CN102186806A - 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 PDFInfo
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- CN102186806A CN102186806A CN2009801405318A CN200980140531A CN102186806A CN 102186806 A CN102186806 A CN 102186806A CN 2009801405318 A CN2009801405318 A CN 2009801405318A CN 200980140531 A CN200980140531 A CN 200980140531A CN 102186806 A CN102186806 A CN 102186806A
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- carbonate
- alkanol
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- unconverted
- dialkyl
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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
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Abstract
The 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.
Description
The present invention relates to from the logistics that contains organic carbonate and alkanol impurity, remove the method for alkanol impurity.
The example of organic carbonate is cyclic alkylidene carbonic ether (for example ethylidene carbonic ether) and non-annularity dialkyl carbonate (for example diethyl carbonate).Be well known that in the presence of appropriate catalyst by making oxirane (for example oxyethane) and carbon dioxide reaction prepare the cyclic alkylidene carbonic ether.These methods for example have been disclosed among the US4508927 and US5508442.
Can produce dialkyl carbonate by making the reaction of alkylene carbonate and alkanol.Under the situation of alkylene carbonate (for example ethylidene carbonic ether) and alkanol (for example ethanol) reaction therein, product is dialkyl carbonate (for example diethyl carbonate) and alkanediol (for example monoethylene glycol).This method is known and the example is disclosed among the US5359118.This document discloses wherein by alkylene carbonate and C
1-C
4Chain triacontanol ester exchange preparation two (C
1-C
4Alkyl) method of carbonic ether and alkanediol.
Can produce the organic carbonate logistics that contains one or more alkanol impurity through alkylene carbonate by the difference place in the described entire method of olefin oxide production dialkyl carbonate.An example of this alkanol impurity is ether alkanol, for example alkoxy chain triacontanol.For example, ethanol is with in the ethylidene carbonate reaction becomes the reactor of diethyl carbonate and monoethylene glycol therein, the side reaction that ethanol and oxyethane generate cellosolvo (ethyl glycol list ether (ethyl oxitol)) may take place, and described oxyethane becomes oxyethane and carbonic acid gas to form by ethylidene carbonic ether reversed reaction.In addition, can form ethyl glycol list ether by the side reaction of ethanol and ethylidene carbonic ether, its reactive mode release of carbon dioxide also produces ethyl glycol list ether.Again further, the side reaction that may take place between ethanol and the monoethylene glycol produces ethyl glycol list ether and water.Even more further, can form ethyl glycol list ether through the decarboxylation of hydroxyethyl ethyl carbonate ester.
Therefore, become the product logistics of the reactor of diethyl carbonate and monoethylene glycol can comprise unconverted ethanol, unconverted ethylidene carbonic ether, diethyl carbonate, monoethylene glycol and above-mentioned ethyl glycol list ether impurity with the ethylidene carbonate reaction from ethanol wherein.The existence of described alkoxy chain triacontanol impurity can be harmful to any production technique subsequently.Described alkoxy chain triacontanol impurity can for example terminate in the dialkyl carbonate, and described dialkyl carbonate is as the parent material by described dialkyl carbonate and the synthetic diphenyl carbonate of phenol.For example, dialkyl carbonate is that diethyl carbonate and alkoxy chain triacontanol impurity are under the situation of ethyl glycol list ether therein, and described ethyl glycol list ether can react with the phenol parent material and/or with the diphenyl carbonate product.
The direct reaction of phenol and ethyl glycol list ether can cause producing phenyl 2-ethoxyethylether, has therefore lost valuable phenol reactant thing.In addition, this reaction causes introducing during the course undesirable chemical, therefore causes separation problem.
Diphenyl carbonate and the reaction of ethyl glycol list ether cause the product loss because produce phenyl 2-ethoxyethyl group carbonic ether.In addition, back one product aggregates in the polycarbonate material effect of playing " poisonous substance " at any diphenyl carbonate subsequently.For example, when diphenyl carbonate and dihydroxyphenyl propane (BPA) reaction, form polycarbonate and phenol.Diphenyl carbonate can react with BPA, and this is because phenol is good relatively leavings group.But can not use dialkyl carbonate (for example diethyl carbonate) by producing polycarbonate with the BPA reaction, this is because alkanol is not good leavings group.Alkoxy chain triacontanol (for example ethyl glycol list ether) neither be good leavings group.Therefore, phenyl 2-ethoxyethyl group carbonic ether be present in with the diphenyl carbonate raw material of BPA reaction in situation under, phenol discharges from described phenyl 2-ethoxyethyl group carbonic ether easily, but ethyl glycol list ether is then not all right, and it will stop polymerization process at an end of chain.Therefore, before diphenyl carbonate and BPA reaction, must from diphenyl carbonate, remove phenyl 2-ethoxyethyl group carbonic ether.
