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WO1997001523A1 - Decomposition d'ethers de cycloalkyle - Google Patents

Decomposition d'ethers de cycloalkyle Download PDF

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Publication number
WO1997001523A1
WO1997001523A1 PCT/SE1996/000851 SE9600851W WO9701523A1 WO 1997001523 A1 WO1997001523 A1 WO 1997001523A1 SE 9600851 W SE9600851 W SE 9600851W WO 9701523 A1 WO9701523 A1 WO 9701523A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
ofthe
cyclic
aldehyde
decomposition
Prior art date
Application number
PCT/SE1996/000851
Other languages
English (en)
Inventor
Börje WICKBERG
Original Assignee
Perstorp Ab
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 Perstorp Ab filed Critical Perstorp Ab
Priority to AU63246/96A priority Critical patent/AU6324696A/en
Publication of WO1997001523A1 publication Critical patent/WO1997001523A1/fr

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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
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C07C29/90—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound using hydrogen only
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings

Definitions

  • the present invention refers to a process for decomposition of a cyclic alkyl ether, which in its cyclic structure comprises a 1 ,3-dioxa group.
  • Such cyclic diethers are reaction products between at least one alcohol and at least one aldehyde and are substantially cyclic acetals, such as 1 ,3-dioxolanes, 1 ,3-dioxanes and 1 ,3,5-trioxepanes, whereby acetal designates an organic dialkoxy compound (alkyl diether) - R ⁇ mpps Chemie-Lexikon 8. Aufl. 1981 - and whereby cyclic acetal accordingly designates an organic cyclic dialkoxy compound (cyclic alkyl diether).
  • Di, tri and polyalcohols having a neopentyl structure such as neopentyl glycol, trimethylolpropane, trimethylolethane and pentaerythritol are normally synthesised in an alkali catalysed aldolcondensation of formaldehyde and a second aldehyde. Yielded aldolaldehyde is then reduced to corresponding alcohol by means of a so called Cannizzaro reaction with a further amount of formaldehyde in the presence of a strong base. The reaction can alternatively be carried out by means of catalytic hydration. The synthesis as well as a recovery of obtained reaction product yield normally secondary products such as acetals.
  • a neopentyl structure such as neopentyl glycol, trimethylolpropane, trimethylolethane and pentaerythritol are normally synthesised in an alkali catalysed ald
  • the syntheses yield primarily linear acetals, which when exposed to acidic treatment, for instance when passing an ion exchanger, during the recovery are transformed into cyclic acetals, such as 1 ,3-dioxanes.
  • This kind of synthesis can be exemplified by below processes, wherein pentaerythritol and neopentyl glycol are synthesised.
  • Pentaerythritol can for instance be synthesised in an aldolcondensation according to above, wherein 3 moles of formaldehyde and 1 mole of isobutyric aldehyde are reacted to yield trimethylolacetaldehyde, followed by a Cannizzaro reaction with 1 further mole of formaldehyde in the presence of 1 equivalent of sodium hydroxide or potassium hydroxide.
  • Neopentyl glycol can be synthesised accordingly by aldolcondensation of 1 mole of formaldehyde and 1 mole of isobutyric aldehyde yielding hydroxypivaldehyde, which then is reduced by means of 1 further mole of formaldehyde according to above or by catalytic hydration.
  • Cyclic acetals are also yielded during recovery if a synthesised di, tri or polyalcohol under acidic conditions is in contact with an aldehyde. This occurs for instance during an evaporation procedure, wherein water and excess of aldehyde, such as formaldehyde, are evaporated. Formation of acetals occurs when a 1 ,3-diol structure in the di, tri or polyalcohol reacts with for instance formaldehyde to corresponding 1 ,3-dioxane.
