WO2014005417A1 - Procédé de préparation du carbonate de diméthyle - Google Patents

Procédé de préparation du carbonate de diméthyle Download PDF

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Publication number
WO2014005417A1
WO2014005417A1 PCT/CN2013/000236 CN2013000236W WO2014005417A1 WO 2014005417 A1 WO2014005417 A1 WO 2014005417A1 CN 2013000236 W CN2013000236 W CN 2013000236W WO 2014005417 A1 WO2014005417 A1 WO 2014005417A1
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WO
WIPO (PCT)
Prior art keywords
reaction
carbonate
lipase
dimethyl carbonate
ionic liquid
Prior art date
Application number
PCT/CN2013/000236
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English (en)
Chinese (zh)
Inventor
张海波
王剑英
刘骏
郭宏涛
兰瑛
周晓海
Original Assignee
深圳市绿微康生物工程有限公司
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.)
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Application filed by 深圳市绿微康生物工程有限公司 filed Critical 深圳市绿微康生物工程有限公司
Publication of WO2014005417A1 publication Critical patent/WO2014005417A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates

Definitions

  • the invention relates to the field of biochemical industry, in particular to a method for preparing dimethyl carbonate by catalytically catalyzing a ionic liquid as a lipase. Background technique
  • the ionic liquid Compared with ordinary organic solvents, the ionic liquid has the following advantages:
  • the ionic liquid does not volatilize and is environmentally friendly. It is relatively safe in industrial production. It can adjust its solubility to substances through the design of anion and cation.
  • the ionic liquid is incompatible with some organic solvents, and can form an organic solvent-ionic liquid two-phase system or an organic solvent-water ionic liquid. Three-phase system. In general, ionic liquids should be in three forms -J , ⁇ , as a pure solvent; (2) as a co-solvent in the aqueous phase system; (3) as a co-solvent in a two-phase system. Lipase is the most widely reported enzyme in biocatalytic reactions in ionic liquids.
  • a fat peak of 0.3% of the mass fraction of the reactants is added to the step 3).
  • FIG. 3 is a schematic diagram showing the relationship between the reaction of methanol and propylene carbonate to prepare dimethyl carbonate and the reaction time by using an ionic liquid as a lipase promoter;
  • Figure 5 is a schematic view showing the relationship between the molar ratio of dimethyl carbonate and the material by reacting sterol with ethylene carbonate by using an ionic liquid as a promoter of a lipase;
  • the reactant methanol and propylene carbonate were sequentially added, and the molar ratio of methanol to propylene carbonate was 16:1, and the ionic liquid was 2 ml/g ( Based on the ester weight, v/w)); then the addition of 0.3% of the mass fraction of the extended Penicillium lipase; adding water, water content of 1% (based on ester weight, w / w)), stirring for transesterification,
  • the reaction temperature is 55 ° C
  • the reaction time is l ⁇ 160 h
  • the reaction pressure is 0.1 Mpa.
  • the ionic liquid-containing lipase is used as a catalyst for catalyzing the reaction of decyl alcohol with ethylene carbonate to prepare dinonyl carbonate and the reaction temperature.
  • FIG. 4 shows that ethylene carbonate increases with temperature. The conversion rate of the ester is gradually increased. When the reaction temperature is 55 °C, the conversion rate of ethylene carbonate is the highest, which is 85%; when the reaction temperature is 60 °C, the conversion rate of ethylene carbonate is still 84%; As the temperature increases, the conversion of ethylene carbonate gradually decreases.
  • the reactant methanol and ethylene carbonate are sequentially added, and the molar ratio of decyl alcohol to ethylene carbonate is 4:1-50:1.
  • Ionic liquid 2ml / g (based on ester weight, v / w); then added 0.3% of the reaction substance fraction of Penicillium expansum lipase; add water, water content of 1% (based on ester weight, w / w), stirring
  • the transesterification reaction was carried out at a reaction temperature of 55 ° C, a reaction time of 72 h, and a reaction pressure of 0.1 Mpa.
  • the selectivity of the reaction was greater than 90% after 72 h of reaction.
  • the lipase is removed by filtration, excess methanol is removed by decanting, and the product dimethyl carbonate is obtained.
  • the lipase is washed with acetone, dried at 40 ° C, and can be reused, and the catalytic activity is not reduce.
  • the molar ratio of the reactant sterol and ethylene carbonate or decyl alcohol to propylene carbonate, methanol to ethylene carbonate or decyl alcohol to propylene carbonate is added. 16: 1 ; then add 0.3% of the reaction mass fraction of the green ⁇ w ⁇ , ⁇ ⁇ / VIII, water content of 1% (based on the ester weight, w / w ), stirring to carry out the transesterification reaction, the reaction temperature of 55 ° C, The reaction time was 72 h, and the reaction pressure was 0.1 Mpa. After the reaction, the product dinonyl carbonate was obtained.
  • reaction solution was used for the analysis of diterpene carbonate content, and the conversion of ethylene carbonate was calculated to be 65% and the conversion ratio of propylene carbonate was 63% from the measured amount of dimethyl ester. .
  • the conversion rate of ethylene carbonate is as high as 81% ⁇ 91%
  • the conversion rate of propylene carbonate is as high as 81% ⁇ 92%
  • the conversion rate of ethylene carbonate is increased by 16% ⁇ 26%
  • the conversion rate of propylene carbonate Increased by 18% to 29%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