More than exemplified under the situation that forms the organic carbonate logistics that contains alkanol impurity therein, wished to take place organic carbonate wherein and remove described alkanol impurity before changing into any technology subsequently of valuable end product.For example, need before reacting, diethyl carbonate and phenol from the diethyl carbonate logistics that contains ethyl glycol list ether impurity, remove any ethyl glycol list ether impurity.
Become the above-mentioned example of diethyl carbonate and monoethylene glycol with the ethylidene carbonate reaction with reference to ethanol wherein, can also contain the product logistics of unconverted ethanol and ethylidene carbonic ether and ethyl glycol list ether by product by fractionation by distillation.In following table, mentioned the boiling point of various components in described product logistics.
| Component | Boiling point (℃) |
| Ethanol | 78.4 |
| Diethyl carbonate | 126-128 |
| Ethyl glycol list ether | 135 |
| Monoethylene glycol | 197.3 |
| The ethylidene carbonic ether | 260.4 |
Above-mentioned distillation can cause containing diethyl carbonate and unconverted alcoholic acid overhead stream, and the tower base stream that contains monoethylene glycol and unconverted ethylidene carbonic ether.Most probably, all ethyl glycol list ether terminate in the overhead stream.But depend on the actual conditions when distilling, a part of ethyl glycol list ether can terminate in the tower base stream.Subsequently, can described overhead stream further be separated into the tower base stream that contains unconverted alcoholic acid overhead stream and contain diethyl carbonate and ethyl glycol list ether impurity by distillation, described overhead stream is capable of circulation to be got back in the reactor that wherein produces diethyl carbonate and monoethylene glycol.
As mentioned above, organic carbonate changes into valuable end product in any technology subsequently before, must therefrom remove the alkanol impurity that may disturb described technology subsequently and/or any further technology.For above-mentioned example, this means and from the tower base stream that contains diethyl carbonate and ethyl glycol list ether impurity, to remove ethyl glycol list ether impurity.In principle, further distilation steps be can pass through, ethyl glycol list ether and diethyl carbonate separated.But because the boiling-point difference little (ginseng sees the above table) of diethyl carbonate and ethyl glycol list ether, therefore this separation bothers very much, needs many distilation steps and stage.Therefore, need to seek simple method and from the organic carbonate logistics that contains alkanol impurity, remove this alkanol impurity.
It has surprisingly been found that by make the organic carbonate logistics and extract the solvent contact and separation and Extraction solvent phase and organic carbonate mutually, from this logistics, remove this alkanol impurity by alkanol impurity being extracted in the extraction solvent phase.
Therefore, the present invention relates to remove the method for alkanol impurity from the logistics that contains organic carbonic ether and alkanol impurity, this method comprises makes described logistics contact with extracting solvent, with separation and Extraction solvent phase and organic carbonate mutually.
Must therefrom to remove the organic carbonate in the logistics of alkanol impurity can be two (C to alkane according to the present invention
1-C
5) alkyl carbonate, wherein alkyl (straight chain, side chain and/or ring-type) can be identical or different, for example is methyl, ethyl and propyl group; Or two (C
5-C
7) aryl carbonates, wherein aryl can be identical or different, for example phenyl; Or (C
1-C
5) alkyl (C
5-C
7) aryl carbonates, wherein alkyl and aryl are as defined above; Or ring-type (C
1-C
10) alkylene carbonate, for example ethylidene carbonic ether, propylene carbonate, butylidene carbonic ether or styryl carbonic ether; Or the mixture of these organic carbonates.Particularly, organic carbonate is a dialkyl carbonate, more specifically is diethyl carbonate.
The described alkanol impurity that must remove from the logistics that contains organic carbonate and alkanol impurity according to the present invention can be the ether alkanol, is alkoxy chain triacontanol more specifically, is specially cellosolvo most, as mentioned above.
The amount of described alkanol impurity can be specially 0.3-8wt% in the 0.1-10wt% scope in the logistics that contains organic carbonate and alkanol impurity, more specifically is 0.5-6wt% and is specially 0.5-5wt% most.
