EP1809590A1 - Procede pour produire des polyoxymethylene dimethylethers - Google Patents

Procede pour produire des polyoxymethylene dimethylethers

Info

Publication number
EP1809590A1
EP1809590A1 EP05797855A EP05797855A EP1809590A1 EP 1809590 A1 EP1809590 A1 EP 1809590A1 EP 05797855 A EP05797855 A EP 05797855A EP 05797855 A EP05797855 A EP 05797855A EP 1809590 A1 EP1809590 A1 EP 1809590A1
Authority
EP
European Patent Office
Prior art keywords
methylal
reaction
trioxane
mixture
fraction
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Withdrawn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
EP05797855A
Other languages
German (de)
English (en)
Inventor
Heiner Schelling
Eckhard Ströfer
Rolf Pinkos
Andrea Haunert
Gerd-Dieter Tebben
Hans Hasse
Sergej Blagov
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.)
BASF SE
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
Priority claimed from DE200410053839 external-priority patent/DE102004053839A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1809590A1 publication Critical patent/EP1809590A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/12—Polymerisation of acetaldehyde or cyclic oligomers thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones

Definitions

  • the invention relates to a process for the preparation of Polyoxymethylendimethyl ⁇ ethers.
  • Polyoxymethylene dimethyl ether represents a homologous series of the general formula
  • n is a number> 1.
  • the polyoxymethylene dimethyl ethers are acetals. They are prepared, like methylal, by reaction of methanol with aqueous formaldehyde in the presence of an acidic catalyst. Like other acetals, they are stable under neutral or alkaline conditions, but are already attacked by dilute acids. By hydrolysis, they are converted in a first step to hemiacetals and methanol. In a second step, the hemiacetals are hydrolyzed to formaldehyde and methanol.
  • Polyoxymethylendimethylether be prepared by heating polyoxymethylene glycol or paraformaldehyde with methanol in the presence of traces of sulfuric acid or hydrochloric acid at temperatures of 150 to 180 0 C and reaction times of 12 to 15 hours. This leads to decomposition reactions with the formation of carbon dioxide and the formation of dimethyl ether.
  • polyoxymethylene dimethyl ethers have become important as diesel fuel additives.
  • oxygen-containing compounds which have only a few or no C-C bonds, such as, for example, methanol, are added to this.
  • such compounds are often insoluble in diesel fuel and reduce the cetane number and / or the flash point of the diesel fuel mixture. No.
  • the obtained Polyoxymethylendimethylether are added in amounts of 5 to 30 wt .-% of a diesel fuel.
  • No. 6,392,102 describes the preparation of polyoxymethylene dimethyl ethers by reacting a feed stream comprising methanol and formaldehyde, which was obtained by oxidation of dimethyl ether, in the presence of an acidic catalyst and simultaneous separation of the reaction products in a catalytic distillation column. In this case, methylal, methanol, water and Polyoxymethylendimethyl- ether are obtained.
  • a disadvantage of the known processes for the preparation of the lower polyoxymethylene dimethyl ether is that predominantly the dimer is obtained.
  • a disadvantage of the processes which emanate from formaldehyde and methanol is also that water is formed as the reaction product which hydrolyzes polyoxymethylene dimethyl ether already formed in the presence of the acidic catalysts. In this case, the unstable hemiacetals are formed. The unstable hemiacetals reduce the flash point of the diesel fuel mixture and thus affect its quality. However, a too low flash point of the diesel fuel mixture means that the specifications specified by relevant DIN standards are no longer met. Hal ⁇ bacetale are difficult to separate because of comparable boiling points of polyoxymethylene methyl ethers.
  • the dimer formed as the main product has a low boiling point and thus also reduces the flash point, making it less suitable as a diesel fuel additive.
  • the object of the invention is to provide an improved process for the preparation of polyoxymethylene dimethyl ethers which does not have the disadvantages of the prior art.
  • the object of the invention is in particular to provide a process for the preparation of Polyoxymethylendimethylethern with a particularly high proportion of trimer and tetramer.
