WO2010063694A1 - Process for removing an alkanol impurity from an organic carbonate stream - Google Patents

Process for removing an alkanol impurity from an organic carbonate stream Download PDF

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Publication number
WO2010063694A1
WO2010063694A1 PCT/EP2009/066110 EP2009066110W WO2010063694A1 WO 2010063694 A1 WO2010063694 A1 WO 2010063694A1 EP 2009066110 W EP2009066110 W EP 2009066110W WO 2010063694 A1 WO2010063694 A1 WO 2010063694A1
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WO
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Prior art keywords
carbonate
alkanol
impurity
stream containing
extraction solvent
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Application number
PCT/EP2009/066110
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English (en)
French (fr)
Inventor
Cyrille Paul Allais
Garo Garbis Vaporciyan
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Shell Internationale Research Maatschappij B.V.
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Publication date
Application filed by Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Priority to JP2011538003A priority Critical patent/JP5579737B2/ja
Priority to CN200980140531.8A priority patent/CN102186806B/zh
Publication of WO2010063694A1 publication Critical patent/WO2010063694A1/en

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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
    • C07C68/08—Purification; Separation; Stabilisation

Definitions

  • the present invention relates to a process for removing an alkanol impurity from a stream containing an organic carbonate and the alkanol impurity.
  • organic carbonates are cyclic alkylene carbonates (such as ethylene carbonate) and non-cyclic dialkyl carbonates (such as diethyl carbonate) . It is well known to make cyclic alkylene carbonate by reaction of alkylene oxide (such as ethylene oxide) with carbon dioxide in the presence of a suitable catalyst. Such processes have been described for example in US4508927 and US5508442.
  • Dialkyl carbonates can be produced by reaction of alkylene carbonate with alkanol. Where alkylene carbonate (such as ethylene carbonate) is reacted with alkanol (such as ethanol) , the products are dialkyl carbonate (such as diethyl carbonate) and alkanediol (such as monoethylene glycol) .
  • alkanol such as ethanol
  • dialkyl carbonate such as diethyl carbonate
  • alkanediol such as monoethylene glycol
  • organic carbonate streams containing one or more alkanol impurities may be produced.
  • alkanol impurity is an ether alkanol, for example an alkoxy alkanol.
  • ethylene oxide formed by back-reaction of ethylene carbonate into ethylene oxide and carbon dioxide, into 2- ethoxyethanol (ethyl oxitol) may take place.
  • ethyl oxitol may be formed by a side-reaction of ethanol with ethylene carbonate in such a way that carbon dioxide is released and ethyl oxitol is produced.
  • a side-reaction between ethanol and monoethylene glycol may take place producing ethyl oxitol and water.
  • ethyl oxitol may be formed via decarboxylation of hydroxyethyl ethyl carbonate.
  • the product stream from a reactor where ethanol and ethylene carbonate are reacted into diethyl carbonate and monoethylene glycol may comprise unconverted ethanol, unconverted ethylene carbonate, diethyl carbonate, monoethylene glycol and the above- mentioned ethyl oxitol impurity.
  • the presence of said alkoxy alkanol impurity may be detrimental in any subsequent production process.
  • Said alkoxy alkanol impurity may for example end up in the dialkyl carbonate that is used as a starting material for the synthesis of diphenyl carbonate from said dialkyl carbonate and phenol.
  • dialkyl carbonate is diethyl carbonate and the alkoxy alkanol impurity is ethyl oxitol
  • said ethyl oxitol may react with the phenol starting material and/or with the diphenyl carbonate product .
  • Alkoxy alkanols (such as ethyl oxitol) are neither good leaving groups. Therefore, in case phenyl 2-ethoxyethyl carbonate is present in a diphenyl carbonate feed to be reacted with BPA, phenol will be released easily from said phenyl 2-ethoxyethyl carbonate but not ethyl oxitol which will consequently stop the polymerization process at one end of the chain. Consequently, phenyl 2-ethoxyethyl carbonate has to be removed from diphenyl carbonate before the latter is contacted with BPA.
  • the distillation as referred to above may result in a top stream containing diethyl carbonate and unconverted ethanol and a bottom stream containing monoethylene glycol and unconverted ethylene carbonate. Most likely, all of the ethyl oxitol ends up in the top stream. However, depending on the specific conditions under which distillation is carried out, part of the ethyl oxitol may end up in the bottom stream. Subsequently, said top stream may be further separated by means of distillation into a top stream containing unconverted ethanol which can be recycled to the reactor where diethyl carbonate and monoethylene glycol are produced, and a bottom stream containing diethyl carbonate and the ethyl oxitol impurity.
