CN102126957A - Method for preparing carbonic ester and ethylene alcohol by ionic liquid catalysis - Google Patents
Method for preparing carbonic ester and ethylene alcohol by ionic liquid catalysis Download PDFInfo
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- CN102126957A CN102126957A CN2011100062574A CN201110006257A CN102126957A CN 102126957 A CN102126957 A CN 102126957A CN 2011100062574 A CN2011100062574 A CN 2011100062574A CN 201110006257 A CN201110006257 A CN 201110006257A CN 102126957 A CN102126957 A CN 102126957A
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Abstract
The invention relates to a method for preparing carbonic ester and ethylene alcohol by ionic liquid catalysis. The method is characterized in that: ethylene carbonate and fatty alcohol are taken as raw materials, and an ionic liquid catalyst is used in a reacting process, so that ethylene alcohol and carbonate can be synthesized with high transformation ratio and selectivity at the reaction temperature of between 373 K and 453 K within the reaction time of 0.25-6 hours under the condition that the molar ratio of the ethylene carbonate to the fatty alcohol is 1:4-1:32.
Description
Technical field:
The present invention relates to green, clean catalysis technical field, specifically referring to a kind of is raw material with NSC 11801 and Fatty Alcohol(C12-C14 and C12-C18), in the ionic liquid-catalyzed method of passing through transesterification reaction synthesizing glycol and carbonic ether down.
Background technology:
Ethylene glycol is important Organic Chemicals, is mainly used in the production polyester.Constantly increase along with the develop rapidly of China's PET industry in recent years and automobile volume of production and marketing enlarge the deicing fluid demand that is driven, the ethylene glycol consumption continues to increase.Methylcarbonate is a kind of nontoxic, readily biodegradable, environmentally friendly green basic chemical industry raw material, can be used as solvent, gasoline dope, lithium-ion battery electrolytes, bisphenol-a polycarbonate monomer and carbonylation, methylate and the carbonyl methylating reagent, be widely used in chemical field.Two kinds of important chemical product of ethylene glycol and methylcarbonate can make simultaneously by NSC 11801 and methyl alcohol transesterify, and in the last few years, the research of relevant this respect had been subjected to increasing attention.
The catalyzer of having reported at present that passes through transesterification reaction synthesizing glycol and carbonic ether has: alkali metal hydroxide, alkaline earth metal carbonate, organic bases, quaternary ammonium salt, quaternary alkylphosphonium salt, tetrafluoroborate, solid alkali (as metal oxide), the triphenylphosphine of cross-linked resin load, silicon dioxide carried water glass, the quaternary amine of ion exchange resin, chitosan loaded quaternary amine or the like, these catalyst system exist such as catalytic activity not high more or less, stability is not high, severe reaction conditions, problems such as catalyzer cost height.In addition, transesterification reaction is balanced reaction, and general equilibrium conversion is lower, and the active general carbon number along with alcohol of alcohol increases and reduces.The present invention develops the high-effect ionic liquid catalyst, aims to provide the high-efficiency synthesis method of a kind of ionic liquid-catalyzed preparation ethylene glycol and carbonic ether.
Summary of the invention
The present invention's research is under relatively mild condition, and efficient, highly selective realizes by NSC 11801 and Fatty Alcohol(C12-C14 and C12-C18) being raw material prepares ethylene glycol and carbonic ether by transesterification reaction method.
Reaction expression of the present invention is:
Fatty Alcohol(C12-C14 and C12-C18) is monohydroxy-alcohol, dibasic alcohol or glycerine, without any special restriction.Described monohydroxy-alcohol is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and the hexalin; Dibasic alcohol is selected from a kind of in ethylene glycol, propylene glycol, butyleneglycol and the hexylene glycol.Wherein preferably monohydroxy-alcohol, particularly methyl alcohol.
A kind of ionic liquid-catalyzed method for preparing carbonic ether and ethylene glycol, it is characterized in that with NSC 11801 and Fatty Alcohol(C12-C14 and C12-C18) be raw material, use a kind of in the following 1-4 class ionic-liquid catalyst, in temperature of reaction is 373-453K, reaction times is 0.25-6 hour, NSC 11801 and Fatty Alcohol(C12-C14 and C12-C18) mol ratio are 1: 4-1: under 32 conditions, by transesterification reaction synthesizing glycol and carbonic ether; Wherein 1-4 class ionic-liquid catalyst structure is as follows:
n＝1-12 X＝Cl，Br，I，BF
4，PF
6
In the following formula-R
1,-R
2,-R
3,-R
4,-R
5Be substituted radical on the positively charged ion in the 1-4 class catalyzer, be selected from a kind of in the alkyl of carbon number between 1-14 respectively, can be identical, also can be different.