  • Cyclic 1 ,3-diethers as disclosed above are also yielded during other polyalcohol syntheses, such as acid catalysed etherification, as disclosed in for instance the U.S. Patent 3,673,226.
  • Cyclic diethers such as acetals can also be obtained by direct reaction between a di, tri or polyalcohol and an aldehyde. These reactions can be exemplified by 1 ,3-dioxolane (glycol formal) which is yielded when a mixture comprising formaldehyde, ethylene glycol and an acid catalyst is heated and by 1 ,3,5-trioxepane, a cyclic glycol formal having 2 oxymethylene groups, which is yielded when a mixture of 1 ,3-dioxolane, formaldehyde and an acid catalyst is heated. Glycerol can similarly yield acetals, such as 4-hydroxymethyl- l ,3- dioxolane and 5-hydroxy- l ,3-dioxane
  • Linear acetals are normally easy to decomposed, for instance by treating a diluted aqueous solution with a strong acid, optionally in the presence of a lower alcohol added to improve the solubility of the acetal.
  • Cyclic acetals comprising a 1 ,3-dioxa group are, however, normally very difficult to decompose. This is especially valid for acetals wherein included di, tri or polyalcohol is 2- or 2,2-substituted.
  • An acetal having a 1 ,3-dioxa group is thermodynamically favoured by a very stable structure.
  • the present invention refers to a process for decomposition of cyclic acetals being difficult to decompose as discussed above.
  • the process comprises above disclosed acidic decomposition and a simultaneously performed catalytic hydrogenation, whereby liberated aldehyde is removed from the equilibrium by means of a reaction yielding corresponding alcohol, such as formaldehyde yielding methanol, according to reaction scheme (B) below, which is a continuation of reaction scheme (A):
  • the invention is suitable for processing of for instance secondary product mixture obtained during a di, tri or polyalcohol synthesis and/or during processing of thereby obtained reaction solutions and mixtures, which secondary product mixture comprises at least one of said cyclic diethers, cyclic acetals, being difficult to decompose and which diether comprises a 1 ,3-dioxa group.
  • the decomposition process according to the invention can of course also be used for decomposition of said diethers obtained or produced by other means.
  • the decomposition increases, in case the di, tri or polyalcohol yielded from the decomposition is the same product as the one used in the original synthesis, the yield of said original synthesis.
  • the liberated di, tri or polyalcohol can also be used as raw material in the original synthesis. In such a case, the decomposition also increases the yield in that the liberated alcohol can be re-circulated.
  • Decomposition of cyclic formals yields methanol.
  • Methanol can after recovery be used in for instance the production of formaldehyde, which is an important raw material in the production of a large number of di, tri and polyalcohols as disclosed above.
  • Decomposition of cyclic acetals of higher aldehydes yields higher alcohols.
  • Such a higher alcohol is, should it contain two or more hydroxyl groups, of the same importance as component in for instance esters, polyesters, ethers, polyethers, polyurethanes, synthetic lubricants and similar monomeric or polymeric products as said liberated di, tri or polyalcohols.
  • a cyclic alkyl ether which in its cyclic structure comprises a 1 ,3 -dioxa group, such as cyclic diethers of the acetal type
  • an aqueous solution or an aqueous suspension comprising at least one cyclic diether is pH adjusted to a pH value of 1-6, preferably 1-4.
  • the solution or suspension is then in the presence of at least one metallic catalyst and during inlet of hydrogen heated to a reaction temperature of 100-200°C, preferably 120- 180°C. whereby the cyclic diether is decomposed and included alcohol and aldehyde are liberated and whereby the aldehyde through catalytic hydrogenation reacts to corresponding alcohol
