EP0230530A2 - Procédé pour la séparation et la purification de polyglycérines ou de résidus contenant des polyglycérines - Google Patents

Procédé pour la séparation et la purification de polyglycérines ou de résidus contenant des polyglycérines Download PDF

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Publication number
EP0230530A2
EP0230530A2 EP86114849A EP86114849A EP0230530A2 EP 0230530 A2 EP0230530 A2 EP 0230530A2 EP 86114849 A EP86114849 A EP 86114849A EP 86114849 A EP86114849 A EP 86114849A EP 0230530 A2 EP0230530 A2 EP 0230530A2
Authority
EP
European Patent Office
Prior art keywords
polyglycerol
polyglycerols
dimethoxypropane
ketals
distillation
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.)
Granted
Application number
EP86114849A
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German (de)
English (en)
Other versions
EP0230530A3 (en
EP0230530B1 (fr
Inventor
Gerald Dr. Dipl.-Chem. Jakobson
Werner Dr. Dipl.-Chem. Siemanowski
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.)
Cavity GmbH
Original Assignee
Deutsche Solvay Werke 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 Deutsche Solvay Werke GmbH filed Critical Deutsche Solvay Werke GmbH
Priority to AT86114849T priority Critical patent/ATE60795T1/de
Publication of EP0230530A2 publication Critical patent/EP0230530A2/fr
Publication of EP0230530A3 publication Critical patent/EP0230530A3/de
Application granted granted Critical
Publication of EP0230530B1 publication Critical patent/EP0230530B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D19/00—Recovery of glycerol from a saponification liquor