Embodiment
A kind of ionic liquid-catalyzed method for preparing carbonic ether and ethylene glycol of the present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Implementation method: in the 100mL stainless steel autoclave, add catalyzer butyl pyridinium chloride 1.2mmol, NSC 11801 10.5g (0.12mol) and methyl alcohol 38mL (0.96mol), closed reactor slowly rises to 413K by the temperature controller controlled temperature, and pressure is 0.3MPa, reaction 1h, be cooled to room temperature, the mixed solution of gained is carried out gas chromatographic analysis, the ethylene carbonate ester conversion rate is 72%, the selectivity 99% of ethylene glycol, the selectivity of methylcarbonate are 99%.
Embodiment 2
With embodiment 1, catalyst system therefor is a butyl bromination 4-Dimethylamino pyridine, and catalyst levels is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 66%, and the selectivity of ethylene glycol is 98%, and the selectivity of methylcarbonate is 99%.
Embodiment 3
With embodiment 1, the catalyst system therefor consumption is 0.12mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 58%, and the selectivity of ethylene glycol is 98%, and the selectivity of methylcarbonate is 99%.
Embodiment 4
With embodiment 1, the catalyst system therefor consumption is 12mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 86%, and the selectivity of ethylene glycol is 99%, and the selectivity of methylcarbonate is 99%.
Embodiment 5
With embodiment 1, catalyst system therefor is a choline chloride 60, and catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 78%, and the selectivity of ethylene glycol is 97%, and the selectivity of methylcarbonate is 99%.
Embodiment 6
With embodiment 7, temperature of reaction is 373K, and pressure is 0.1MPa, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 56%, and the selectivity of ethylene glycol is 99%, and the selectivity of methylcarbonate is 99%.
Embodiment 7
With embodiment 1, temperature of reaction is 453K, and pressure is 1MPa, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 79%, and the selectivity of ethylene glycol is 98%, and the selectivity of methylcarbonate is 99%.
Embodiment 8
With embodiment 1, the reaction times is 0.3h, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 46%, and the selectivity of ethylene glycol is 99%, and the selectivity of methylcarbonate is 99%.
Embodiment 9
With embodiment 1, the reaction times is 6h, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 82%, and the selectivity of ethylene glycol is 99%, and the selectivity of methylcarbonate is 99%.
Embodiment 10
With embodiment 1, the methyl alcohol volume is 19mL (0.48mmol), and other are constant, and obtaining the ethylene carbonate ester conversion rate is 56%, and the selectivity of ethylene glycol is 99%, and the selectivity of methylcarbonate is 99%.
Embodiment 11
With embodiment 1, the methyl alcohol volume is 152mL (3.84mol), and other are constant, and obtaining the ethylene carbonate ester conversion rate is 90%, and the selectivity of ethylene glycol is 99%, and the selectivity of methylcarbonate is 99%.
Embodiment 12
With embodiment 1, catalyst system therefor is a dodecyl iodate pyridine, and catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 70%, and the selectivity of ethylene glycol is 97%, and the selectivity of methylcarbonate is 99%.
Embodiment 13
With embodiment 1, catalyst system therefor is an ethyl Tetrafluoroboric acid 4-Dimethylamino pyridine, and catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 68%, and the selectivity of ethylene glycol is 97%, and the selectivity of methylcarbonate is 99%.
Embodiment 14
With embodiment 1, catalyst system therefor is a dodecyl phosphofluoric acid 4-Dimethylamino pyridine, and catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 65%, and the selectivity of ethylene glycol is 98%, and the selectivity of methylcarbonate is 99%.
Embodiment 15
With embodiment 1, catalyst system therefor is the octyl pyridinium chloride, and catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 67%, and the selectivity of ethylene glycol is 98%, and the selectivity of methylcarbonate is 99%.
Embodiment 16
With embodiment 1, catalyst system therefor is a normal hexane base chlorination 4-Dimethylamino pyridine, and catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 69%, and the selectivity of ethylene glycol is 98%, and the selectivity of methylcarbonate is 99%.
Embodiment 17
With embodiment 1, catalyst system therefor is N, N, N
/, N
/-tetramethyl--N
//-methyl-N
//-butyl guanidine villaumite, catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 76%, and the selectivity of ethylene glycol is 98%, the selectivity of methylcarbonate is 99%.