  • the aqueous solution or aqueous suspension has in preferred embodiments a water content of 25-95, preferably 40-80, per cent by weight and the solution or suspension is pH adjusted to said pH value by an acid having a pKa value of at most 5. Hydrogen is preferably let in continuously during decomposition and hydrogenation, which reactions preferably are performed under a pressure of 10-150, such as 30-80, bar.
  • Various embodiments of the invention employ as catalyst one or more metals and/or metal oxides selected from the group consisting of rhodium, ruthenium, platinum and palladium deposited on an inert support, preferably activated carbon.
  • the amount of catalytically active metal or metal oxide deposited on the support is suitably 0. 1-50, such as 0.5-20, per cent by weight of the total weight of the catalyst.
  • the catalyst can furthermore be employed as a powder or as granules and added in an amount of 0.01-10, preferably 0. 1-1 , per cent by weight, calculated on the water-free substances, defined as 100 minus the water content, of the aqueous solution or aqueous suspension.
  • the decomposition is according to various embodiments carried out either in batches, whereby the catalyst preferably is employed as a powder, or as a continuos process, whereby the catalyst preferably consists of granules.
  • the catalyst is in a batch-by-batch decomposition suitably added in an amount of 0.05-5%, preferably 0. 1-1%, calculated as defined above.
  • Cyclic diethers suitable to decompose by means of the process according to the present invention are for instance dioxetanes, dioxolanes, dioxanes and trioxepanes, all comprising a 1 ,3-dioxa group, whereby one or more carbon atoms can be hydroxy, alkanyl, hyrdroxyalkanyl, alkenyl, hydroxyalkenyl, alkynyl, hydroxyalkynyl, aryl or hydroxyaryl substituted.
  • R j , R 2 , R 3 , R 4 , R 5 and R 6 independently are hydrogen, hydroxyl, alkanyl, alkenyl, alkynyl, aryl, hydroxy substituted alkanyl, hydroxy substituted alkenyl, hydroxy substituted alkynyl or hydroxy substituted aryl.
  • Formula (I) and (II) above include reaction products between an aldehyde and an di, tri or polyalcohol having a 1 ,3-diol structure.
  • Formula (I) and Formula (II) furthermore include reaction products between for instance formaldehyde and neopentyl glycol, glycerol, trimethylolpropane, trimethylolethane or pentaerythritol, such as 4-hydroxymethyl- l ,3-dioxolane, 5-hydroxy- l ,3-dioxane, 5-ethyl-5-hydroxymethyl- 1 ,3 -dioxane, 5, 5-di(hydroxymethyl)- 1 ,3 -dioxane and 5, 5-dimethyl- 1 ,3 -dioxane.
  • a cyclic diether comprising a 1 ,3-dioxa group, which ether is a reaction product between an aldehyde, preferably formaldehyde, and a dimer, trimer or polymer of said di, tri and polyalcohols, such as ditrimethylolpropane, ditrimethylolethane, diglycerol, dipentaerythritol, tripentaerythritol and polypentaerythritol, can advantageously be decomposed using the process according to the present invention.
  • Said cyclic diethers can be a part of or yielded from various secondary product mixtures obtained during the synthesis and/or recovery of a di, tri or polyalcohol, such as neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol and/or a dimer, trimer or polymer thereof.
  • a di, tri or polyalcohol such as neopentyl glycol, trimethylolpropane, trimethylolethane, pentaerythritol and/or a dimer, trimer or polymer thereof.
  • Example 1 Recovery as decomposition and catalytic hydrogenation of cyclic acetals in a secondary product mixture obtained during synthesising of ditrimethylolpropane.
  • Example 2. Decomposition and catalytic hydrogenation of a synthesised cyclic diether (cyclic formal), whereby a high degree of transformation is determined.
  • Yielded trimethylolpropane and its dimer can by means of processes known in the art, such as low pressure distillation, be recovered.