  • the alkanol impurity has to be removed therefrom as that might interfere said subsequent process and/or any further processes.
  • oxitol impurity In principle, ethyl oxitol and diethyl carbonate could be separated by means of a further distillation step. However because of the small difference in boiling point between diethyl carbonate and ethyl oxitol (see above table) , such separation is very cumbersome requiring many distillation steps and stages. Therefore, there is a need to find a simple method of removing an alkanol impurity from an organic carbonate stream containing such alkanol impurity.
  • the present invention relates to a process for removing an alkanol impurity from a stream containing an organic carbonate and the alkanol impurity, comprising contacting the stream with an extraction solvent and separating the extraction solvent phase from the organic carbonate phase.
  • the organic carbonate in the stream from which the alkanol impurity has to be removed in accordance with the present invention may be a di (Ci-C 5 ) alkyl carbonate, wherein the alkyl groups (straight, branched and/or cyclic) may be the same or different, such as methyl, ethyl and propyl; or a di (C 5 -C 7 ) aryl carbonate, wherein the aryl groups may be the same or different, such as phenyl; or a (Ci-C 5 ) alkyl (C 5 -C 7 ) aryl carbonate, wherein the alkyl group and the aryl group are as defined above; or a cyclic (Ci-Cio) alkylene carbonate, such as the carbonate of ethylene, propylene, butadiene or styrene; or a mixture of such organic carbonates.
  • the organic carbonate is a dialkyl carbonate, more specifically diethyl carbonate.
  • the alkanol impurity which has to be removed from the stream containing the organic carbonate and said impurity in accordance with the present invention may be an ether alkanol, more specifically an alkoxy alkanol, most specifically 2-ethoxyethanol, as described above.
  • the amount of the alkanol impurity in the stream containing the organic carbonate and said impurity may be comprised in the range of from 0.1 to 10 wt.%, specifically 0.3 to 8 wt.%, more specifically 0.5 to 6 wt.% and most specifically 0.5 to 5 wt.%.
  • the extraction solvent is a polar extraction solvent.
  • the extraction solvent is selected from the group consisting of water, Ci-C 4 aliphatic ketones, Ci-C 4 aliphatic alcohols and Ci-C 4 aliphatic carboxylic acids.
  • the extraction solvent is water or a Ci- C 4 aliphatic carboxylic acid, such as formic acid, acetic acid, propionic acid or butyric acid.
  • the extraction solvent is water.
  • contacting time may be in the order of 1 minute to 24 hours, for example 3 minutes to 12 hours.
  • the temperature at which the present invention is performed that is to say the temperature of the biphasic mixture of extraction solvent and organic carbonate, may be comprised in the range of from -50 to 100 0 C. Surprisingly, it has been found that at relatively low temperature the alcohol impurity is extracted into the extraction solvent to the greatest extent in the present process. This is illustrated in the Examples below.
  • said temperature is preferably comprised in the range of from 0 to 40 0 C, more preferably 1 to 30 0 C, more preferably 2 to 25 0 C, and most preferably 2 to 10 0 C.
  • the temperature is preferably at least 0 0 C, more preferably at least 1 0 C, more preferably at least 2 0 C, and most preferably at least 3 0 C.
  • the temperature is preferably at most 40 0 C, more preferably at most 35 0 C, more preferably at most 30 0 C, more preferably at most
  • a suitable weight ratio of extraction solvent to the stream containing the organic carbonate and the alkanol impurity is comprised in the range of from 10:1 to 1:10.
  • said weight ratio is comprised in the range of from 5:1 to 1:5, more preferably 3:1 to 1:3, even more preferably 2:1 to 1:2.
  • said weight ratio amounts to 1:1.
  • the pressure at which the present process is carried out may be subatmospheric, atmospheric or superatmospheric pressure.
  • said pressure is atmospheric pressure.
  • the extraction solvent phase should be separated from the organic carbonate phase, in accordance with the invention, so that a stream containing the organic carbonate from which stream alcohol impurity has been removed, remains.
  • an aqueous phase has to be separated from an organic phase. Any skilled person can find a suitable method of separating the extraction solvent phase from the organic carbonate phase in the present process.
  • the stream containing the organic carbonate and the alkanol impurity is a stream containing a dialkyl carbonate that has been produced from reacting an alkanol with an alkylene carbonate
  • the stream usually contains unconverted alkanol reactant in addition to the alkanol impurity.
  • the stream containing the organic carbonate and the alkanol impurity is a stream containing dialkyl carbonate, unconverted alkanol and an alkanol impurity
  • contacting of said stream with an extraction solvent to extract and remove the alkanol impurity in accordance with the present invention is preferably performed after the step wherein dialkyl carbonate is separated from unconverted alkanol.
