WO2015071138A1 - Procédé de séparation du cyclohexanol - Google Patents

Procédé de séparation du cyclohexanol Download PDF

Info

Publication number
WO2015071138A1
WO2015071138A1 PCT/EP2014/073756 EP2014073756W WO2015071138A1 WO 2015071138 A1 WO2015071138 A1 WO 2015071138A1 EP 2014073756 W EP2014073756 W EP 2014073756W WO 2015071138 A1 WO2015071138 A1 WO 2015071138A1
Authority
WO
WIPO (PCT)
Prior art keywords
hexanol
cyclohexanol
mixture
weight
mixtures
Prior art date
Application number
PCT/EP2014/073756
Other languages
German (de)
English (en)
Inventor
Rene Backes
Christian König
Michele Gatti
Original Assignee
Basf Se
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 Basf Se filed Critical Basf Se
Publication of WO2015071138A1 publication Critical patent/WO2015071138A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups

Definitions

  • the present invention relates to a process for the separation of cyclohexanol from mixtures containing cyclohexanol and hexanol, which is characterized in that hexanol is converted to an ether or polyether and then cyclohexanol is separated from the mixture.
  • An important precursor for the production of chemical compounds is cyclohexane. Cyclohexane can be obtained from petroleum by fractional distillation of naphtha or by hydrogenation of benzene.
  • cyclohexane is obtained by oxidation cyclohexanol and cyclohexanone.
  • oxidation and concomitant ring opening e.g. Hexanediol and adipic acid produced.
  • Object of the present invention was to provide a corresponding method.
  • the mixtures are preferably mixtures which are liquid at 20 ° C., 1 bar.
  • the hexanol is preferably 1-hexanol, also known as n-hexanol.
  • the mixtures consist of 1 to 99 wt.%, In particular 5 to 95 wt.% Hexanol
  • the content of further compounds in the mixtures is particularly preferably not more than 20% by weight, very particularly preferably not more than 10% by weight and in particular embodiments not more than 5% by weight or not more than 1% by weight or not more than 0.1 % By weight, based in each case on the total weight of the mixtures.
  • the mixture particularly preferably consists of at least 80% by weight, very particularly preferably at least 90% by weight and in particular embodiments at least 95% by weight or at least 99% by weight or even 99.9% by weight of cyclohexanol and hexanol.
  • the mixture can consist both predominantly of hexanol and predominantly of cyclohexanol.
  • the further compounds which may be included in the mixtures may be any compounds; in particular, they may be starting materials, end products, by-products, solvents or auxiliaries, such as catalysts, which are contained in the mixtures by previous reactions and work-ups. Suitable examples are secondary products which are obtained by oxidations and other reactions of cyclohexane and their work-up, for example cyclohexanone, cyclohexanediol, hexanediol, caprolactone or adipic acid.
  • the hexanol contained in the mixtures is converted to an ether or polyether.
  • an alkylene oxide is added to the mixtures.
  • the alkylene oxide may be, for example, ethylene oxide (EO), propylene oxide (PO) or butylene oxides or mixtures of different alkylene oxides, in particular mixtures of EO and PO. Preferred is ethylene oxide.
  • Hexanol is reacted with the alkylene oxide to form an ether or polyether. It is the per se known alkoxylation of hydroxyl groups, as has already been frequently described, e.g. also in DE 10 2004008302. It has been found that in the above mixture first of all an alkoxylation of the primary hydroxyl group of the hexanol takes place while the secondary hydroxyl group of the cyclohexanol is not or hardly alkoxylated.
  • the molar ratio of the alkylene oxide to the hexanol is preferably at least 0.8: 1, more preferably at least 1: 1.
  • the molar ratio of the alkylene oxide to the hexanol is preferably not more than 2: 1, in particular not more than 1, 2: 1 or 1:05: 1
  • the ether or polyether obtained again has a terminal, primary hydroxyl group which is again preferably alkoxylated in comparison to the secondary hydroxyl group of the cyclohexanol.
  • the molar ratio of ethylene oxide to hexanol can therefore be e.g. 0.8: 1 to 20: 1.
