• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Procedure to synthesize glycidol. The invention relates to a method for obtaining glycidol in semicontinuous or continuous mode by decarboxylation of glycerol carbonate under reduced pressure, at a temperature less than or equal to 130ºC and in the presence of alkali metal and alkaline earth metal alkoxide catalysts, metal oxides, mixed metal oxides, metal stannates, and mixed metal stannates, all optionally supported on sio2, γ -al2 o3, mgo and zro2. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2603643A1
    申请号:ES201531136
    申请日:2015-07-30
    公开日:2017-02-28
    发明作者:José Ramón OCHOA GÓMEZ；Olga GÓMEZ DE MIRANDA JIMÉNEZ DE ABERASTUI；Noelia BLANCO PÉREZ；Belén MAESTRO MADURGA；Soraya PRIETO FERNÁNDEZ
    申请人:Fundacion Tecnalia Research and Innovation；
    IPC主号:
    专利说明:

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    protected terminals, for example forming ethers, such as, for example, polyethylene glycol 400, 600 or 2000 dimethyl ether, or tetramethylene glycol dimethyl ether.
    The reaction can be carried out both semi-continuously and continuously. In the first mode glycerol carbonate and catalyst are introduced into the reactor and glycidol is continuously removed by evaporation under reduced pressure. In the second procedure, glycerol carbonate is continuously fed at a predetermined flow rate to the reactor in which the catalyst has previously been introduced, and glycidol is continuously removed by evaporation under reduced pressure.
    In a particular embodiment, the catalysts are (C1-Cn) alkali metal and alkaline earth metal alkoxides, and are preferably selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide. The term "(C1-Cn) alkoxide" refers to the radical -O (C1-Cn) alkyl, wherein the term "alkyl" refers to a linear or branched, saturated hydrocarbon chain containing 1 to n carbon atoms. The alkoxide group is saturated containing only simple bonds. The saturated "(C1-Cn) alkoxide" may be substituted or unsubstituted as described in this description.
    In another particular embodiment, metal oxide type catalysts are selected from the group consisting of alkali metal and alkaline earth metal oxides and metals selected from zirconium, niobium, scandium, ytrium, lanthanum, zinc, cerium and tin, which can be used unsupported or supported on SiO2, -Al2O3, MgO and ZrO2; that is, optionally supported on SiO2, -Al2O3, MgO and ZrO2.
    In another particular embodiment, the catalysts are mixed metal oxides and are selected from the group consisting of mixtures of two or more alkali metal and alkaline earth metal oxides and metals selected from zirconium, niobium, scandium, ytrium, lanthanum, zinc, cerium and tin, which can be used unsupported or supported on SiO2, -Al2O3, MgO and ZrO2.
    In another particular embodiment, the catalysts are metal stannates and mixed metal stannates and are selected from the group consisting of metal stannates and mixed metal stannates of alkali and alkaline earth metals, preferably sodium and potassium. These catalysts are optionally supported on SiO2, -Al2O3, MgO and ZrO2. Metal stannate type catalysts are obtained by calcining the corresponding commercial hydrated stannates at temperatures above 200 ° C. Mixed metal stannate type catalysts
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    both are obtained by mechanically mixing the corresponding hydrated commercial stannates and calcining at temperatures above 200 ° C, or dissolving the corresponding commercial stannates hydrated in water, evaporating the water, drying the residue and calcining at temperatures above 200 ° C. The metal stannate and mixed metal stannate supported catalysts can, for example, be obtained by impregnating the support with an aqueous solution of the
    or of the metal stannates to deposit, drying the mixture and calcining. The term "stannate" includes ortho-stannates and meta-stannates. Therefore, the invention relates to metal ortho-stannates and meta-stannates and mixed metal ortho-stannates and meta-stannates.
    Catalysts formed by mixed oxides and oxides, supported or unsupported, can be manufactured by any of the methods well known in the art. Thus, for example, they can be obtained by: mechanical mixing; wet impregnation of the oxide that acts as a support with solutions of precursor agents of the oxide to be deposited (non-limiting examples are the nitrates, sulfates, chlorides, acetates, formates and oxalates of the corresponding metals) followed by drying and calcination; co-precipitation in basic medium of metal hydroxides from aqueous solutions of salts containing the corresponding metals (non-limiting examples are the nitrates, sulfates, chlorides, acetates, formates and oxalates of the corresponding metals) followed by drying and calcination; precipitation in basic medium of metal hydroxides on one of the oxides from aqueous solutions of salts containing the corresponding metals (non-limiting examples are nitrates, sulfates, chlorides, acetates, formates and oxalates of the corresponding metals) followed by drying and calcination; and sol-gel procedures. A large number of references about these and other reference procedures can be found in the literature. See, for example, Handbook in Heterogeneous Catalysis, Ed. Ertl, Knözinger, Schüth, Weitkamp, 2nd edition, vol 2, Wiley-VCH, 2008.