  • Separation of the dialkyl carbonate from unconverted alkanol may be effected by means of distillation. Such distillation results in a top stream containing the unconverted alkanol (such as ethanol) and a bottom stream containing the dialkyl carbonate (such as diethyl carbonate) , in a case where the unconverted alkanol has been reacted in a preceding step with an alkylene - -
  • the present invention advantageously results in the removal of an alkanol impurity in organic carbonate streams, which alkanol impurity might have interfered in any subsequent process using said organic carbonate if it would not have been removed.
  • the present invention also relates to a process for the preparation of a dialkyl carbonate and an alkanediol comprising:
  • step (d) separating unconverted alkanol from the top stream containing unconverted alkanol, dialkyl carbonate and the alkanol impurity obtained in step (b) to obtain a bottom stream containing dialkyl carbonate and the alkanol impurity, which process further comprises
  • step (e) contacting the bottom stream containing dialkyl carbonate and the alkanol impurity obtained in step (d) with an extraction solvent and separating the extraction solvent phase from the organic carbonate phase.
  • the transesterification catalyst to be used in step (a) of the above-mentioned process may be one of many suitable homogeneous and heterogeneous transesterification catalysts known from prior art.
  • suitable homogeneous transesterification catalysts have been described in US5359118 and include hydrides, oxides, hydroxides, alkanolates, amides, or salts of alkali metals, i.e., lithium, sodium, potassium, rubidium and cesium.
  • Preferred homogeneous transesterification catalysts are hydroxides or alkanolates of potassium or sodium.
  • Other suitable homogeneous transesterification catalysts are alkali metal salts, such as acetates, propionates, butyrates, or carbonates.
  • Suitable catalysts are described in US5359118 and the references mentioned therein, such as EP274953A, US3803201, EP1082A, and EP180387A.
  • Suitable heterogeneous transesterification catalysts to be used in step (a) of the above-mentioned process include ion exchange resins that contain functional groups.
  • Suitable functional groups include tertiary amine groups and quaternary ammonium groups, and also sulphonic acid and carboxylic acid groups.
  • Further suitable catalysts include alkali metal and alkaline earth metal silicates. Suitable catalysts have been disclosed in
  • the heterogeneous catalyst may be selected from ion exchange resins comprising a polystyrene matrix and tertiary amine functional groups. - -
  • Amberlyst A-21 (ex Rohm & Haas) comprising a polystyrene matrix to which N, N-dimethylamine groups have been attached.
  • Eight classes of transesterification catalysts, including ion exchange resins with tertiary amine and quaternary ammonium groups, are disclosed in J F Knifton et al . , J. MoI. Catal, 61_ (1991) 389ff.
  • transesterification conditions for step (a) of the above-mentioned process are known in the art and suitably include a temperature from 40 to 200 0 C, and a pressure from 50 to 5000 kPa (0.5 to 50 bar) .
  • the present invention relates to a process for making a diaryl carbonate, comprising contacting, in the presence of a transesterification catalyst, an aryl alcohol with a stream containing a dialkyl carbonate from which stream an alkanol impurity has been removed in accordance with any one of the above-described processes.
  • the present invention relates to a process for making a diaryl carbonate, comprising contacting a stream containing a dialkyl carbonate and an alkanol impurity with an extraction solvent and separating the extraction solvent phase from the organic carbonate phase in accordance with any one of the above- described processes, and then contacting, in the presence of a transesterification catalyst, an aryl alcohol with the stream containing the dialkyl carbonate.
  • said diaryl carbonate is diphenyl carbonate and said aryl alcohol is phenol.
  • transesterification catalyst and other transesterification conditions are equally applicable to said process for making a diaryl carbonate .
  • a certain amount of a solution A containing 99.16 wt. % of diethyl carbonate (DEC), 0.76 wt . % of ethyl oxitol (EtOx; 2-ethoxyethanol) and 0.04 wt . % of ethanol (EtOH) was placed in a glass vial.
  • a certain amount of deionised water (extraction solvent) was then added to said vial.
  • the temperature, the amounts of solution A and water added, and the weight ratio of amount of added water to amount of added solution A, in Experiments 1-5 are mentioned in the table below.
  • the vial was then closed and homogenized by shaking for 5 minutes before it was allowed to phase separate at the above-mentioned temperature for one day. During said one-day period, the contents of the vials was re- homogenized three times. At the end of the experiment, the aqueous phase was separated from the organic phase and the composition of the samples was analyzed by means of gas chromatography, the results of which are shown in the table below. - -

