DE1041488B - Process for the production of oxido alcohols - Google Patents
Process for the production of oxido alcoholsInfo
- Publication number
- DE1041488B DE1041488B DEC9063A DEC0009063A DE1041488B DE 1041488 B DE1041488 B DE 1041488B DE C9063 A DEC9063 A DE C9063A DE C0009063 A DEC0009063 A DE C0009063A DE 1041488 B DE1041488 B DE 1041488B
- Authority
- DE
- Germany
- Prior art keywords
- oxido
- vapors
- solution
- alcohols
- production
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Oxidoalkoholen Bei der Verseifung von Halogenhydrin mit wäßrigen Alkalien entstehen bekanntlich verdünnte Lösungen, die neben der gewünschten Oxidoverbindung Alkalihalogenid enthalten. Die Gewinnung der Oxidoverbindung aus diesen Salzlösungen gestaltet sich besonders dann schwierig, wenn die Oxidoverbindung bei Temperaturen über 100° C siedet oder mit Wasser kein unter 100° C siedendes Azeotrop bildet, da alle Oxidoverbindungen bei höheren Temperaturen leicht hvdratisiert werden. Eine benachbarte funktionelle Gruppe begünstigt diese Ringöffnung besonders. Die angeführten Schwierigkeiten bestehen beispielsweise bei der Aufarbeitung wäßriger Glycidlösungen, wie sie bei der Verseifung von Glycerin-Monochlorhydrin mit verdünnter Natronlauge entstehen. Die Herstellung einer salzfreien Glycidlösung ist unumgänglich, wenn man reines, wasserfreies Glycid erhalten will oder auch die Glycid-Wasser-Lösung unter an sich bekannten Bedingungen zu Glycerin hydratisiert. In jedem Falle stört die Anwesenheit des Salzes bei der Aufarbeitung der wäßrigen Lösung wegen der Bildung von Polyglycerinen und gefärbten Produkten. In diesem Zusammenhang ist bereits vorgeschlagen worden, das Kochsalz durch Zugabe eines geeigneten Lösungsmittels, z. B. Isopropylalköhol, auszufällen, durch Filtration abzutrennen und sodann die zurückbleibende Lösung durch Destillation wieder aufzuarbeiten. Diese Arbeitsweise ist umständlich und erfordert den Einsatz zusätzlicher Chemikalien. Weiter ist ein Verfahren bekanntgeworden, bei dem man im Vakuum in das erwärmte Monochlorhydrin verdünnte Natronlauge eintropfen läßt und das gebildete Glycid in dem Maße abtreibt, in dem es sich bildet. Diese Arbeitsweise hat den Nachteil, daß infolge des hohen Siedepunktes des Glycids verhältnismäßig kleine Mengen mit dem Wasserdampf übergehen, so daß man nur sehr verdünnte Glycid- bzw. Glycerinlösungen erhält.Process for the preparation of oxido alcohols In the saponification of Halohydrin with aqueous alkalis are known to produce dilute solutions which contain alkali halide in addition to the desired oxido compound. The extraction of the Oxido compounds from these salt solutions are particularly difficult if the oxido compound boils at temperatures above 100 ° C or with water none forms an azeotrope boiling below 100 ° C, since all oxido compounds are at higher temperatures can be easily updated. A neighboring functional group favors this Ring opening especially. The difficulties cited exist, for example, in the work-up of aqueous glycide solutions, such as those used in the saponification of glycerol monochlorohydrin with dilute sodium hydroxide solution. The production of a salt-free glycid solution is indispensable if you want to get pure, anhydrous glycid or also the Glycid-water solution hydrated to glycerine under conditions known per se. In any case, the presence of the salt interferes with the work-up of the aqueous Solution because of the formation of polyglycerols and colored products. In this context it has already been suggested to add a suitable solvent to the table salt, z. B. Isopropyl alcohol to precipitate, separate by filtration and then the remaining solution to be worked up again by distillation. This way of working is cumbersome and requires the use of additional chemicals. Next is a Process has become known in which one in a vacuum in the heated monochlorohydrin Lets dilute sodium hydroxide solution drip in and the glycid formed drives off to the extent that in which it is formed. This mode of operation has the disadvantage that as a result of the high The boiling point of the glycide relatively small amounts pass over with the water vapor, so that only very dilute glycid or glycerol solutions are obtained.