  • the molar ratio of the ethylene oxide to the hexanol is preferably at least 1: 1 (see above) and in particularly preferred embodiments at least 2: 1 or at least 5: 1.
  • the excess of EO facilitates complete conversion of the hexanol to an ether or polyether, but too much excess is not necessary.
  • the molar ratio of EO to hexanol is therefore generally not more than 20: 1 or 10: 1.
  • the reaction of the hexanol with the alkylene oxide is preferably carried out in the presence of a base as a catalyst.
  • Suitable bases are, for example, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkaline earth metal alkoxides or basic nitrogen compounds.
  • Suitable alkali metal hydroxides are in particular NaOH or KOH, which can also be used in the form of their aqueous solutions.
  • Suitable alkali metal alkoxides are, in particular, the sodium or potassium salts of primary aliphatic alcohols, preferably linear or branched C 1 to C 10 alkanols; in particular the sodium or potassium salt of tertiary butanol (sodium or potassium tertiary butoxide) may be mentioned.
  • Suitable basic nitrogen compounds are For example, compounds having a primary or secondary amino group, in particular imidazole and N-methylimidazole.
  • basic nitrogen compounds are used as catalysts, very particular preference is given to imidazole.
  • the catalyst is preferably used in amounts of from 0.005 to 1 parts by weight, in particular from 0.01 to 0.5 parts by weight per 100 parts by weight of hexanol.
  • the reaction is preferably carried out at 50 to 200 ° C, in particular at 70 to 140 ° C.
  • the reaction can be carried out at reduced pressure, atmospheric pressure or overpressure. In general, the pressure is 0.001 to 20 bar, in particular 0.001 to 6 bar.
  • the duration of the reaction is preferably chosen so that at least 90%, in particular at least 95% or at least 99% of the hexanol are converted to an ether or polyether.
  • the alkoxylation of the hexanol can e.g. determined or monitored by gas chromatography.
  • the cyclohexanol contained in the mixture is not or hardly alkoxylated. In general, less than 5% by weight, in particular less than 2% by weight, of the cyclohexanol present in the mixture is alkoxylated during the reaction.
  • Cyclohexanol can therefore be readily separated from the mixture, e.g. by distillation.
  • the above process can be carried out batchwise, semi-continuously (continuous feed of only one starting material, of the mixture or of the alkylene oxide) or to the full extent continuously (continuous supply of all starting materials, continuous removal of the product mixture, optionally followed from a continuous distillation separation of the cyclohexanol).
  • the above process is a particularly simple and inexpensive process for the separation of hexanol and cyclohexanol. Hexanol is thereby obtained as alkoxylated hexanol. Alkoxylated hexanol is a valuable product which is suitable for many uses, for example in lubricants, cleaning agents, as a surface-active auxiliary, as an emulsifying or dispersing assistant.
  • the process according to the invention is therefore not only a separation process but at the same time a further reaction of one of the components to be separated into a further finished product of value. Examples
  • Examples 1 to 10 relate to the alkoxylation of various mixtures of 1-hexanol / cyclohexanol with varying amounts of ethylene oxide.
  • the proportion of alkoxylated hexanol and cyclohexanol in the product mixture was determined by gas chromatography.
  • the OH number was determined according to DIN 53240.
  • Ratio of hexanol to cyclohexanol 2 1, 1 mol EO per hydroxyl group of 1-hexanol using imidazole as a catalyst
  • the product mixture obtained had an OH number of 439.8 mg KOH / g.
  • Ratio of hexanol to cyclohexanol 5 1, 1 mol EO per hydroxyl group of 1 -hexanol using imidazole as a catalyst
  • a mixture of 147.1 g of 1-hexanol, 29.4 g of cyclohexanol and 0.1 g of imidazole was introduced at 25 ° C in a 300 ml reactor under nitrogen.
  • the reactor was heated to 120 ° C and dosed 63.4 g of ethylene oxide. After a reaction time of 4 h was evacuated for 40 minutes at 40 ° C and so removed unreacted EO. It was then cooled to 25 ° C. There were obtained 224.8 g of product mixture. 43% of the hexanol used was ethoxylated.