Embodiment 18
With embodiment 1, catalyst system therefor is N, N, N
/, N
/-tetramethyl--N
//, N
//-dibutyl guanidine a tetrafluoro borate, catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 70%, and the selectivity of ethylene glycol is 98%, the selectivity of methylcarbonate is 99%.
Embodiment 19
With embodiment 1, catalyst system therefor is N, N, N
/, N
/-tetramethyl--N
//-butyl-N
//-hexadecyl base guanidine salt compounded of iodine, catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 55%, and the selectivity of ethylene glycol is 98%, the selectivity of methylcarbonate is 99%.
Embodiment 20
With embodiment 1, catalyst system therefor is 4-hydroxyl butyl-N, N, and the N-trimethylammonium bromide, catalytic amount is 1.2mmol, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 67%, and the selectivity of ethylene glycol is 98%, the selectivity of methylcarbonate is 99%.
Embodiment 21
With embodiment 1, catalyst system therefor is 4-hydroxyl dodecyl-N, N, N-trimethyl ammonium hexafluoro borate, catalytic amount is 1.2mmol, other are constant, obtaining the ethylene carbonate ester conversion rate is 65%, and the selectivity of ethylene glycol is 98%, and the selectivity of methylcarbonate is 99%.
Embodiment 22
With embodiment 1, used Fatty Alcohol(C12-C14 and C12-C18) is an ethanol, and mole number is 0.96mol, and the reaction times is 6h, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 52%, and the selectivity of ethylene glycol is 97%, and the selectivity of diethyl carbonate is 98%.
Embodiment 23
With embodiment 1, used Fatty Alcohol(C12-C14 and C12-C18) is a Virahol, and mole number is 0.96mol, and the reaction times is 6h, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 46%, and the selectivity of ethylene glycol is 98%, and the selectivity of carbonic acid diisopropyl alcohol ester is 98%.
Embodiment 24
With embodiment 1, used Fatty Alcohol(C12-C14 and C12-C18) is a hexalin, and mole number is 0.96mol, and the time is 8h, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 32%, and the selectivity of ethylene glycol is 94%, and the selectivity of carbonic acid diisopropyl alcohol ester is 96%.
Embodiment 25
With embodiment 1, used Fatty Alcohol(C12-C14 and C12-C18) is an ethylene glycol, and mole number is 0.96mol, and the time is 8h, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 26%, and the selectivity of ethylene glycol is 69%, and the selectivity of carbonic acid binaryglycol ester is 64%.
Embodiment 26
With embodiment 1, used Fatty Alcohol(C12-C14 and C12-C18) is a glycerine, and mole number is 0.96mol, and the time is 10h, and other are constant, and obtaining the ethylene carbonate ester conversion rate is 16%, and the selectivity of ethylene glycol is 70%, and the selectivity of carbonic acid two glyceryl ester is 64%.
Claims (5)
1. ionic liquid-catalyzed method for preparing carbonic ether and ethylene glycol, it is characterized in that with NSC 11801 and Fatty Alcohol(C12-C14 and C12-C18) be raw material, use a kind of in the following 1-4 class ionic-liquid catalyst, in temperature of reaction is 373-453K, reaction times is 0.25-6 hour, NSC 11801 and Fatty Alcohol(C12-C14 and C12-C18) mol ratio are 1: 4-1: under 32 conditions, by transesterification reaction synthesizing glycol and carbonic ether; Wherein 1-4 class ionic-liquid catalyst structure is as follows:
n＝1-12 X＝Cl，Br，I，BF
4，PF
6
Among the last figure-R
1,-R
2,-R
3,-R
4,-R
5Be substituted radical on the positively charged ion in the 1-4 class catalyzer, be selected from a kind of in the alkyl of carbon number between 1-14 respectively, can be identical, also can be different.
2. a kind of ionic liquid-catalyzed method for preparing carbonic ether and ethylene glycol according to claim 1 is characterized in that used Fatty Alcohol(C12-C14 and C12-C18) is monohydroxy-alcohol, dibasic alcohol or glycerine.
3. a kind of ionic liquid-catalyzed method for preparing carbonic ether and ethylene glycol according to claim 2 is characterized in that described monohydroxy-alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, a kind of in butanols and the hexalin; Described dibasic alcohol is selected from ethylene glycol, propylene glycol, a kind of in butyleneglycol and the hexylene glycol.