Definitions

  • the present invention relates to a process for the separation and purification of polygycerols or polyglycerol-containing residues.
  • DE-OS 21 33 281 is a method for the production of pure polyglycerols by purifying a crude polyglycerol product, obtained by reacting glycerol at high temperature in the presence of an alkaline catalyst, by preparing a slurry of a filter aid and an aqueous solution of the crude polyglycerol, separating the solid and liquid phase of the slurry and the liquid phase passes successively through an anion and cation exchange resin.
  • such cleaning leads to difficulties in operation due to constipation and still does not lead to a simultaneous separation of the individual polyglycerols.
  • the object of the present invention was therefore to avoid these disadvantages and to provide a process for the separation and purification of polyglycerols or polyglycerol-containing residues, with the aid of which the most complete possible purification and separation into the individual polyglycerols can be achieved, which is at the same time environmentally friendly .
  • this object is achieved by reacting the polyglycerols or residues containing polyglycerol in the presence of an acidic catalyst with an acetal or ketal at elevated temperature at atmospheric pressure or reduced pressure to give the corresponding cyclic acetals or ketals, the reaction mixture into the individual cyclic acetals or Separates ketals by distillation and splits the individual components into the corresponding pure polyglycerols in the presence of an acid catalyst or acid cation exchanger.
  • the reaction of the polyglycerols or polyglycerol residues in the presence of the acid catalyst is reacted directly with a ketal or acetal, preferably a Dialkoxypropan conducted to de I corresponding cyclic ketals or acetals, wherein no water, but an alcohol is formed, which at the reaction is continuously distilled off as an azeotrope with excess acetal or ketal.
  • a ketal or acetal preferably a Dialkoxypropan conducted to de I corresponding cyclic ketals or acetals, wherein no water, but an alcohol is formed, which at the reaction is continuously distilled off as an azeotrope with excess acetal or ketal.
  • the weight ratio of the polyglycerols or polyglycerol-containing residues (total weight) to the acetal to be used is 1: 1.5 to 1: 4, preferably 1: 1.7 to 1: 2.5 and the reaction takes place at temperatures of 20-90 ° C. preferably 50-70 ° C. At temperatures of 20 - 70 ° C the reaction takes place under negative pressure, from 70 - 90 ° C under normal pressure.
  • the acidic catalysts used in the formation of the cyclic acetals or ketals are inorganic acids
  • .Lissis acids higher-boiling organic acids or sulfonic acids, preferably perchloric acid, in amounts of 0.005 to 1 wt .-%, preferably 0.05 to 0.5 wt .-%, based on polyglycerol or polyglycerol-containing residue.
  • the sulfonic acids include p-Toluenesulfonic acid, benzenesulfonic acid, ethanesulfonic acid and methanesulfonic acid are suitable.
  • reaction of the polyglycerols or polyglycerol-containing residues with the acetal or ketal takes place without an additional solvent. According to one embodiment, the reaction takes place with temporary replacement of the excess acetal or ketal by an inert polar solvent.
  • inert polar solvents u. a. Dioxzi, dimethylformamide, dimethyl sulfoxide or dimethoxyethane, preferably dimethylformamide used.
  • the process according to the invention can advantageously be carried out if 2,2-dimethoxypropane is used as the ketal.
  • the reaction with polyglycerol or polglycerin-containing residue produces methanol, which is particularly easily removed from the cycli during the reaction as an azeotrope with 2,2-dimethoxypropane see ketals can be distilled off.
  • the acidic reaction solution was neutralized with solid sodium carbonate, clarified by filtration and the remaining azeotrope and excess 2,2-dimethoxypropane evaporated in vacuo.
  • the residue obtained which mainly consists of the mixture of the diisopropylidene derivatives of the three polyglycerols, was obtained by fractional distillation under a pressure of 0.5 mbar into the three components diisopropylidene diglycerol (0.540 kg ⁇ 97% of theory), diisopropylidene triglycerol (0.417 kg ⁇ 91% of theory) and diisopropylidene tetraglycerol (0.230 kg ⁇ 93% of theory) and a residue separated.
  • the process according to the invention can be carried out particularly advantageously as a cycle process, as will be explained in the following example.
  • the resulting polyglycerols or residues containing polyglycerol in the synthetic glycerol production are treated with 2.2 in the presence of an acidic catalyst (p-toluenesulfonic acid, 0.2% by weight) at elevated temperature and negative pressure (50-70 ° C., 300-700 mbar) -Dimethoxypropan (ratio: 1.7 kg per kg polyglycerol) implemented and the resulting alcohol (methanol) during the reaction as an azeotrope with over removed 2,2-dimethoxypropane and possibly used inert polar solvent by distillation.
  • an acidic catalyst p-toluenesulfonic acid, 0.2% by weight
  • negative pressure 50-70 ° C., 300-700 mbar
  • methanol methanol
  • reaction mixture obtained is separated by distillation into the individual cyclic ketals and the individual components of the cyclic ketals in the presence of an acidic cation exchanger, e.g. B. on the basis of a sulfonated styrene-divinylbenzene copolymer, split in the aqueous ' medium into the corresponding pure polyglycerols such as diglycerol, triglycerol, tetraglycerol or pentaglycerol and acetone.
  • an acidic cation exchanger e.g. B. on the basis of a sulfonated styrene-divinylbenzene copolymer, split in the aqueous ' medium into the corresponding pure polyglycerols such as diglycerol, triglycerol, tetraglycerol or pentaglycerol and acetone.
  • the azeotrope of methanol and 2,2-dimethoxypropane is separated by treatment with alkali and distillation in 2,2-dimethoxypropane and methanol and both acetone and methanol - with the known formation of 2,2-dimethoxypropane in an acidic cation exchanger - and the recovered 2,2-dimethoxypropane are returned to the process.
  • the azeotrope (bp approx. 61 - 62 ° C) consisting of methanol and unreacted ketal (2,2-dimethoxypropane) can easily be removed from the reaction mixture.
  • the azeotrope is broken down into its constituents (ketal and methanol) by treatment with about 15% NaOH sets, whereby methanol passes into the aqueous phase and the 2,2-dimethoxypropane forms an independent phase.
  • the alcohol can be recovered by distillation from the sodium hydroxide solution, the sodium hydroxide solution being used again.
  • the azeotrope can also be broken down into the two components by direct feeding into a distillation column.
  • the acid-catalyzed cleavage of the cyclic ketals produces, in addition to the pure polyglycerols, acetone, which, together with the recovered methanol, is converted to 2,2-dimethoxypropane in a known manner in an acidic cation exchanger, which is reacted again with the polyglycerol or with the polyglycerol-containing residue becomes.
  • the cyclic ketals obtained in almost quantitative yield as intermediates in the purification of the polyglycerols or polyglycerol-containing residues with the aid of the 2,2-dimethoxypropane preferably used as ketal in the process according to the invention are:
  • the corresponding polyglycerols diglycerol, triglycerol, tetraglycerol and pentaglycerol can be obtained from these cyclic ketals in high yield and in high purity by acidic cleavage.
  • the process according to the invention is thus characterized by an almost complete conversion of the polyglycerols into their cyclic acetals or ketals or diisopropylidene derivatives, easy separation by distillation thereof and virtually loss-free recovery of the pure polyglycerols. This process also eliminates environmental pollution from salt loads.
  • cycle method according to the invention also represents an environmentally friendly reaction sequence in that the by-products methanol and acetone are returned to the process.
  • diisopropylidene derivatives obtained in high yield and in pure form by the process according to the invention are outstandingly suitable as building blocks in further syntheses, since the reduced OH functionality leads to products with a defined structure and composition.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Detergent Compositions (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
EP86114849A 1986-01-09 1986-10-25 Procédé pour la séparation et la purification de polyglycérines ou de résidus contenant des polyglycérines Expired - Lifetime EP0230530B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86114849T ATE60795T1 (de) 1986-01-09 1986-10-25 Verfahren zur trennung und reinigung von polyglycerinen oder polyglycerinhaltigen rueckstaenden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3600388 1986-01-09
DE19863600388 DE3600388A1 (de) 1986-01-09 1986-01-09 Verfahren zur trennung und reinigung von polyglycerinen oder polyglycerinhaltigen rueckstaenden