In the method for the invention, the logistics that contains organic carbonic ether and alkanol impurity with extract solvent and contact and cause forming extraction solvent phase and organic carbonate mutually.In order to make the extraction solvent phase contain described alkanol impurity, pure impurity is extracting the solvent planted agent than easier to be molten in organic carbonate.Preferably, extracting solvent is that polarity is extracted solvent.More preferably, extract solvent and be selected from water, C
1-C
4Aliphatic ketone, C
1-C
4Fatty alcohol and C
1-C
4Aliphatic carboxylic acid.More preferably, extracting solvent is water or C
1-C
4Aliphatic carboxylic acid, for example formic acid, acetate, propionic acid or butyric acid.Most preferably, extracting solvent is water.
In the method for the invention, the logistics that contains organic carbonic ether and alkanol impurity with should be enough to finish leaching process the duration of contact of extracting solvent.Can be 1 minute-24 hours magnitude described duration of contact, for example is 3 minutes-12 hours.
Enforcement temperature of the present invention is promptly extracted the temperature of the two-phase mixture of solvent and organic carbonate can be in-50 to 100 ℃ scope.It has surprisingly been found that in the method for the invention pure impurity extracts in the solvent at utmost to extract under low temperature relatively.This is described in following embodiment.Therefore, in the present invention, described temperature preferably in 0-40 ℃ of scope, more preferably 1-30 ℃, more preferably 2-25 ℃ and most preferably 2-10 ℃.According to the present invention, described temperature is preferably at least 0 ℃, and more preferably at least 1 ℃, more preferably at least 2 ℃ and most preferably at least 3 ℃.In addition, according to the present invention, preferably at the most 40 ℃ of described temperature, more preferably at the most 35 ℃, more preferably at the most 30 ℃, more preferably at the most 25 ℃, more preferably at the most 20 ℃, more preferably at the most 15 ℃ and most preferably at the most 10 ℃.
The suitable weight ratio of extracting solvent and the logistics that contains organic carbonic ether and alkanol impurity is 10: 1-1: in 10 the scope.Preferably, described weight ratio is 5: 1-1: in 5 the scope, and more preferably 3: 1-1: 3, even more preferably 2: 1-1: 2.Most preferably, described weight ratio is 1: 1.
The enforcement pressure of the inventive method can be to be lower than normal atmosphere, to equal normal atmosphere or to be higher than atmospheric pressure.Preferably, described pressure is normal atmosphere.
According to the present invention, after described extraction, extracting solvent phase should be separated with organic carbonate, so that keep the logistics that contains organic carbonate that pure impurity has therefrom removed.Water is to extract under the situation of solvent therein, must water phase separated and organic phase.In the method for the invention, those skilled in the art can find suitable method separation and Extraction solvent phase and organic carbonate mutually.
The logistics that contains organic carbonic ether and alkanol impurity therein is to contain under the flow situation of dialkyl carbonate (it is produced by the reaction of alkanol and alkylene carbonate); this logistics also contains unconverted alkanol reactant usually except containing alkanol impurity.The reference of wherein describing this organic carbonate logistics formation is incorporated in the specification sheets of the present invention.
The logistics that contains organic carbonate and alkanol impurity therein is to contain under the situation of the logistics of dialkyl carbonate, unconverted alkanol and alkanol impurity, preferably separate therein after the step of dialkyl carbonate and unconverted alkanol according to the present invention, described logistics is contacted, to extract and to remove alkanol impurity with extracting solvent.
Can dialkyl carbonate be separated with unconverted alkanol by distillation.Unconverted therein alkanol produces under the situation of dialkyl carbonate and alkanediol with the alkylene carbonate reaction in previous step, this distillation causes containing the overhead stream of unconverted alkanol (for example ethanol), and the tower base stream that contains dialkyl carbonate (for example diethyl carbonate).
The present invention advantageously causes removing the alkanol impurity in the organic carbonate logistics, if described alkanol impurity it be not removed and may disturb any technology subsequently of using described organic carbonate.
Therefore, the invention still further relates to the method for preparing dialkyl carbonate and alkanediol, this method comprises:
(a) in the presence of transesterification catalyst, make the reaction of alkylene carbonate and alkanol, to obtain to contain the product mixtures of unconverted alkylene carbonate, unconverted alkanol, dialkyl carbonate, alkanediol and alkanol impurity;
(b) from reaction mixture, separate unconverted alkylene carbonate and alkanediol, to obtain to contain the overhead stream of unconverted alkanol, dialkyl carbonate and alkanol impurity;
(c) reclaim alkanediol; With
(d) separate unconverted alkanol in the overhead stream that contains unconverted alkanol, dialkyl carbonate and alkanol impurity that from step (b), obtains, to obtain to contain the tower base stream of dialkyl carbonate and alkanol impurity, described method further comprises:
(e) tower base stream that contains dialkyl carbonate and alkanol impurity that obtains in the step (d) is contacted with the extraction solvent, with separation and Extraction solvent phase and organic carbonate mutually.