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/EP2009/066110 2008-12-01 2009-12-01 Process for removing an alkanol impurity from an organic carbonate stream WO2010063694A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2011538003A JP5579737B2 (ja) 2008-12-01 2009-12-01 有機カーボナート流からアルカノール不純物を除去する方法
CN200980140531.8A CN102186806B (zh) 2008-12-01 2009-12-01 从有机碳酸酯物流中脱除链烷醇杂质的方法

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EP08170388 2008-12-01
EP08170388.6 2008-12-01

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WO2010063694A1 true WO2010063694A1 (en) 2010-06-10

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9284254B2 (en) 2012-09-20 2016-03-15 Sabic Global Technologies B.V. Process for the continuous manufacture of aryl alkyl carbonate and/or diaryl carbonate using vapor recompression
WO2020126989A1 (en) * 2018-12-18 2020-06-25 Shell Internationale Research Maatschappij B.V. Process for preparing dialkyl carbonate and alkanediol
WO2021063853A1 (en) * 2019-10-03 2021-04-08 Shell Internationale Research Maatschappij B.V. Process for preparing dialkyl carbonate and alkanediol
EP3831805A1 (en) * 2019-12-06 2021-06-09 Shell Internationale Research Maatschappij B.V. Process for the preparation of a dialkyl carbonate and an alkanediol
WO2021110627A1 (en) 2019-12-06 2021-06-10 Shell Internationale Research Maatschappij B.V. Process for removing an ether alkanol impurity from an organic carbonate stream