    The catalyst concentration, as a percentage by weight with respect to glycerol carbonate, can vary between 0.001% and 10%, but is preferably between 0.001% and 1%, since higher concentrations in many cases lead to a decrease in yield. Without wishing to be bound in any way to the theory, it is believed that the cause is that high concentrations of catalyst dramatically increase the ring-opening polymerization of both glycerol carbonate
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    by decarboxylation of glycidol carbonate, with a yield that allows the process to be industrially viable.
    Example 7 (of the invention)
    A reaction was carried out as in Example 6, but with a catalyst concentration of 0.60%, a reaction time of 5 hours and a temperature of 125 ° C. The yield of glycidol was 68.4%.
    Example 8 (of the invention)
    A reaction was carried out according to the semi-continuous mode of operation, using as a Cs2O catalyst supported on MgO with a Cs2O content of 30% by weight, prepared by the wet impregnation process and calcined at 600 ° C. The catalyst concentration was 0.2%, the reaction time of 6.5 hours, the pressure of 0.25 kPa and the temperature of 130 ° C. The glycidol yield was 70.5%.
    Example 9 (of the invention)
    A reaction was carried out according to the semi-continuous mode of operation, using as a Cs2O catalyst supported on MgO with a Cs2O content of 30% by weight, prepared by the wet impregnation process and calcined at 600 ° C. The catalyst concentration was 0.27%, the reaction time of 4.5 hours, the pressure of 0.25 kPa and the temperature of 130 ° C. The glycidol yield was 70.4%.
    Example 10 (of the invention)
    A reaction was carried out according to the semi-continuous mode of operation, using Cs2O catalyst obtained by calcining cesium carbonate at 600 ° C. The catalyst concentration was 0.2%, the reaction time of 3 hours, the pressure of 0.25 kPa and the temperature of 130 ° C. The glycidol yield was 67%.
    Example 11 (of the invention)
    A reaction was carried out according to the semi-continuous mode of operation, using as a catalyst calcined CaO at 900 ° C. The catalyst concentration was 0.16%, the reaction time of 6 hours, the pressure of 0.25 kPa and the temperature of 130 ° C. The glycidol yield was 67%.
    Example 12 (of the invention)
    A reaction was performed according to the semi-continuous mode of operation, using as
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    权利要求:
    Claims (1)
    [1]
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    同族专利:
    公开号 | 公开日
    US20180319756A1|2018-11-08|
    EP3330261A4|2019-03-20|
    JP2018524395A|2018-08-30|
    EP3330261A1|2018-06-06|
    ES2603643B1|2017-12-13|
    US10640478B2|2020-05-05|
    WO2017017307A1|2017-02-02|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2856413A|1956-07-23|1958-10-14|Jefferson Chem Co Inc|Method for preparing glycidol|
    US5164497A|1990-09-20|1992-11-17|Union Carbide Chemicals & Plastics Technology Corporation|Decarboxylation processes using mixed metal oxide catalysts|
    DE4225870A1|1992-08-05|1994-02-10|Basf Ag|Process for the preparation of glycerol carbonate|
    FR2760747B1|1997-03-12|1999-06-04|Organisation Nationale Interpr|PROCESS FOR THE MANUFACTURE OF GLYCIDOL OR A GLYCIDYL COMPOUND|
    WO2007145278A1|2006-06-15|2007-12-21|Kao Corporation|Process for production of glycidol|
    US7868192B1|2009-07-15|2011-01-11|Kao Corporation|Process for producing glycidol|
    KR101416706B1|2012-11-14|2014-07-09|한국과학기술연구원|Method for preparing glycidol|
    CN103554060A|2013-09-13|2014-02-05|华中科技大学|Catalyst used for synthesizing glycidol from glycerol and dimethyl carbonate by employing one-step method|GB2572385A|2018-03-28|2019-10-02|Green Lizard Tech Ltd|Process for the preparation of glycidol|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201531136A|ES2603643B1|2015-07-30|2015-07-30|PROCEDURE FOR SYNTHETIZING GLICIDOL|ES201531136A| ES2603643B1|2015-07-30|2015-07-30|PROCEDURE FOR SYNTHETIZING GLICIDOL|
    US15/748,599| US10640478B2|2015-07-30|2016-07-28|Glycidol synthesis method|
    EP16829907.1A| EP3330261A4|2015-07-30|2016-07-28|Glycidol synthesis method|
    JP2018504787A| JP6839172B2|2015-07-30|2016-07-28|How to synthesize glycidol|
    PCT/ES2016/070573| WO2017017307A1|2015-07-30|2016-07-28|Glycidol synthesis method|
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