  • Ratio of hexanol to cyclohexanol 10 1, 1 mol EO per hydroxyl group of 1-hexanol using imidazole as catalyst
  • a mixture of 143.6.1 g of 1-hexanol, 14.4 g of cyclohexanol and 0.1 g of imidazole was at 25 ° C in a 300 ml reactor under nitrogen. The reactor was heated to 120 ° C and dosed 61, 9 g of ethylene oxide. After a reaction time of 4 h, the mixture was evacuated at 40 ° C. for 40 minutes, thus removing unreacted EO. It was then cooled to 25 ° C. There were obtained 205 g of product mixture.
  • the product mixture obtained had an OH number of 412.4 mg KOH / g.
  • Ratio of hexanol to cyclohexanol 2 1, 2 moles of EO per hydroxyl group of 1 -hexanol using imidazole as a catalyst
  • a mixture of 93.1 g of 1-hexanol, 46.5 g of cyclohexanol and 0.1 g of imidazole was introduced at 25 ° C in a 300 ml reactor under nitrogen.
  • the reactor was heated to 120 ° C and dosed 80.3 g of ethylene oxide.
  • the mixture was evacuated at 40 ° C. for 40 minutes, thus removing unreacted EO. It was then cooled to 25 ° C. There were obtained 196 g of product mixture.
  • the product mixture obtained had an OH number of 372.1 mg KOH / g.
  • Ratio of hexanol to cyclohexanol 5 1, 2 moles of EO per hydroxyl group of 1 -hexanol using imidazole as a catalyst
  • a mixture of 106.6 g of 1-hexanol, 21, 3 g of cyclohexanol and 0.1 g of imidazole was charged at 25 ° C in a 300 ml reactor under nitrogen.
  • the reactor was heated to 120 ° C and dosed 91, 9 g of ethylene oxide. After a reaction time of 4 h, the mixture was evacuated at 40 ° C. for 40 minutes, thus removing unreacted EO. It was then cooled to 25 ° C. There were obtained 194.4 g of product mixture. 62% of the hexanol used was ethoxylated.
  • the product mixture obtained had an OH number of 348.7 mg KOH / g.
  • Ratio of hexanol to cyclohexanol 10 1, 2 moles of EO per hydroxyl group of 1 -hexanol using imidazole as a catalyst
  • a mixture of 1 12.1 g of 1-hexanol, 1 1, 2 g of cyclohexanol and 0.1 g of imidazole was introduced at 25 ° C in a 300 ml reactor under nitrogen.
  • the reactor was heated to 120 ° C and dosed 96.6 g of ethylene oxide.
  • the mixture was evacuated at 40 ° C. for 40 minutes, thus removing unreacted EO. It was then cooled to 25 ° C. There were obtained 196 g of product mixture.
  • the product mixture obtained had an OH number of 336.1 mg KOH / g.
  • Ratio of hexanol to cyclohexanol 10 1, 1 mol EO per hydroxyl group of 1 -hexanol using KOH as a catalyst
  • a mixture of 129.8 g of 1-hexanol, 12.98 g of cyclohexanol and 1.2 g of KOH (50% solution in water) was placed at 25 ° C in a 300 ml reactor under nitrogen.
  • the reactor was heated to 120 ° C and dosed 55.98 g of ethylene oxide.
  • the mixture was evacuated at 40 ° C. for 40 minutes, thus removing unreacted EO. It was then cooled to 25 ° C. There were obtained 188 g of product mixture.
  • Ratio hexanol to cyclohexanol 10 1, 1 mole of EO per hydroxyl group of 1-hexanol using potassium tertiärbutylat f as Catalyst
  • a mixture of 143.0 g of 1-hexanol, 14.3 g of cyclohexanol and 1 .1 g f BuOK was measured at 25 ° C placed in a 300 ml reactor under nitrogen. The reactor was heated to 120 ° C and dosed 61.6 g of ethylene oxide. After a reaction time of 4 h, the mixture was evacuated at 40 ° C. for 40 minutes, thus removing unreacted EO. It was then cooled to 25 ° C. There were obtained 206 g of product mixture.
  • the product mixture obtained had an OH number of 407 mg KOH / g.
  • Ratio of hexanol to cyclohexanol 2 1, 1 mol PO per hydroxyl group of 1-hexanol using imidazole as a catalyst
  • a mixture of 1 15.9 g of 1-hexanol, 58.0 g of cyclohexanol and 0.24 g of imidazole (50% solution in water) was placed at 25 ° C in a 300 ml reactor under nitrogen.
  • the reactor was heated to 120 ° C and dosed to 65.9 g of propylene oxide. After a reaction time of 4 h was evacuated 40 minutes at 40 ° C and so unreacted PO removed. It was then cooled to 25 ° C. There were obtained 220 g of product mixture.
  • the product mixture obtained had an OH number of 426 mg KOH / g.
  • Ratio of hexanol to cyclohexanol 5 1, 1 mol PO per hydroxyl group of 1-hexanol using imidazole as a catalyst
  • the product mixture obtained had an OH number of 414 mg KOH / g.