Es wurde gefunden, daß man Oxidoalkohole durch Verseifen von entsprechenden Chlorhydrinen vorteilhafter herstellen kann, wenn man Chlorhydrine mit wäßrigem Alkali bei niedrigen Temperaturen teilweise verseift, das erhaltene Reaktionsgemisch im Vakuum bei möglichst kurzer Verweilzeit vollständig unter rascher Abführung der entstandenen Brüden verdampft und dann die Brüden kondensiert. Das ist in keinem Falle mit einer üblichen Blasendestillationsanlage oder einem Umlaufverdampfer möglich, da hier die Verweilzeiten bei der erhöhten Destillationstemperatur zu lang sind und Hydratation bzw. Kondensation eintritt. Es darf jeweils nur so viel Lösung an der Heizfläche der erhöhten Temperatur ausgesetzt werden, daß die flüchtigen Bestandteile spontan verdampfen und in Form der Brüden abgeführt werden können, während gleichzeitig das trockene Alkalihalogenid von der Verdampferoberfläche entfernt wird.It has been found that oxido alcohols can be obtained by saponifying corresponding Chlorohydrins can be produced more advantageously if you combine chlorohydrins with aqueous Alkali partially saponified at low temperatures, the reaction mixture obtained in a vacuum with the shortest possible residence time completely with rapid removal of the evaporated vapors and then condensed the vapors. That is not in any Case possible with a conventional bubble distillation system or a circulation evaporator, because here the residence times at the elevated distillation temperature are too long and hydration or condensation occurs. There can only be so much solution at a time exposed to the heating surface of the elevated temperature that the volatile constituents evaporate spontaneously and can be discharged in the form of vapors while simultaneously the dry alkali halide is removed from the evaporator surface.
Die Art der zur Durchführung des vorliegenden Verfahrens benutzten Verdampfer ist grundsätzlich gleichgültig. Es muß nur dafür gesorgt werden, daß die Verweilzeit der Lösung bei der erhöhten Temperatur möglichst kurz ist. Als besonders geeignet erwiesen sich Dünnschichtverdampfer bekannter Bauart. Man kann auch die kalte Lösung im Vakuum auf eine rotierende Scheibe auftropfen lassen, von der sie gegen die erwärmte Wand des Verdampfergefäßes geschleudert wird, wo Wasser und Glycid verdampfen, während das Alkalihalogenid trocken zu Boden fällt.The type of used to perform this procedure Vaporizer is basically indifferent. It just has to be ensured that the residence time of the solution at the elevated temperature is as short as possible. As special Thin-film evaporators of known design have proven suitable. You can also do that let the cold solution drip onto a rotating disc in a vacuum, from which it is thrown against the heated wall of the evaporator vessel, where water and glycide evaporate as the alkali halide falls dry to the bottom.
Durch Kondensation der Brüden erhält man eine Lösung, die genau so viel Wasser und Oxidoverbindung enthält wie die Ausgangslösung vor dem Abscheiden des Alkalihalogenides. Diese Lösung kann also schon als solche verhältnismäßig hochprozentig sein, insbesondere, wenn die Verseifung des Halogenhydrins bei gewöhnlicher oder nur mäßig erhöhter Temperatur vorgenommen worden ist. Besonders hoch konzentrierte Glycidlösungen werden erhalten, wenn man die abziehenden Brüden einer fraktionierten Kondensation unterwirft. Eine Hydration der Oxidoverbindung tritt bei dem Durchgang durch den Verdampfer nicht ein. Sie wird vorher vermieden, wenn die verseifte Vorratslösung bei niedriger Temperatur, möglichst unter 20° C, gehalten wird.By condensing the vapors, a solution is obtained that is exactly like this contains a lot of water and oxido compound like the starting solution before separation of the alkali halide. This solution can already be relatively high percentage as such be, especially if the saponification of the halohydrin at ordinary or only moderately elevated temperature has been carried out. Particularly highly concentrated Glycide solutions are obtained when the exhausting vapors are fractionated Subjects to condensation. Hydration of the oxido compound occurs with the passage through the vaporizer does not enter. It is avoided beforehand when the saponified stock solution is kept at a low temperature, if possible below 20 ° C.