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  • 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

La présente invention concerne un procédé de décomposition d'un éther de cycloalkyle comprenant, dans sa structure cyclique, un groupe 1,3-dioxa. Ces diéthers cycliques du type acétal sont des produits de réaction entre au moins un aldéhyde et au moins un alcool. On ajuste sur 1 à 6 le pH d'une solution ou suspension aqueuse comprenant au moins un diéther cyclique. La solution ou suspension est ensuite chauffée à une température de réaction de 100 à 200 °C en présence d'au moins un catalyseur métallique et avec introduction d'hydrogène. L'éther de cycloalkyle est décomposé avec formation d'alcool et d'aldéhyde. L'aldéhyde continue à réagir par hydrogénation catalytique, donnant l'alcool correspondant.
PCT/SE1996/000851 1995-06-29 1996-06-27 Decomposition d'ethers de cycloalkyle WO1997001523A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU63246/96A AU6324696A (en) 1995-06-29 1996-06-27 Decomposition of cycloalkyl ethers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9502355-2 1995-06-29
SE9502355A SE9502355L (sv) 1995-06-29 1995-06-29 Spaltning av cykloalkyletrar

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WO1997001523A1 true WO1997001523A1 (fr) 1997-01-16

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19840276A1 (de) * 1998-09-04 2000-03-09 Degussa Verfahren zur reduzierenden Spaltung von linearen und cyclischen Acetalen, insbesondere Formalen
EP0983985A3 (fr) * 1998-09-04 2000-05-17 Degussa-Hüls Aktiengesellschaft Méthode pour la réduction de la teneur en acétals ou kétals dans des mélanges réactionnels
WO2000073250A1 (fr) * 1999-06-01 2000-12-07 Celanese International Corporation Traitement d'une composition comprenant un trimethylolalcane bis-monolineaire formal
US6251180B1 (en) * 1997-04-09 2001-06-26 Perstorp Ab Shrinkage-reducing agent for cement compositions
FR2931150A1 (fr) * 2008-05-19 2009-11-20 Rhodia Poliamida E Especialidades Ltda Procede de purification du glycerol brut
WO2010006688A2 (fr) 2008-07-15 2010-01-21 Oxea Deutschland Gmbh Procédé de production de néopentylglycol par scission de composés à haut point d'ébullition issus du processus de production
WO2010075616A1 (fr) * 2009-01-05 2010-07-08 Serviço Nacional De Aprendizagem Industrial-Senai/Dr-Ba Procédé de purification de glycérine jaune issue de la transestérification du biodiesel
WO2012102136A1 (fr) * 2011-01-26 2012-08-02 ポリプラスチックス株式会社 Procédé de production d'un concentré d'hémiformal et procédé de production de gaz formaldéhyde
WO2013072006A1 (fr) 2011-11-19 2013-05-23 Oxea Gmbh Procédé d'obtention de di-triméthylolpropane et de flux de produits enrichis en triméthylolpropane à partir des flux de sous-produits de la préparation de triméthylolpropane
DE102011118953A1 (de) 2011-11-19 2013-05-23 Oxea Gmbh Destillatives Verfahren zur Gewinnung von Di-Trimethylolpropan
DE102011122356A1 (de) 2011-12-23 2013-06-27 Oxea Gmbh Verfahren zur Gewinnung von mit Trimethylolpropan angereicherten Produktströmen aus den Nebenströmen der Trimethylolpropanherstellung
WO2014042769A1 (fr) 2012-09-17 2014-03-20 Oxea Bishop, Llc Récupération d'alcools à partir de résidu de purification
US8828137B2 (en) 2007-11-30 2014-09-09 Celanese International Corporation Additive composition for mortars, cements and joint compounds and cementitious compositions made therefrom
US8921618B2 (en) 2012-09-17 2014-12-30 Oxea Bishop Llc Recovery of trimethylolpropane from purification residue

Citations (3)

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Publication number Priority date Publication date Assignee Title
US2888492A (en) * 1955-08-08 1959-05-26 Shell Dev Production of polyols
US3963755A (en) * 1974-07-31 1976-06-15 E. I. Du Pont De Nemours And Company Mixture of 2(2'-propanal)-5-methyl-1,3-dioxane and 2(3'-propanal)-5-methyl-1,3-dioxane
US4044059A (en) * 1974-08-02 1977-08-23 E. I. Du Pont De Nemours And Company One-step method for hydrolyzing and hydrogenating acetal-aldehydes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888492A (en) * 1955-08-08 1959-05-26 Shell Dev Production of polyols
US3963755A (en) * 1974-07-31 1976-06-15 E. I. Du Pont De Nemours And Company Mixture of 2(2'-propanal)-5-methyl-1,3-dioxane and 2(3'-propanal)-5-methyl-1,3-dioxane
US4044059A (en) * 1974-08-02 1977-08-23 E. I. Du Pont De Nemours And Company One-step method for hydrolyzing and hydrogenating acetal-aldehydes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 80, No, 15, 15 April 1974, (Columbus, Ohio, USA), page 326, the Abstract No. 82063m; & JP,A,48 043 084 (MIYAMOTO, AKIRA et al.) 17 December 1973. *