Remove from the logistics that contains organic carbonate and alkanol impurity at the above and to make described logistics comprising of alkanol impurity and to extract that solvent contact and separation and Extraction solvent phase and organic carbonate universal method mutually, all above-described embodiments and preferred version also are applied to above-mentioned described method and prepare respectively in the concrete grammar of dialkyl carbonate and alkanediol, more particularly are applied in the step (e).
Employed transesterification catalyst can be one of the known many suitable homogeneous phases of prior art and heterogeneous transesterification catalyst in the step in above-mentioned method (a).
For example, suitable homogeneous phase transesterification catalyst has been disclosed among the US5359118 and comprises that hydride, oxide compound, oxyhydroxide, alkane alkoxide, acid amides or basic metal are the salt of lithium, sodium, potassium, rubidium and caesium.Preferred homogeneous phase transesterification catalyst is the oxyhydroxide or the alkane alkoxide of potassium or sodium.Other suitable homogeneous phase transesterification catalyst is alkali-metal salt, for example acetate, propionic salt, butyrates or carbonate.Appropriate catalyst is disclosed in US5359118 and the reference mentioned for example among EP274953A, US3803201, EP1082A and the EP180387A within it.
Employed suitable heterogeneous transesterification catalyst comprises the ion exchange resin that contains functional group in the step in above-mentioned method (a).Suitable functional group comprises tertiary amine groups and quaternary ammonium group and sulfonic group and carboxylic acid group.Further appropriate catalyst comprises the silicate of basic metal and alkaline-earth metal.Appropriate catalyst has been disclosed among US4062884 and the US4691041.The ion exchange resin of optional self-contained polystyrene matrix of heterogeneous catalyst and tertiary amine functional group.Example is that Amberlyst A-21 is (available from Rohm﹠amp; Haas), it comprises N, the polystyrene matrix that the N-dimethyl amido is connected thereto.People such as J F Knifton, J.Mol.Catal., 67 (1991), 8 class transesterification catalysts are disclosed among the 389ff, comprising the ion exchange resin with tertiary amine groups and quaternary ammonium group.
The further transesterification conditions that is used for the step (a) of above-mentioned method is known in the art and comprises 40-200 ℃ temperature suitably and the pressure of 50-5000kPa (0.5-50bar).
In addition, the present invention relates to prepare the method for diaryl carbonate, this method is included in the transesterification catalyst existence makes aryl alcohol contact with the logistics that contains dialkyl carbonate down, wherein removes alkanol impurity according to any above-mentioned method from described logistics.
Again further, the present invention relates to prepare the method for diaryl carbonate, this method comprises according to any above-mentioned method makes the logistics that contains diaryl carbonate and alkanol impurity contact with the extraction solvent, with separation and Extraction solvent phase and carbonic ether mutually, and aryl alcohol is contacted with the logistics that contains diaryl carbonate.
Preferably, described diaryl carbonate is that diphenyl carbonate and described aryl alcohol are phenol.
In addition, above-described transesterification catalyst and other transesterification conditions may be used on the described method for preparing diaryl carbonate equally.
Further describe the present invention by following embodiment.
Embodiment
In vial, place a certain amount of 99.16wt% diethyl carbonate (DEC), the 0.76wt% ethyl glycol list ether (EtOx of containing; Cellosolvo) and the solution A of 0.04wt% ethanol (EtOH).Then a certain amount of deionized water (extraction solvent) is joined in the described bottle.The water yield of having mentioned the amount of temperature, the solution A of being added and water in experiment 1-5 in the following table and having been added and the weight ratio of the solution A amount of being added.
| Experiment | T(℃) | H 2O(g) | Solution A (g) | H 2O: solution A (wt) |
| 1 | 3.0 | 3.7 | 3.8 | 1∶1 |
| 2 | 21.2 | 14.9 | 15.0 | 1∶1 |
| 3 | 64.0 | 4.0 | 4.1 | 1∶1 |
| 4 | 64.0 | 3.06 | 4.15 | 0.7∶1 |
Airtight then bottle, and, allow it under above-mentioned temperature, to be separated afterwards 1 day by shaking homogenizing 5 minutes.In the described 1 day time period, the content of homogenizing bottle is 3 times again.Last in experiment, water phase separated and organic phase, and the composition by the gas chromatographic analysis sample, its result is as shown in the table.
(*) %EtOx={ that is removed ([wt%EtOx in solution A]-[wt%EtOx in organic phase])/[wt%EtOx in solution A] } * 100%
Result by last table finds out that making water extract ethyl glycol list ether as the extraction solvent from the mixture that contains diethyl carbonate and described ethyl glycol list ether is the effective means that removes pure impurity from organic carbonate under relative low temperature.