Beispiel 1 1110 g reines Glycerin-Monochlorhydrin werden unter Rühren mit 2000 g 20o/oiger Natronlauge bei 30° C nicht übersteigenden Temperaturen verseift. Die erhaltene wäßrige Glycid-Kochsalz-Lösung wird in einem Dünnschichtverdampfer kontinuierlich bei 20 bis 30 Torr und 80 bis 90° C verdampft. Man erhält dabei als Destillat 752 g Glycid in etwa 30oloiger wäßriger Lösung und 580 g trockenes -,Tatriumchlorid.Example 1 1110 g of pure glycerol monochlorohydrin are added with stirring saponified with 2000 g of 20% sodium hydroxide solution at temperatures not exceeding 30 ° C. The aqueous glycidic salt solution obtained is evaporated in a thin film evaporator continuously evaporated at 20 to 30 Torr and 80 to 90 ° C. One receives thereby as Distillate 752 g of glycid in an aqueous solution of about 30% and 580 g of dry sodium chloride.
Beispiel 2 125 g 2-Methyl-l-chlorpropandiol-2,3 in 75 g Wasser werden bei 51 C mit 200 g 20oloiger Natronlauge vereift. Die erhaltene Lösung wird durch Auftropfenlassen auf eine rotierende Scheibe bei 2 bis 3 mm Hg gegen die 80 bis 90° C warme Innenwand eines Verdampfungsgefäßes geschleudert. Das Destillat besteht aus 86 g hlethylglycid in wäßriger Lösung. Es verbleibt ein Rückstand von 61 g, der überwiegend aus atriumchlorid besteht.Example 2 125 g of 2-methyl-1-chloropropanediol-2,3 in 75 g of water become frozen at 51 ° C. with 200 g of 20-point sodium hydroxide solution. The resulting solution is through Drip on a rotating disc at 2 to 3 mm Hg against the 80 bis 90 ° C warm inner wall of an evaporation vessel centrifuged. The distillate exists from 86 g of ethyl glycide in aqueous solution. There remains a residue of 61 g, which consists mainly of atrium chloride.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEC9063A DE1041488B (en) | 1954-03-19 | 1954-03-19 | Process for the production of oxido alcohols |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEC9063A DE1041488B (en) | 1954-03-19 | 1954-03-19 | Process for the production of oxido alcohols |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1041488B true DE1041488B (en) | 1958-10-23 |
Family
ID=7014457
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEC9063A Pending DE1041488B (en) | 1954-03-19 | 1954-03-19 | Process for the production of oxido alcohols |
Country Status (1)
Country | Link |
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DE (1) | DE1041488B (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009016149A2 (en) * | 2007-07-30 | 2009-02-05 | Solvay (Société Anonyme) | Process for manufacturing glycidol |
US7557253B2 (en) | 2005-05-20 | 2009-07-07 | Solvay (Societe Anonyme) | Method for converting polyhydroxylated aliphatic hydrocarbons into chlorohydrins |
US7939696B2 (en) | 2005-11-08 | 2011-05-10 | Solvay Societe Anonyme | Process for the manufacture of dichloropropanol by chlorination of glycerol |
US8067645B2 (en) | 2005-05-20 | 2011-11-29 | Solvay (Societe Anonyme) | Process for producing a chlorhydrin from a multihydroxylated aliphatic hydrocarbon and/or ester thereof in the presence of metal salts |
US8124814B2 (en) | 2006-06-14 | 2012-02-28 | Solvay (Societe Anonyme) | Crude glycerol-based product, process for its purification and its use in the manufacture of dichloropropanol |
US8197665B2 (en) | 2007-06-12 | 2012-06-12 | Solvay (Societe Anonyme) | Aqueous composition containing a salt, manufacturing process and use |