Publications (3)

Publication Number Publication Date
EP0230530A2 true EP0230530A2 (fr) 1987-08-05
EP0230530A3 EP0230530A3 (en) 1989-05-03
EP0230530B1 EP0230530B1 (fr) 1991-02-06

Family

ID=6291548

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86114849A Expired - Lifetime EP0230530B1 (fr) 1986-01-09 1986-10-25 Procédé pour la séparation et la purification de polyglycérines ou de résidus contenant des polyglycérines

Country Status (5)

Country Link
EP (1) EP0230530B1 (fr)
AT (1) ATE60795T1 (fr)
DE (2) DE3600388A1 (fr)
ES (1) ES2020180B3 (fr)
GR (1) GR3001440T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU623419B2 (en) * 1988-07-25 1992-05-14 Siegfried Peter Process for the recovery of monoglycerides and diglycerides from a mixture containing mono-,di-and triglycerides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19608367A1 (de) 1996-03-05 1997-09-11 Witco Surfactants Gmbh Polyglycerinestersulfosuccinate, Verfahren zu ihrer Herstellung und ihre Verwendung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4360407A (en) * 1982-03-22 1982-11-23 The Dow Chemical Company Process for removing glycerine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU623419B2 (en) * 1988-07-25 1992-05-14 Siegfried Peter Process for the recovery of monoglycerides and diglycerides from a mixture containing mono-,di-and triglycerides

Also Published As

Publication number Publication date
EP0230530A3 (en) 1989-05-03
ES2020180B3 (es) 1991-08-01
EP0230530B1 (fr) 1991-02-06
ATE60795T1 (de) 1991-02-15
GR3001440T3 (en) 1992-09-25
DE3677493D1 (de) 1991-03-14
DE3600388A1 (de) 1987-07-16

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