Claims (11)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08170388.6 | 2008-12-01 | ||
| EP08170388 | 2008-12-01 | ||
| PCT/EP2009/066110 WO2010063694A1 (en) | 2008-12-01 | 2009-12-01 | Process for removing an alkanol impurity from an organic carbonate stream |
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| Publication Number | Publication Date |
|---|---|
| CN102186806A true CN102186806A (en) | 2011-09-14 |
| CN102186806B CN102186806B (en) | 2015-01-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980140531.8A Active CN102186806B (en) | 2008-12-01 | 2009-12-01 | Process for removing an alkanol impurity from an organic carbonate stream |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5579737B2 (en) |
| CN (1) | CN102186806B (en) |
| WO (1) | WO2010063694A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113166031A (en) * | 2018-12-18 | 2021-07-23 | 国际壳牌研究有限公司 | Process for the preparation of dialkyl carbonates and alkanediols |
| CN114555553A (en) * | 2019-10-03 | 2022-05-27 | 国际壳牌研究有限公司 | Process for the preparation of dialkyl carbonates and alkanediols |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2711353B1 (en) | 2012-09-20 | 2018-10-31 | SABIC Global Technologies B.V. | Process for the continuous manufacture of aryl alkyl carbonate and diaryl carbonate using vapor recompression |
| 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 |
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|---|---|---|---|---|
| IT998978B (en) * | 1973-10-26 | 1976-02-20 | Snam Progetti | PROCEDURE FOR PURIFICATION OF ESTERS OF CARBONIC ACID |
| FR2608812B1 (en) * | 1986-12-23 | 1989-04-07 | Organo Synthese Ste Fse | PROCESS FOR THE PREPARATION OF ORGANIC CARBONATES BY TRANSESTERIFICATION |
| DE4216121A1 (en) * | 1992-05-15 | 1993-11-18 | Bayer Ag | Process for the continuous production 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 |
| JPH06263694A (en) * | 1993-03-11 | 1994-09-20 | Mitsubishi Petrochem Co Ltd | Production of diarylcarbonate |
| JP3960528B2 (en) * | 2002-04-11 | 2007-08-15 | 三菱化学株式会社 | Method for producing dimethyl carbonate and ethylene glycol |
| ES2367797T3 (en) * | 2003-06-27 | 2011-11-08 | Asahi Kasei Chemicals Corporation | METHOD FOR PRODUCING AN AROMATIC CARBONATE. |
| WO2005000783A1 (en) * | 2003-06-27 | 2005-01-06 | Asahi Kasei Chemicals Corporation | Method for producing aromatic carbonate |
| RU2461541C2 (en) * | 2007-01-23 | 2012-09-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method of producing alkane diol and dialkyl carbonate |
| ES2435784T3 (en) * | 2007-01-23 | 2013-12-23 | Shell Internationale Research Maatschappij B.V. | Procedure for the preparation of diaryl carbonate |
-
2009
- 2009-12-01 CN CN200980140531.8A patent/CN102186806B/en active Active
- 2009-12-01 JP JP2011538003A patent/JP5579737B2/en active Active
- 2009-12-01 WO PCT/EP2009/066110 patent/WO2010063694A1/en not_active Ceased
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113166031A (en) * | 2018-12-18 | 2021-07-23 | 国际壳牌研究有限公司 | Process for the preparation of dialkyl carbonates and alkanediols |
| CN113166031B (en) * | 2018-12-18 | 2024-01-19 | 国际壳牌研究有限公司 | Methods for the preparation of dialkyl carbonates and alkanediols |
| TWI843779B (en) * | 2018-12-18 | 2024-06-01 | 荷蘭商蜆殼國際研究所 | Process for preparing dialkyl carbonate and alkanediol |
| CN114555553A (en) * | 2019-10-03 | 2022-05-27 | 国际壳牌研究有限公司 | Process for the preparation of dialkyl carbonates and alkanediols |
| CN114555553B (en) * | 2019-10-03 | 2024-04-05 | 国际壳牌研究有限公司 | Process for preparing dialkyl carbonate and alkanediol |
| TWI873194B (en) * | 2019-10-03 | 2025-02-21 | 荷蘭商蜆殼國際研究所 | Process for preparing dialkyl carbonate and alkanediol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012510450A (en) | 2012-05-10 |
| CN102186806B (en) | 2015-01-28 |
| JP5579737B2 (en) | 2014-08-27 |
| WO2010063694A1 (en) | 2010-06-10 |
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