US8258350B2 (en) | 2007-03-07 | 2012-09-04 | Solvay (Societe Anonyme) | Process for the manufacture of dichloropropanol |
US8273923B2 (en) | 2007-06-01 | 2012-09-25 | Solvay (Societe Anonyme) | Process for manufacturing a chlorohydrin |
US8314205B2 (en) | 2007-12-17 | 2012-11-20 | Solvay (Societe Anonyme) | Glycerol-based product, process for obtaining same and use thereof in the manufacturing of dichloropropanol |
US8378130B2 (en) | 2007-06-12 | 2013-02-19 | Solvay (Societe Anonyme) | Product containing epichlorohydrin, its preparation and its use in various applications |
US8415509B2 (en) | 2003-11-20 | 2013-04-09 | Solvay (Societe Anonyme) | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
US8471074B2 (en) | 2007-03-14 | 2013-06-25 | Solvay (Societe Anonyme) | Process for the manufacture of dichloropropanol |
US8507643B2 (en) | 2008-04-03 | 2013-08-13 | Solvay S.A. | Composition comprising glycerol, process for obtaining same and use thereof in the manufacture of dichloropropanol |
US8536381B2 (en) | 2008-09-12 | 2013-09-17 | Solvay Sa | Process for purifying hydrogen chloride |
US8715568B2 (en) | 2007-10-02 | 2014-05-06 | Solvay Sa | Use of compositions containing silicon for improving the corrosion resistance of vessels |
US8795536B2 (en) | 2008-01-31 | 2014-08-05 | Solvay (Societe Anonyme) | Process for degrading organic substances in an aqueous composition |
WO2014198243A1 (en) | 2013-06-10 | 2014-12-18 | Spolek Pro Chemickou A Hutni Vyrobu, Akciova Spolecnost | Process for the manufacture of epoxy-monomers and epoxides |
US9309209B2 (en) | 2010-09-30 | 2016-04-12 | Solvay Sa | Derivative of epichlorohydrin of natural origin |
-
1954
- 1954-03-19 DE DEC9063A patent/DE1041488B/en active Pending
Non-Patent Citations (1)
Title |
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None * |
Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8415509B2 (en) | 2003-11-20 | 2013-04-09 | Solvay (Societe Anonyme) | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
US9663427B2 (en) | 2003-11-20 | 2017-05-30 | Solvay (Société Anonyme) | Process for producing epichlorohydrin |
US8344185B2 (en) | 2005-05-20 | 2013-01-01 | SOLVAY (Société Anonyme | Method for making a chlorhydrine by reaction between a polyhydroxylated aliphatic hydrocarbon and a chlorinating agent |
US8067645B2 (en) | 2005-05-20 | 2011-11-29 | Solvay (Societe Anonyme) | Process for producing a chlorhydrin from a multihydroxylated aliphatic hydrocarbon and/or ester thereof in the presence of metal salts |
US7615670B2 (en) | 2005-05-20 | 2009-11-10 | Solvay (Société Anonyme) | Method for making chlorohydrin in liquid phase in the presence of heavy compounds |
US7893193B2 (en) | 2005-05-20 | 2011-02-22 | Solvay (Société Anonyme) | Method for making a chlorohydrin |
US8591766B2 (en) | 2005-05-20 | 2013-11-26 | Solvay (Societe Anonyme) | Continuous process for preparing chlorohydrins |
US7906691B2 (en) | 2005-05-20 | 2011-03-15 | Solvay (Societe Anonyme) | Method for making chlorohydrin in corrosion-resistant equipment |
US8519198B2 (en) | 2005-05-20 | 2013-08-27 | Solvay (Societe Anonyme) | Method for making an epoxide |
US8420871B2 (en) | 2005-05-20 | 2013-04-16 | Solvay (Societe Anonyme) | Process for producing an organic compound |
US8106245B2 (en) | 2005-05-20 | 2012-01-31 | Solvay (Société Anonyme) | Method for preparing chlorohydrin by converting polyhydroxylated aliphatic hydrocarbons |