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6251180B1 (en) * 1997-04-09 2001-06-26 Perstorp Ab Shrinkage-reducing agent for cement compositions
DE19840276C2 (de) * 1998-09-04 2002-10-31 Perstorp Specialty Chem Ab Verfahren zur reduzierenden Spaltung von linearen und cyclischen Acetalen, insbesondere Formalen
EP0983985A3 (fr) * 1998-09-04 2000-05-17 Degussa-Hüls Aktiengesellschaft Méthode pour la réduction de la teneur en acétals ou kétals dans des mélanges réactionnels
EP0983984A3 (fr) * 1998-09-04 2000-05-17 Degussa-Hüls Aktiengesellschaft Méthode pour la scission réductive d'acétals linéaires et cycliques, notamment de formals
DE19840276A1 (de) * 1998-09-04 2000-03-09 Degussa Verfahren zur reduzierenden Spaltung von linearen und cyclischen Acetalen, insbesondere Formalen
US6232512B1 (en) 1998-09-04 2001-05-15 Degussa-Huls Ag Method for reducing the content of acetals or ketals in alcohol-containing reaction mixtures
US6265623B1 (en) 1998-09-04 2001-07-24 Perstorp Specialty Chemicals Ab Process for the reductive cleavage of linear and cyclic acetals especially formals
KR100748797B1 (ko) * 1999-06-01 2007-08-13 셀라니즈 인터내셔날 코포레이션 트리메틸올알칸 비스-모노 선형 포름알을 포함하는 조성물의 처리 방법
WO2000073250A1 (fr) * 1999-06-01 2000-12-07 Celanese International Corporation Traitement d'une composition comprenant un trimethylolalcane bis-monolineaire formal
US8828137B2 (en) 2007-11-30 2014-09-09 Celanese International Corporation Additive composition for mortars, cements and joint compounds and cementitious compositions made therefrom
FR2931150A1 (fr) * 2008-05-19 2009-11-20 Rhodia Poliamida E Especialidades Ltda Procede de purification du glycerol brut
WO2009141702A1 (fr) * 2008-05-19 2009-11-26 Rhodia Poliamida E Especialidades Ltda Procede de purification du glycerol brut
US9024081B2 (en) 2008-05-19 2015-05-05 Rhodia Poliamida E Especialidades Ltda Purification of crude glycerol
WO2010006688A2 (fr) 2008-07-15 2010-01-21 Oxea Deutschland Gmbh Procédé de production de néopentylglycol par scission de composés à haut point d'ébullition issus du processus de production
DE102008033163A1 (de) 2008-07-15 2010-01-21 Oxea Deutschland Gmbh Verfahren zur Gewinnung von Neopentylglykol durch Spaltung von im Herstellverfahren anfallenden Hochsiedern
WO2010075616A1 (fr) * 2009-01-05 2010-07-08 Serviço Nacional De Aprendizagem Industrial-Senai/Dr-Ba Procédé de purification de glycérine jaune issue de la transestérification du biodiesel
WO2012102136A1 (fr) * 2011-01-26 2012-08-02 ポリプラスチックス株式会社 Procédé de production d'un concentré d'hémiformal et procédé de production de gaz formaldéhyde
JP2012153648A (ja) * 2011-01-26 2012-08-16 Polyplastics Co ヘミホルマール濃縮物の製造方法及びホルムアルデヒドガスの製造方法
WO2013072006A1 (fr) 2011-11-19 2013-05-23 Oxea Gmbh Procédé d'obtention de di-triméthylolpropane et de flux de produits enrichis en triméthylolpropane à partir des flux de sous-produits de la préparation de triméthylolpropane
DE102011118956A1 (de) 2011-11-19 2013-05-23 Oxea Gmbh Verfahren zur Gewinnung von Di-Trimethylolpropan und mit Trimethylolpropan angereicherten Produktströmen aus den Nebenströmen der Trimethylolpropanherstellung
WO2013072007A1 (fr) 2011-11-19 2013-05-23 Oxea Gmbh Procédé d'obtention de di-triméthylolpropane par distillation
US9745236B2 (en) 2011-11-19 2017-08-29 Oxea Gmbh Method for recovering di-trimethylolpropane by distillation
US9045451B2 (en) 2011-11-19 2015-06-02 Oxea Gmbh Method for recovering di-trimethylolpropane and trimethylolpropane-enriched product streams from the side streams of trimethylolpropane production
DE102011118953A1 (de) 2011-11-19 2013-05-23 Oxea Gmbh Destillatives Verfahren zur Gewinnung von Di-Trimethylolpropan
US8987527B2 (en) 2011-12-23 2015-03-24 Oxea Gmbh Process for obtaining trimethylolpropane-enriched product streams from the secondary streams of trimethylolpropane preparation
WO2013091765A1 (fr) 2011-12-23 2013-06-27 Oxea Gmbh Procédé pour l'obtention de flux de produits enrichis en triméthylolpropane à partir des flux secondaires de la production de triméthylolpropane
DE102011122356A1 (de) 2011-12-23 2013-06-27 Oxea Gmbh Verfahren zur Gewinnung von mit Trimethylolpropan angereicherten Produktströmen aus den Nebenströmen der Trimethylolpropanherstellung
US8921618B2 (en) 2012-09-17 2014-12-30 Oxea Bishop Llc Recovery of trimethylolpropane from purification residue
US8759593B2 (en) 2012-09-17 2014-06-24 Oxea Bishop Llc Recovery of alcohols from purification residue
WO2014042769A1 (fr) 2012-09-17 2014-03-20 Oxea Bishop, Llc Récupération d'alcools à partir de résidu de purification

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AU6324696A (en) 1997-01-30
SE9502355D0 (sv) 1995-06-29
SE9502355L (sv) 1996-12-30

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