EP0521852A1 - Procede de production d'acides sulfoniques d'alcane infrieurs a partir de leurs sels alcalins - Google Patents

Procede de production d'acides sulfoniques d'alcane infrieurs a partir de leurs sels alcalins

Info

Publication number
EP0521852A1
EP0521852A1 EP19900909660 EP90909660A EP0521852A1 EP 0521852 A1 EP0521852 A1 EP 0521852A1 EP 19900909660 EP19900909660 EP 19900909660 EP 90909660 A EP90909660 A EP 90909660A EP 0521852 A1 EP0521852 A1 EP 0521852A1
Authority
EP
European Patent Office
Prior art keywords
hcl
chloride
distillation
water
alkanesulfonic
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Withdrawn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
EP19900909660
Other languages
German (de)
English (en)
Inventor
Willi Dr. Wüst
Christoph Dr. Lohr
Rainer Dr. Eskuchen
Hasso Leischner
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 EP0521852A1 publication Critical patent/EP0521852A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification

Definitions

  • the invention relates to an improved method for producing lower purity alkanesulfonic acids from their alkali salts.
  • essentially chloride-free acids of the type mentioned can be produced, although the inexpensive hydrogen chloride is used to release the alkanesulfonic acid from its alkali salt.
  • Short-chain 1-sulfonic acids in particular C1- to C4-sulfonic acids, have been proposed for industrial cleaning as a substitute for phosphoric acid and / or nitric acid in cleaning agents which are in particular phosphate-free.
  • suitable sulfonic acid qualities for realistic purposes are not available in large quantities in realistic prices. Only acids that are practically free of chloride ions can be used in industrial cleaning agents. Their extraction is only possible with such a considerable effort according to previous processes that representatives of the lower alkanesulfonic acids, for example methanesulfonic acid, which are particularly interesting per se, can only be bought as an expensive special chemical.
  • Short-chain acids of this type can be prepared by oxidation of the corresponding mercaptans with nitric acid or peracids and iodine in the presence of bromide ions in dimethyl sulfoxide. This procedure however, only give moderate yields. In addition, mercaptans are too expensive for large-scale processes.
  • Short-chain alkanesulfonic acids can also be prepared from alkanes by sulfochlorination with subsequent saponification of the alkanesulfonyl chloride or by sulfoxidation. However, the sulfonation takes place on the hydrocarbon chain in a statistical distribution and, if appropriate, also several times, so that the selective production of 1-sulfonic acids is not possible.
  • reaction of olefins with sodium bisulfite and subsequent release of the alkanesulfonic acids are also undesirable by-products.
  • the present invention is based on the surprising finding that working in alcoholic liquid phases in the sense of the teaching of the last-mentioned earlier application for releasing the alkanesulfonic acid from its alkali salts is dispensed with, and the alcoholic liquid phase can thus be replaced by an aqueous reaction phase. if one works under the process conditions described below, determined and selected.
  • the invention accordingly relates to a process for the preparation of lower alkanesulfonic acids from their alkali salts by reacting them with hydrogen chloride and separating the reaction mixture, the new process being characterized in that the alkali metal salts thereof are desired in order to obtain an alkanesulfonic acid which is virtually free of chloride ions If necessary in admixture with alkali chloride, in the form of a concentrated aqueous salt slurry with a multiple molar excess of hydrogen chloride, based on alkanesulfonic acid, which separates the solid phase now present, the excess hydrogen chloride from the isolated liquid phase, if desired together with a portion withdrawing the water by distillation and the practically chloride-free alkanesulfonic acid together with the residual water as the bottom phase of the distillation.
  • the essence of the action according to the invention is the surprising finding that by using a considerable excess of HCl in the conversion of the alkali metal salt of the alkanesulfonic acids present in aqueous solution or slurry with the liberation of the free acid and simultaneous formation of the alkali metal chloride, the solubility of the alkali metal chloride can be reduced so much in the concentrated aqueous phase. - 4 -
  • the process is particularly suitable for the production of C1- to C6-alkanesulfonic acids and is of particular importance for compounds of this type with 1 to 4 carbon atoms.
  • methanesulfonic acid can easily be obtained from its alkali salts by the new process.
  • the preferred alkali salts in the context of the reaction described according to the invention are the sodium salts.
  • the decisive working aid by means of which it is possible to work in an aqueous medium in the reaction type described here, is the use of hydrogen chloride in the step of releasing the alkanesulfonic acid in a multiple molar excess.
  • Hydrogen chloride is preferably used in at least about 3 molar amounts based on the alkali salt of alkanesulfonic acid present. This HCI excess is unproblematic for the overall balance of the process, because the portions of the hydrogen chloride which are not required for salt formation can be returned to the next process stage in the circuit.
  • HCl amounts of at most about 5 mol - based on the alkali salt of alkanesulfonic acid - are used. A range of approximately 3.2 to 4 mol of HCl has proven to be particularly suitable. - 5 -
  • a slurry of alkali metal chloride, in particular sodium chloride is formed in a liquid phase which contains the free alkane sulfonic acid dissolved together with HCl.
  • the solubility of the sodium chloride in this liquid is negligible due to excess HCI.
  • the sodium chloride present as a solid is separated from the liquid phase in a suitable manner, for example by filtration or centrifugation. This separation can be carried out at normal temperature or at best moderately elevated temperatures, for example in the temperature range up to about 60 ° C. Often at the time of
  • the subsequent separation of the liquid phase obtained can be carried out by distillation, in particular in a multi-stage form.
  • a two-stage separation by distillation is carried out in such a way that the hydrogen chloride is first driven off and returned to the main process.
  • An HCl / water mixture can then be separated off in the final stage of this separation of the liquid phase.
  • the process is preferably carried out in a weak vacuum, so that temperatures below 100 ° C. can be maintained, in particular temperatures of the liquid phase in the range from approximately 80 to 90 ° C. may be suitable.
  • This HCl / water azeotrope which is separated off in the second process stage, can also be returned to the main reaction, in which case only the amount of water circulated should be taken into account.
  • the free alkanesulfonic acid As a light-colored, chloride-free reaction product.
  • the water balance of the overall process is regulated in such a way that the free alkanesulfonic acid obtained here also has a low residual water content of at least about 1 to a maximum of about 30% by weight and preferably of about 10 to 20% by weight .
  • the highly concentrated alkanesulfonic acids obtained in this way can, if desired after being diluted with further water, be used for the particular purpose.
  • the chloride content of the alkanesulfonic acids is in the acceptable trace range. For example, it is easily possible to obtain methanesulfonic acid from its sodium salt with chloride contents well below 500 ppm in the described way.
  • a salt mixture consisting of 145 g of sodium methanesulfonate, 144 g of NaCl and water were used, which originated from the reaction of methyl chloride with aqueous sulfite solution and subsequent concentration on a rotary evaporator.
  • the salt mixture was dissolved in 450 g of fuming hydrochloric acid (37%) and the precipitated NaCl was filtered off.