  • methylal with trioxane In the reaction of methylal with trioxane to the Polyoxymethylendimethylethern no water is formed as a byproduct.
  • the reaction is generally carried out at a temperature of 50 to 200 0 C, preferably 90 to 150 0 C, and a pressure of 1 to 20 bar, preferably 2 to 10 bar.
  • the molar ratio of methylal: trioxane is generally 0.1 to 10, preferably 0.5 to 5.
  • the acidic catalyst may be a homogeneous or heterogeneous acidic catalyst.
  • Suitable acidic catalysts are mineral acids such as largely anhydrous sulfuric acid, sulfonic acids such as trifluoromethanesulfonic acid and para-toluenesulfonic acid, heteropolyacids, acidic ion exchange resins, zeolites, aluminosilicates, silica, alumina, titania and zirconia.
  • Oxidative catalysts may be doped with sulfate or phosphate groups to increase their acid strength, generally in amounts of from 0.05 to 10% by weight.
  • the reaction can be carried out in a stirred tank reactor (CSTR) or a tubular reactor. If a heterogeneous catalyst is used, a fixed bed reactor is preferred. If a fixed catalyst bed is used, the product mixture can then be contacted with an anion exchange resin to obtain a substantially acid-free product mixture.
  • CSTR stirred tank reactor
  • the amount of water introduced by methylal and trioxane and by the catalyst is in total ⁇ 1% by weight, preferably ⁇ 0.5% by weight, more preferably ⁇ 0.2% by weight and in particular ⁇ 0.1% by weight. -%, Based on the reaction mixture of methylal, trioxane and the catalyst. For this purpose, virtually anhydrous trio xan and methylal used and limited if necessary by the catalystkohl ⁇ introduced amount of water.
  • the hemiacetals (monoethers) or polyoxymethylene glycols formed by hydrolysis in the presence of water from already formed polyoxymethylene dimethyl ether have a boiling point comparable to that of the polyoxymethylene dimethyl ethers, thereby making it difficult to separate the polyoxymethylene dimethyl ethers from these by-products.
  • a fraction containing the trimer and tetramers is separated from the product mixture of the reaction of methylal with trioxane and unreacted methylal, trioxane and polyoxymethylene dimethyl ether are reacted with n ⁇ 3 is attributed to the acid-catalyzed reaction.
  • the polyoxymethylene dimethyl ethers with n> 4 are additionally recycled into the reaction. Due to the recycling, especially trimer and tetramer are obtained.
  • the first distillation column for example, at a pressure of 0.5 to 1, 5 bar
  • the second distillation column for example, at a pressure of 0.05 to 1 bar
  • the third distillation column for example, at a pressure of 0.001 to 0.5 bar operated
  • the first and the second fraction more preferably additionally also the fourth fraction are recycled to the reaction.
  • a homogeneous catalyst for example a mineral acid or a sulfonic acid, it remains in the fourth fraction and is recycled with it into the acid-catalyzed reaction.
  • FIG. 1 shows a process flow diagram according to an embodiment of the method according to the invention.
  • the product stream 4 is passed through a bed 5 of anion exchange resin, whereby a substantially acid-free product mixture 6 is obtained.
  • This is fed into a first distillation column 7, in which methylal is separated off as the recycle stream 8 via the top.
  • a recycle stream 15 of pentameric and higher Polyoxymethylendimethylethern (n> 4) is obtained.
  • FIG. 2 shows the process flow diagram according to a further embodiment of the method according to the invention.
  • a homogeneous catalyst is used, which is fed into the reactor 3 t as a further feed stream 16.
  • a bed of anionic ion exchange resin downstream of the reactor 3 is dispensed with and the product stream 4 of the reaction is fed directly to the first distillation column 7.
  • the bottom draw 15 of the third distillation column additionally contains the homogeneous catalyst.
  • a small partial stream 17 can be separated from the recirculation stream 15 and discharged from the process, the catalyst loss being compensated by the feed stream 16.
  • Example 7 As the comparison of Example 7 with Examples 5 and 6 shows, the recirculation of the dimer into the reaction leads to particularly high yields of trimer and tetramer.