4. a kind of ionic liquid-catalyzed method for preparing carbonic ether and ethylene glycol according to claim 1 is characterized in that catalyzer is selected from a kind of in 1 and 3.
5. a kind of ionic liquid-catalyzed method for preparing carbonic ether and ethylene glycol according to claim 1 is characterized in that catalyst levels is lower than 10% of NSC 11801 amount of substance.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633605A (en) * | 2012-03-20 | 2012-08-15 | 青岛科技大学 | Chemical depolymerization recovery method for waste compact disks |
| CN103418433A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Loading type quaternary phosphonium catalyst, manufacturing method and application thereof |
| CN103641720A (en) * | 2013-12-17 | 2014-03-19 | 福州大学 | Method of synthesizing diethyl carbonate by basic ionic liquid as catalyst |
| CN104043480A (en) * | 2014-05-09 | 2014-09-17 | 天津大学 | Ionic liquid catalyst and dimethyl carbonate synthesis method |
| CN105669366A (en) * | 2015-12-31 | 2016-06-15 | 天津中福工程技术有限公司 | Method for synthesizing diethyl carbonate by adopting alkaline ionic liquid as catalyst |
| CN109704968A (en) * | 2019-02-21 | 2019-05-03 | 南开大学 | A kind of method of ionic liquid-catalyzed Synthesis of dimethyl carbonate |
| CN111825836A (en) * | 2019-04-23 | 2020-10-27 | 中国科学院过程工程研究所 | Preparation method of polycarbonate |
| CN113004147A (en) * | 2021-03-10 | 2021-06-22 | 中国科学院过程工程研究所 | Method for preparing dialkyl carbonate from cyclic carbonate by using polymeric ionic liquid catalyst |
| CN113185407A (en) * | 2021-04-23 | 2021-07-30 | 华东理工大学 | Method for synthesizing dimethyl carbonate through ester exchange reaction |
| CN113563190A (en) * | 2021-07-14 | 2021-10-29 | 广州金鑫泰化工有限公司 | Preparation method of dimethyl carbonate |
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Cited By (14)
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| CN102633605A (en) * | 2012-03-20 | 2012-08-15 | 青岛科技大学 | Chemical depolymerization recovery method for waste compact disks |
| CN102633605B (en) * | 2012-03-20 | 2015-06-10 | 青岛科技大学 | Chemical depolymerization recovery method for waste compact disks |
| US9416093B2 (en) | 2012-05-16 | 2016-08-16 | China Petroleum & Chemical Corporation | Supported quaternary phosphonium catalyst, preparation and use thereof |
| CN103418433A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Loading type quaternary phosphonium catalyst, manufacturing method and application thereof |
| CN103641720A (en) * | 2013-12-17 | 2014-03-19 | 福州大学 | Method of synthesizing diethyl carbonate by basic ionic liquid as catalyst |
| CN104043480A (en) * | 2014-05-09 | 2014-09-17 | 天津大学 | Ionic liquid catalyst and dimethyl carbonate synthesis method |
| CN105669366A (en) * | 2015-12-31 | 2016-06-15 | 天津中福工程技术有限公司 | Method for synthesizing diethyl carbonate by adopting alkaline ionic liquid as catalyst |
| CN109704968A (en) * | 2019-02-21 | 2019-05-03 | 南开大学 | A kind of method of ionic liquid-catalyzed Synthesis of dimethyl carbonate |
| CN109704968B (en) * | 2019-02-21 | 2021-10-15 | 南开大学 | Method for synthesizing dimethyl carbonate by ionic liquid catalysis |
| CN111825836A (en) * | 2019-04-23 | 2020-10-27 | 中国科学院过程工程研究所 | Preparation method of polycarbonate |
| CN111825836B (en) * | 2019-04-23 | 2021-09-17 | 中国科学院过程工程研究所 | Preparation method of polycarbonate |
| CN113004147A (en) * | 2021-03-10 | 2021-06-22 | 中国科学院过程工程研究所 | Method for preparing dialkyl carbonate from cyclic carbonate by using polymeric ionic liquid catalyst |
| CN113185407A (en) * | 2021-04-23 | 2021-07-30 | 华东理工大学 | Method for synthesizing dimethyl carbonate through ester exchange reaction |
| CN113563190A (en) * | 2021-07-14 | 2021-10-29 | 广州金鑫泰化工有限公司 | Preparation method of dimethyl carbonate |
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