Landscapes

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

Abstract

Selon un procédé de production d'acides sulfoniques d'alcane inférieurs à partir de leurs sels alcalins, on fait réagir ceux-ci avec du HCl et on sépare le mélange de réaction. Selon ce nouveau procédé, on mélange les sels alcalins des acides sulfoniques d'alcane, le cas échéant mélangés avec du chlorure alcalin, qui se présentent sous forme d'une boue saline aqueuse concentrée, avec un excédent molaire de HCl plusieurs fois supérieur à la quantité d'acide sulfonique d'alcane, puis on sépare la phase solide ainsi obtenue, on élimine par distillation l'excédent d'HCl contenu dans la phase liquide isolée, le cas échéant avec une partie de l'eau, et on récupère les acides sulfoniques d'alcane pratiquement dépourvus de chlorure avec l'eau résiduelle dans la phase résiduelle de la distillation. Ce procédé permet ainsi d'obtenir des acides sulfoniques d'alcane pratiquement dépourvus d'ions de chlorure.
EP19900909660 1989-06-28 1990-06-19 Procede de production d'acides sulfoniques d'alcane infrieurs a partir de leurs sels alcalins Withdrawn EP0521852A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3921130 1989-06-28
DE19893921130 DE3921130A1 (de) 1989-06-28 1989-06-28 Verfahren zur herstellung von niederen alkansulfonsaeuren aus ihren alkalisalzen

Publications (1)

Publication Number Publication Date
EP0521852A1 true EP0521852A1 (fr) 1993-01-13

Family

ID=6383747

Family Applications (2)

Application Number Title Priority Date Filing Date
EP90111508A Withdrawn EP0405289A1 (fr) 1989-06-28 1990-06-19 Procédé pour la préparation d'acides alcanesulfoniques à partir de leurs sels alcalins
EP19900909660 Withdrawn EP0521852A1 (fr) 1989-06-28 1990-06-19 Procede de production d'acides sulfoniques d'alcane infrieurs a partir de leurs sels alcalins

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP90111508A Withdrawn EP0405289A1 (fr) 1989-06-28 1990-06-19 Procédé pour la préparation d'acides alcanesulfoniques à partir de leurs sels alcalins

Country Status (4)

Country Link
EP (2) EP0405289A1 (fr)
JP (1) JPH04506520A (fr)
DE (1) DE3921130A1 (fr)
WO (1) WO1991000269A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2018005878A (es) * 2015-11-10 2018-08-15 Basf Se Metodo para la purificacion de acidos alcanosulfonicos.
CN112079750A (zh) * 2019-06-12 2020-12-15 联化科技(盐城)有限公司 一种甲基磺酸的制备方法
WO2021023582A1 (fr) 2019-08-07 2021-02-11 Basf Se Récupération d'acide méthane sulfonique anhydre à partir de l'effluent de fond d'une colonne de distillation

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3480636A (en) * 1966-09-29 1969-11-25 Smithkline Corp Process for preparing alpha-nitrosulfonic acids
DE3812846A1 (de) * 1988-04-18 1989-11-02 Henkel Kgaa Verfahren zur herstellung von c(pfeil abwaerts)1(pfeil abwaerts)-c(pfeil abwaerts)6(pfeil abwaerts)-alkansulfonsaeuren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9100269A1 *

Also Published As

Publication number Publication date
EP0405289A1 (fr) 1991-01-02
WO1991000269A1 (fr) 1991-01-10
JPH04506520A (ja) 1992-11-12
DE3921130A1 (de) 1991-01-10

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