Landscapes

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

Abstract

L'invention concerne un procédé de séparation du cyclohexanol de mélanges contenant du cyclohexanol et de l'hexanol. L'invention est caractérisée en ce que l'on transforme l'hexanol en un éther ou un polyéther puis on sépare le cyclohexanol du mélange.
PCT/EP2014/073756 2013-11-15 2014-11-05 Procédé de séparation du cyclohexanol WO2015071138A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13193010.9 2013-11-15
EP13193010 2013-11-15

Publications (1)

Publication Number Publication Date
WO2015071138A1 true WO2015071138A1 (fr) 2015-05-21

Family

ID=49578214

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/073756 WO2015071138A1 (fr) 2013-11-15 2014-11-05 Procédé de séparation du cyclohexanol

Country Status (1)

Country Link
WO (1) WO2015071138A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10259797B2 (en) 2015-11-04 2019-04-16 Basf Se Process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific HMF esters
US10385033B2 (en) 2015-07-22 2019-08-20 Basf Se Process for preparing furan-2,5-dicarboxylic acid
US10428039B2 (en) 2015-11-04 2019-10-01 Basf Se Process for preparing furan-2,5-dicarboxylic acid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2706707A (en) * 1950-05-05 1955-04-19 Exxon Research Engineering Co Extractive distillation of oxygenated organic compounds
DE1111162B (de) * 1957-10-09 1961-07-20 Labofina Sa Verfahren zur Gewinnung und Trennung von Alkoholen aus organischem Milieu
JP2001163813A (ja) * 1999-12-13 2001-06-19 Lion Corp グリコールエーテルの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2706707A (en) * 1950-05-05 1955-04-19 Exxon Research Engineering Co Extractive distillation of oxygenated organic compounds
DE1111162B (de) * 1957-10-09 1961-07-20 Labofina Sa Verfahren zur Gewinnung und Trennung von Alkoholen aus organischem Milieu
JP2001163813A (ja) * 1999-12-13 2001-06-19 Lion Corp グリコールエーテルの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200167, Derwent World Patents Index; AN 2001-592518, XP002734560 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10385033B2 (en) 2015-07-22 2019-08-20 Basf Se Process for preparing furan-2,5-dicarboxylic acid
US10259797B2 (en) 2015-11-04 2019-04-16 Basf Se Process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific HMF esters
US10428039B2 (en) 2015-11-04 2019-10-01 Basf Se Process for preparing furan-2,5-dicarboxylic acid

Similar Documents

Publication Publication Date Title
DE19928128C1 (de) Verfahren zur Herstellung von Ethercarbonsäuren mit niedrigem Restalkohol
WO2015071138A1 (fr) Procédé de séparation du cyclohexanol
DE102011012846B4 (de) Verfahren zur Durchführung von mehrphasigen Aldolkondensationsreaktionen zu gemischten α,β-ungesättigten Aldehyden
DE10353934A1 (de) Verfahren zur Herstellung von Metallsalzen der Trifluormethansulfonsäure und deren Verwendung als Veresterungskatalysatoren
EP3697751B1 (fr) Procédé de préparation de diméthyléther de polyoxyméthylène
EP0181536B1 (fr) Procédé pour la préparation de alcoyl-1 ou cycloalcoyl-1 pipérazines
EP0137433B1 (fr) Procédé de préparation continue d'alcools
WO2014083138A1 (fr) Procédé d'aldolisation catalytique d'aldéhydes
DE2056198B2 (de) Verfahren zur kontinuierlichen Herstellung von Propylenoxid aus Propylenchlorhydrin
EP0789744B1 (fr) Procede de fabrication de tensioactifs non ioniques a groupes terminaux fermes
EP0111861B1 (fr) Procédé de préparation d'amines
EP0025940B1 (fr) Procédé pour l'hydroxylation de composés oléfiniquement insaturés
EP1581481A1 (fr) Neutralisation amelioree de produits de synthese d'isophoronenitrile
WO2001077051A1 (fr) Procede de production d'ethers d'alcenyle
EP0491142B1 (fr) Procédé pour la préparation de mélanges d'acétals de glycérine cycliques d'acroléine
EP0080118B1 (fr) Procédé pour la préparation des acétales tétraalkyl de malondialdéhyde
WO1998038153A1 (fr) Procede de preparation de n,n,n',n'-tetra-(2-hydroxyethyl)ethylenediamine
EP0802895B1 (fr) Procede pour produire des tensioactifs non ioniques proteges par des groupes terminaux
EP1889825A1 (fr) Procédé pour la synthèse du 1,2-propanediol
DE102014113197A1 (de) Verfahren und Anlage zur Herstellung von Fettalkoholen
EP1007500A1 (fr) Procede de preparation d'esters de glycol d'alkylene a repartition limitee d'homologues
WO1998009932A1 (fr) Procede de production d'alcyne-diols ou de melanges d'alcyne-diols avec des alcyne-monools
DE2533158A1 (de) Verfahren zur herstellung von isopropylalkohol
EP1188737A1 (fr) Procédé de traitement de courants de matières comprenant l' oxyde de mésityle
DE1800462C3 (de) Verfahren zur Alkoxylierung von Substanzen mit alkoholischen Hydroxylgruppen

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14793166

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14793166

Country of ref document: EP

Kind code of ref document: A1