catalyst with 5% Pd on carbon was used as the catalyst, which had been reduced in the form of an aqueous suspension with hydrogen before use.
  • the plant was initially charged with a suspension of, based on dry matter, 35 g of catalyst in 2400 g of demineralized water.
  • 30 g of ether alcohol (approx. 1.2% by weight) and 3.3 g of NaOH (as 25% sodium hydroxide solution) were metered into the system.
  • the respective free ether alcohol content was calculated from the amount of oxygen absorbed by the reaction solution up to that point and the amount of ether alcohol dosed up to that point.
  • total amount of ether alcohol metered 720 g (1.95 gmol) total amount of NaOH added (as 100% NaOH): 78.0 g (1.95 gmol)
  • Average or maximum content of unreacted ether alcohol 3 or 4% by weight
  • Example 2 Analogously to the process of Example 1, an addition product of an average of 5 moles of ethylene oxide was oxidized to 1 mole of the technical fatty alcohol of the chain length C 1 -C 4 described in Example 1. After a reaction time of 6.7 hours, a 23.5% solution of the sodium salt of the corresponding ether carboxylic acid was obtained in a conversion of approximately 97%, calculated from the oxygen consumption. In the same way, an adduct of an average of 9 moles of ethylene oxide and 1 mole of a technical fatty alcohol of chain length C 2 -C 8 was oxidized. After a response time of 6.2 For hours, a 19.5% solution of the sodium salt of the corresponding ether carboxylic acid was obtained with a conversion of approx. 105% calculated from the oxygen consumption.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Un procédé permet d'obtenir des sels alcalins des acides carboxyliques d'éther par oxydation d'alcools d'éther dans une phase aqueuse avec de l'oxygène ou des gaz contenant de l'oxygène à des températures élevées, en présence d'hydroxydes de métaux alcalins et de catalyseurs en métaux précieux. A cet effet, on met en contact une couche mince d'une solution aqueuse des alcools d'éther contenant une lessive alcaline, appliquée sur un substrat solide ou sous forme de fines particules, avec de l'oxygène ou avec les gaz qui contiennent de l'oxygène sous forme d'une phase continue. La concentration d'alcools d'éther dans la phase aqueuse est comprise entre 0,1 et 15 % en poids du poids total de la phase aqueuse. Ce procédé permet d'obtenir des concentrations élevées de solutions aqueuses des sels alcalins des acides carboxyliques d'éther.
EP90912729A 1989-09-01 1990-08-23 Procede de production de sels alcalins d'acides carboxyliques d'ether Withdrawn EP0489781A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3929063 1989-09-01
DE3929063A DE3929063A1 (de) 1989-09-01 1989-09-01 Verfahren zur herstellung von alkalisalzen von ethercarbonsaeuren

Publications (1)

Publication Number Publication Date
EP0489781A1 true EP0489781A1 (fr) 1992-06-17

Family

ID=6388431

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90912729A Withdrawn EP0489781A1 (fr) 1989-09-01 1990-08-23 Procede de production de sels alcalins d'acides carboxyliques d'ether

Country Status (7)