Landscapes

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

Abstract

L'invention concerne un procédé pour produire du polyoxyméthylène diméthyléther de formule H<SUB>3</SUB>CO(CH<SUB>2</SUB>O)<SUB>n</SUB>CH<SUB>3</SUB>, où n = 2 10. Selon ce procédé, du méthylal et dutrioxane sont mis dans un réacteur à réagir en présence d'un catalyseur acide. L'invention est caractérisée en ce que la quantité d'eau introduite dans le mélange réactionnel par le méthylal, le trioxane et/ou le catalyseur est < 1 % en poids, relativement au mélange réactionnel. Le mélange réactionnel permet d'obtenir par distillation une fraction contenant du polyoxyméthylène diméthyléther où n = 3 et 4, le méthylal, le trioxane et le polyoxyméthylène diméthyléther où n < 3 et éventuellement n > 4 étant réintroduits dans la transformation.
EP05797855A 2004-10-25 2005-10-19 Procede pour produire des polyoxymethylene dimethylethers Withdrawn EP1809590A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102004051814 2004-10-25
DE200410053839 DE102004053839A1 (de) 2004-11-04 2004-11-04 Verfahren zur Herstellung von Polyoxymethylendimethylethern
PCT/EP2005/011234 WO2006045506A1 (fr) 2004-10-25 2005-10-19 Procédé pour produire des polyoxyméthylène diméthyléthers

Publications (1)

Publication Number Publication Date
EP1809590A1 true EP1809590A1 (fr) 2007-07-25

Family

ID=35962680

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05797855A Withdrawn EP1809590A1 (fr) 2004-10-25 2005-10-19 Procede pour produire des polyoxymethylene dimethylethers

Country Status (5)

Country Link
US (1) US20070260094A1 (fr)
EP (1) EP1809590A1 (fr)
JP (1) JP2008517960A (fr)
CA (1) CA2581502A1 (fr)
WO (1) WO2006045506A1 (fr)