Cette invention concerne un procédé permettant de préparer du carbonate de diméthyle en utilisant un liquide ionique comme promoteur de lipase pour la catalyse. Le procédé comprend les étapes consistant à ajouter le liquide ionique dans un dispositif réactionnel, puis à ajouter successivement comme réactifs l'alcool méthylique et le carbonate d'éthylène, ou l'alcool méthylique et le carbonate de propylène dans le dispositif réactionnel, à ajouter la lipase aux réactifs et enfin à agiter pour que la réaction de transestérification se produise, pour ainsi obtenir le produit de carbonate de diméthyle après la réaction. L'invention utilise le liquide ionique comme promoteur de la lipase pour catalyser l'alcool méthylique et le carbonate d'éthylène ou l'alcool méthylique et le carbonate de propylène et exécuter la transestérification et préparer le carbonate de diméthyle. Le processus selon l'invention n'est pas seulement un processus à vitesse de conversion, à sélectivité et à universalité élevées, il s'agit également d'un processus simple, aux conditions de réaction modérées, au coût faible, qui est respectueux de l'environnement, dans lequel la lipase est recyclable, et qui présente ainsi des applications larges.
PCT/CN2013/000236 2012-07-03 2013-03-06 Procédé de préparation du carbonate de diméthyle WO2014005417A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210226548.9A CN103525874B (zh) 2012-07-03 2012-07-03 制备碳酸二甲酯的方法
CN201210226548.9 2012-07-03

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WO2014005417A1 true WO2014005417A1 (fr) 2014-01-09

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WO (1) WO2014005417A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015087341A1 (fr) 2013-12-12 2015-06-18 Council Of Scientific & Industrial Research Procédé amélioré de préparation de carbonate de diméthyle en utilisant des liquides ioniques comme catalyseur
CN112961871A (zh) * 2021-02-26 2021-06-15 源创核新(北京)新材料科技有限公司 一种重组质粒、包含其的基因工程菌及其在制备碳酸二甲酯中的应用
CN115108911A (zh) * 2022-05-26 2022-09-27 南京工业大学 一种环氧烷直接酯化制备碳酸二甲酯的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669366A (zh) * 2015-12-31 2016-06-15 天津中福工程技术有限公司 一种采用碱性离子液体作催化剂合成碳酸二乙酯的方法
CN110878020B (zh) * 2019-12-04 2021-11-30 大连理工大学 一种在低压下直接制备碳酸二甲酯的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4661609A (en) * 1986-07-31 1987-04-28 Texaco Inc. Process for cosynthesis of ethylene glycol and dimethyl carbonate
JP2003342236A (ja) * 2002-05-30 2003-12-03 Mitsubishi Chemicals Corp ジメチルカーボネートの製造方法
CN102126956A (zh) * 2010-11-30 2011-07-20 中国科学院过程工程研究所 一种制备碳酸二甲酯联产乙二醇的催化方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4661609A (en) * 1986-07-31 1987-04-28 Texaco Inc. Process for cosynthesis of ethylene glycol and dimethyl carbonate
JP2003342236A (ja) * 2002-05-30 2003-12-03 Mitsubishi Chemicals Corp ジメチルカーボネートの製造方法
CN102126956A (zh) * 2010-11-30 2011-07-20 中国科学院过程工程研究所 一种制备碳酸二甲酯联产乙二醇的催化方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DE, D.T. ET AL.: "Understanding structure-stability relationships of Candida antartica lipase B in ionic liquids.", BIOMACROMOLECULES, vol. 6, no. 3, May 2005 (2005-05-01), pages 1457 - 1464 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015087341A1 (fr) 2013-12-12 2015-06-18 Council Of Scientific & Industrial Research Procédé amélioré de préparation de carbonate de diméthyle en utilisant des liquides ioniques comme catalyseur
CN112961871A (zh) * 2021-02-26 2021-06-15 源创核新(北京)新材料科技有限公司 一种重组质粒、包含其的基因工程菌及其在制备碳酸二甲酯中的应用
CN115108911A (zh) * 2022-05-26 2022-09-27 南京工业大学 一种环氧烷直接酯化制备碳酸二甲酯的方法

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CN103525874A (zh) 2014-01-22

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