US8389777B2 (en) | 2005-05-20 | 2013-03-05 | Solvay (Société Anonyme) | Continuous method for making chlorhydrines |
US7557253B2 (en) | 2005-05-20 | 2009-07-07 | Solvay (Societe Anonyme) | Method for converting polyhydroxylated aliphatic hydrocarbons into chlorohydrins |
US8173823B2 (en) | 2005-05-20 | 2012-05-08 | Solvay (Société Anonyme) | Method for making an epoxide |
US7906692B2 (en) | 2005-05-20 | 2011-03-15 | Solvay (Societe Anonyme) | Method for making a chlorohydrin by chlorinating a polyhydroxylated aliphatic hydrocarbon |
US8106246B2 (en) | 2005-11-08 | 2012-01-31 | Solvay (Societe Anonyme) | Process for the manufacture of dichloropropanol by chlorination of glycerol |
US7939696B2 (en) | 2005-11-08 | 2011-05-10 | Solvay Societe Anonyme | Process for the manufacture of dichloropropanol by chlorination of glycerol |
US8124814B2 (en) | 2006-06-14 | 2012-02-28 | Solvay (Societe Anonyme) | Crude glycerol-based product, process for its purification and its use in the manufacture of dichloropropanol |
US8258350B2 (en) | 2007-03-07 | 2012-09-04 | Solvay (Societe Anonyme) | Process for the manufacture of dichloropropanol |
US8471074B2 (en) | 2007-03-14 | 2013-06-25 | Solvay (Societe Anonyme) | Process for the manufacture of dichloropropanol |
US8273923B2 (en) | 2007-06-01 | 2012-09-25 | Solvay (Societe Anonyme) | Process for manufacturing a chlorohydrin |
US8197665B2 (en) | 2007-06-12 | 2012-06-12 | Solvay (Societe Anonyme) | Aqueous composition containing a salt, manufacturing process and use |
US8378130B2 (en) | 2007-06-12 | 2013-02-19 | Solvay (Societe Anonyme) | Product containing epichlorohydrin, its preparation and its use in various applications |
US8399692B2 (en) | 2007-06-12 | 2013-03-19 | Solvay (Societe Anonyme) | Epichlorohydrin, manufacturing process and use |
FR2919609A1 (en) * | 2007-07-30 | 2009-02-06 | Solvay | PROCESS FOR PRODUCING GLYCIDOL |
WO2009016149A3 (en) * | 2007-07-30 | 2009-04-02 | Solvay | Process for manufacturing glycidol |
WO2009016149A2 (en) * | 2007-07-30 | 2009-02-05 | Solvay (Société Anonyme) | Process for manufacturing glycidol |
US8715568B2 (en) | 2007-10-02 | 2014-05-06 | Solvay Sa | Use of compositions containing silicon for improving the corrosion resistance of vessels |
US8314205B2 (en) | 2007-12-17 | 2012-11-20 | Solvay (Societe Anonyme) | Glycerol-based product, process for obtaining same and use thereof in the manufacturing of dichloropropanol |
US8795536B2 (en) | 2008-01-31 | 2014-08-05 | Solvay (Societe Anonyme) | Process for degrading organic substances in an aqueous composition |
US8507643B2 (en) | 2008-04-03 | 2013-08-13 | Solvay S.A. | Composition comprising glycerol, process for obtaining same and use thereof in the manufacture of dichloropropanol |
US8536381B2 (en) | 2008-09-12 | 2013-09-17 | Solvay Sa | Process for purifying hydrogen chloride |
US9309209B2 (en) | 2010-09-30 | 2016-04-12 | Solvay Sa | Derivative of epichlorohydrin of natural origin |
US9573917B2 (en) | 2013-06-10 | 2017-02-21 | Spolek Pro Chemickou A Hutni Vyrobu A.S. | Process for the manufacture of epoxy-monomers and epoxides |
WO2014198243A1 (en) | 2013-06-10 | 2014-12-18 | Spolek Pro Chemickou A Hutni Vyrobu, Akciova Spolecnost | Process for the manufacture of epoxy-monomers and epoxides |
US9963436B2 (en) | 2013-06-10 | 2018-05-08 | Spolek Pro Chemickou A Hutni Vyrobu | Process for the manufacture of epoxy-monomers and epoxides |
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