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DE10361516A1 (de) * 2003-12-23 2005-07-28 Basf Ag Verfahren zur Abtrennung von Trioxan aus einem Trioxan/Formaldehyd/Wasser-Gemisch mittels Druckwechsel-Rektifikation
DE102005027702A1 (de) * 2005-06-15 2006-12-21 Basf Ag Verfahren zur Herstellung von Polyoxymethylendimethylethern aus Methanol und Formaldehyd
DE102005027690A1 (de) * 2005-06-15 2006-12-21 Basf Ag Verfahren zur Herstellung von Polyoxmethylendialkylethern aus Trioxan und Dialkylether
DE102005027701A1 (de) * 2005-06-15 2006-12-21 Basf Ag Verfahren zur Herstellung von Polyoxymethylendimethylethern aus Methanol und Formaldehyd
CN101182367A (zh) 2007-07-31 2008-05-21 中国科学院兰州化学物理研究所 聚甲氧基甲缩醛的制备方法
CN101665414B (zh) 2008-09-04 2012-12-12 中国科学院兰州化学物理研究所 离子液体催化合成聚甲氧基甲缩醛的方法
WO2011067229A1 (fr) * 2009-12-01 2011-06-09 Basf Se Utilisation de trioxane, obtenu à partir d'un procédé de séparation du trioxane d'un mélange trioxane/formaldéhyde/eau, pour la préparation de polyoxyméthylène dialkyléthers
CN102249868A (zh) 2010-05-18 2011-11-23 中国科学院兰州化学物理研究所 甲醛与甲醇缩醛化反应制备聚甲氧基二甲醚的工艺过程
CN102249869A (zh) 2010-05-18 2011-11-23 中国科学院兰州化学物理研究所 离子液体催化合成聚甲氧基二甲醚的工艺过程
CN103121924B (zh) * 2011-11-18 2014-12-10 中国石油化工股份有限公司 聚甲醛二甲醚的制备方法
CN103121926B (zh) * 2011-11-18 2015-02-11 中国石油化工股份有限公司 聚甲氧基甲缩醛制备方法
CN103664547B (zh) * 2012-09-05 2016-01-13 中国石油化工股份有限公司 合成聚甲醛二甲醚的方法
CN103739458B (zh) * 2012-10-17 2016-02-10 中国石油化工股份有限公司 聚甲醛二甲基醚的制备方法
CN103772164A (zh) 2012-10-18 2014-05-07 中国科学院兰州化学物理研究所 连续制备聚甲氧基二烷基醚的反应系统和工艺方法
CN103772163B (zh) 2012-10-18 2016-04-13 中国科学院兰州化学物理研究所 连续制备聚甲氧基二甲基醚的反应系统和工艺方法
DE102013001490A1 (de) * 2013-01-28 2014-08-14 Man Truck & Bus Ag Kraftstoff für Selbstzündungsmotoren basierend auf Monooxymethylendimethylether
CN103333055B (zh) 2013-06-09 2015-03-18 北京东方红升新能源应用技术研究院有限公司 一种浆态床催化加氢精制聚甲醛二烷基醚的方法
CN103333059B (zh) 2013-06-09 2014-09-17 北京东方红升新能源应用技术研究院有限公司 一种固定床催化加氢精制聚甲醛二烷基醚的方法
CN103664550B (zh) 2013-06-09 2015-05-27 北京东方红升新能源应用技术研究院有限公司 一种合成聚甲氧基甲缩醛的方法
CN104447236B (zh) * 2013-09-24 2016-08-10 中国石油化工股份有限公司 聚甲醛二甲基醚的提纯方法
CN104447238B (zh) * 2013-09-24 2016-06-08 中国石油化工股份有限公司 提纯聚甲醛二甲基醚的方法
CN104447237B (zh) * 2013-09-24 2016-08-24 中国石油化工股份有限公司 以甲醇制聚甲醛二甲醚的工艺方法
CN104513141A (zh) 2013-09-29 2015-04-15 苏州奥索特新材料有限公司 一种制备聚甲氧基二甲基醚的反应系统和方法
CN103709019A (zh) * 2013-12-09 2014-04-09 中国科学院兰州化学物理研究所 一种酸性离子液体催化合成低碳多醚类化合物的方法
CN104971667B (zh) 2014-04-01 2017-05-24 清华大学 一种由甲缩醛和多聚甲醛制备聚甲氧基二甲醚的流化床装置及方法
CN104974025B (zh) 2014-04-11 2017-12-08 清华大学 一种生产聚甲氧基二甲醚的方法
CN104031194A (zh) * 2014-06-27 2014-09-10 北京东方红升新能源应用技术研究院有限公司 聚甲氧基二甲醚作为环保型溶剂油的新用途
DE102014112021A1 (de) 2014-08-22 2016-02-25 Karlsruher Institut für Technologie Verfahren zur Herstellung von Oxymethylendialkylethern und deren Verwendung
CN105348053A (zh) * 2015-11-18 2016-02-24 常州大学 一种基于金属盐催化剂催化制备聚甲醛二甲醚的方法
CN107286002B (zh) * 2016-04-12 2020-09-04 中国石油化工股份有限公司 聚甲氧基二甲醚2的精制方法
CN107286003B (zh) * 2016-04-12 2020-06-09 中国石油化工股份有限公司 聚甲氧基二甲醚分离的工艺方法
CN107286001B (zh) * 2016-04-12 2020-10-30 中国石油化工股份有限公司 聚甲氧基二甲醚分离方法
DE102016222657A1 (de) 2016-11-17 2018-05-17 OME Technologies GmbH Verfahren zur Herstellung von Polyoxymethylendimethylethern aus Formaldehyd und Methanol in wässrigen Lösungen
US10377689B2 (en) 2016-11-17 2019-08-13 OME Technologies GmbH Process for preparing polyoxymethylene dimethyl ethers from formaldehyde and methanol in aqueous solutions
US10322397B2 (en) 2017-09-01 2019-06-18 Gas Technologies Llc Upgrading of a raw blend into a diesel fuel substitute: poly(dimethoxymethane)
CN108484371B (zh) * 2018-04-27 2021-05-07 东华工程科技股份有限公司 一种合成聚甲氧基二甲醚的反应系统
DE102019101927A1 (de) * 2019-01-25 2020-07-30 Technische Universität Darmstadt Verfahren zur Herstellung von Oxymethylenethern
CN112724000B (zh) * 2019-10-14 2022-12-09 中国石油化工股份有限公司 一种聚甲氧基二甲醚的生产方法
PL3831897T3 (pl) 2019-12-06 2024-02-26 Hubergroup Deutschland Gmbh Kompozycja farby drukowej lub lakieru zawierająca eter oksymetylenowy
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Also Published As

Publication number Publication date
CA2581502A1 (fr) 2006-05-04
WO2006045506A1 (fr) 2006-05-04
JP2008517960A (ja) 2008-05-29
US20070260094A1 (en) 2007-11-08

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