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963586A (en) * 1973-10-26 1976-06-15 Snam Progetti S.P.A. Extractive distillation of a dimethyl carbonate feed with water
EP0274953A1 (fr) * 1986-12-23 1988-07-20 Societe Francaise D'organo-Synthese Procédé de préparation de carbonates organiques par transesterification
US5328615A (en) * 1993-01-29 1994-07-12 Amoco Corporation Alkyl carbonate recovery process
US5338878A (en) * 1993-01-29 1994-08-16 Amoco Corporation Alkyl carbonate extraction process
US5359118A (en) * 1992-05-15 1994-10-25 Bayer Aktiengesellschaft Process for the continuous preparation of dialkyl carbonates
EP1640357A1 (en) * 2003-06-27 2006-03-29 Asahi Kasei Chemicals Corporation Method for producing aromatic carbonate

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06263694A (ja) * 1993-03-11 1994-09-20 Mitsubishi Petrochem Co Ltd ジアリールカーボネートの製造方法
JP3960528B2 (ja) * 2002-04-11 2007-08-15 三菱化学株式会社 ジメチルカーボネート及びエチレングリコールの製造方法
ES2367797T3 (es) * 2003-06-27 2011-11-08 Asahi Kasei Chemicals Corporation Método para producir un carbonato aromático.
US20080255336A1 (en) * 2007-01-23 2008-10-16 Timothy Michael Nisbet Process for the preparation of diaryl carbonate
TWI414515B (zh) * 2007-01-23 2013-11-11 Shell Int Research 製備烷二醇及碳酸二烷酯的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963586A (en) * 1973-10-26 1976-06-15 Snam Progetti S.P.A. Extractive distillation of a dimethyl carbonate feed with water
EP0274953A1 (fr) * 1986-12-23 1988-07-20 Societe Francaise D'organo-Synthese Procédé de préparation de carbonates organiques par transesterification
US5359118A (en) * 1992-05-15 1994-10-25 Bayer Aktiengesellschaft Process for the continuous preparation of dialkyl carbonates
US5328615A (en) * 1993-01-29 1994-07-12 Amoco Corporation Alkyl carbonate recovery process
US5338878A (en) * 1993-01-29 1994-08-16 Amoco Corporation Alkyl carbonate extraction process
EP1640357A1 (en) * 2003-06-27 2006-03-29 Asahi Kasei Chemicals Corporation Method for producing aromatic carbonate

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9284254B2 (en) 2012-09-20 2016-03-15 Sabic Global Technologies B.V. Process for the continuous manufacture of aryl alkyl carbonate and/or diaryl carbonate using vapor recompression
WO2020126989A1 (en) * 2018-12-18 2020-06-25 Shell Internationale Research Maatschappij B.V. Process for preparing dialkyl carbonate and alkanediol
CN113166031A (zh) * 2018-12-18 2021-07-23 国际壳牌研究有限公司 用于制备碳酸二烷基酯和链烷二醇的方法
CN113166031B (zh) * 2018-12-18 2024-01-19 国际壳牌研究有限公司 用于制备碳酸二烷基酯和链烷二醇的方法
US12110269B2 (en) 2018-12-18 2024-10-08 Shell Usa, Inc. Process for preparing dialkyl carbonate and alkanediol
WO2021063853A1 (en) * 2019-10-03 2021-04-08 Shell Internationale Research Maatschappij B.V. Process for preparing dialkyl carbonate and alkanediol
US12098125B2 (en) 2019-10-03 2024-09-24 Shell Usa, Inc. Process for preparing dialkyl carbonate and alkanediol
EP3831805A1 (en) * 2019-12-06 2021-06-09 Shell Internationale Research Maatschappij B.V. Process for the preparation of a dialkyl carbonate and an alkanediol
WO2021110627A1 (en) 2019-12-06 2021-06-10 Shell Internationale Research Maatschappij B.V. Process for removing an ether alkanol impurity from an organic carbonate stream

Also Published As

Publication number Publication date
CN102186806B (zh) 2015-01-28
JP5579737B2 (ja) 2014-08-27
CN102186806A (zh) 2011-09-14
JP2012510450A (ja) 2012-05-10

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