Country Link
EP (1) EP0489781A1 (fr)
JP (1) JPH05503686A (fr)
AU (1) AU6288790A (fr)
CA (1) CA2066452A1 (fr)
DE (1) DE3929063A1 (fr)
WO (1) WO1991003454A1 (fr)
ZA (1) ZA906979B (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5463114A (en) * 1994-04-13 1995-10-31 Henkel Kommanditgesellschaft Auf Aktien Process for the production of ether carboxylic acids and salts thereof
DE10117222B4 (de) 2001-04-06 2004-12-30 Goldschmidt Ag Verfahren zur Herstellung von Glycinderivaten
JP5511369B2 (ja) 2009-12-28 2014-06-04 花王株式会社 カルボン酸の製造方法
JP5520089B2 (ja) * 2010-03-10 2014-06-11 花王株式会社 エーテルカルボキシレートの製造方法
JP5520088B2 (ja) * 2010-03-10 2014-06-11 花王株式会社 エーテルカルボキシレートの製造方法
JP2013067565A (ja) * 2011-09-20 2013-04-18 Kao Corp カルボン酸塩の製造方法
JP5985965B2 (ja) * 2011-12-28 2016-09-06 花王株式会社 ポリオキシアルキレンアルキルエーテルカルボン酸又はその塩の製造方法
CN115894208A (zh) * 2022-12-09 2023-04-04 万华化学集团股份有限公司 一种醇醚羧酸盐的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2936123C2 (de) * 1979-09-07 1987-04-09 Hoechst Ag, 6230 Frankfurt Verfahren zur Herstellung von Alkoxyessigsäuren
US4348509A (en) * 1981-07-06 1982-09-07 Shell Oil Company Alkoxyalkanoic acid preparation
DE3135946A1 (de) * 1981-09-10 1983-03-24 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von alkoxyessigsaeuren
IT1175314B (it) * 1983-12-28 1987-07-01 Anic Spa Procedimento per la preparazione di sali di metallo alcalino di acidi polietossicarbossilici
DE3728222A1 (de) * 1987-08-24 1989-03-09 Henkel Kgaa Verfahren zur herstellung von ethercarbonsaeuren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9103454A1 *

Also Published As

Publication number Publication date
CA2066452A1 (fr) 1991-03-02
JPH05503686A (ja) 1993-06-17
AU6288790A (en) 1991-04-08
WO1991003454A1 (fr) 1991-03-21
DE3929063A1 (de) 1991-03-07
ZA906979B (en) 1991-06-26

Similar Documents

Publication Publication Date Title
DE1643255A1 (de) Verfahren zur Herstellung von p-Aminophenol
DE3137828A1 (de) Kontinuierliche verfahren und katalytische zusammensetzung zur entfernung von schwefelwasserstoffgas aus einem fluidstrom
DE3017518C2 (de) Verfahren zur Herstellung von N-Phosphonomethyl-Glycin
EP0413215B1 (fr) Procédé de préparation de carbonates de dialkyle
EP0304763A1 (fr) Procédé de préparation d'acides éthercarboxyliques
EP0489781A1 (fr) Procede de production de sels alcalins d'acides carboxyliques d'ether
EP0947493B1 (fr) Procédé pour l'hydrogénation sélective en phase liquide de composés carbonyles alpha,bèta-insaturés
DE2053115C3 (de) Verfahren zur kontinuierlichen Durchführung heterogener katalytischer Reaktionen in flüssiger Phase im Fließbett
EP0555697A1 (fr) Procédé de préparation de carbonates de dialkyle
US5292940A (en) Process for the preparation of alkali metal salts of ether-carboxylic acids
EP0208987B1 (fr) Procédé de fabrication de catalyseurs et leur utilisation pour des réactions d'hydrogénation et d'amination
EP0596483B1 (fr) Procédé de fabrication du formiate de méthyle
WO1995028375A1 (fr) Procede de preparation d'acides ether carboxyliques et de leurs sels
DE2901912C2 (fr)
EP1697292A1 (fr) Procede pour produire de la tetrahydrogeranylacetone
DE1065846B (de) Verfahren zur Herstellung von Carbonsäuren durch Oxydation von Aldehyden mit molekularem Sauerstoff
DE1468584A1 (de) Verfahren zur Oxydation von alkylsubstituierten aromatischen Verbindungen in fluessiger Phase
CH412871A (de) Verfahren zur Herstellung von Cyclohexancarbonsäure
DE1107212B (de) Verfahren zur Herstellung von Aldehyden durch die Oxo-Synthese
DE1268138B (de) Verfahren zur Herstellung von Allylacetat
DE977576C (de) Verfahren zur Wiedergewinnung von Kobaltkatalysatoren
DE1643255C (de) Verfahren zur Herstellung von p Aminophenol
DE1583911A1 (de) Verfahren zur Wiedergewinnung von Nickel und/oder Kobalt aus ausgebrauchten Katalystormassen
AT93481B (de) Verfahren zur Herstellung einer Kontaktmasse unter Verwendung von Metallsalzen flüchtiger organischer Säuren.
DE1593673A1 (de) Verfahren zur Herstellung von Propionitril

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19920220

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19940718

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19950607