CN105712884A - Preparation method of dimethyl carbonate and propylene glycol - Google Patents
Preparation method of dimethyl carbonate and propylene glycol Download PDFInfo
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- CN105712884A CN105712884A CN201410738250.5A CN201410738250A CN105712884A CN 105712884 A CN105712884 A CN 105712884A CN 201410738250 A CN201410738250 A CN 201410738250A CN 105712884 A CN105712884 A CN 105712884A
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Abstract
The invention relates to a preparation method of dimethyl carbonate and propylene glycol. According to the preparation method, CO2 and epoxy propane are taken as the raw materials, alkali metal halides are taken as the catalyst, methanol is taken as the solvent, propylene carbonate is generated through cyclo-addition reaction, and finally dimethyl carbonate and propylene glycol are generated through trans-esterification reactions between propylene carbonate and methanol in the presence of a catalyst without separation. The provided catalytic system has the advantages of low cost and high catalytic activity and selectivity, and thus has a wide industrial application prospect.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to a kind of method preparing dimethyl carbonate joint production of propylene glycol.
Background technology
Dimethyl carbonate (DimethylCarbonate) is called for short DMC, it it is a kind of green non-poisonous industrial chemicals with extensive use, containing groups such as methyl, methoxyl group, carbonyls in the molecular structure of dimethyl carbonate, the extremely toxic substance such as phosgene, dimethyl sulfate can be substituted and carry out the various reaction such as carbonylation, ester exchange, therefore dimethyl carbonate is widely used in the fields such as material, medicine, pesticide, dyestuff, electronic chemical product, and dimethyl carbonate also acts as polar organic solvent and gasoline additive in addition.Ester-interchange method is one of main method of synthesis DMC, and the method is by epoxide and CO2Reaction generates cyclic carbonate, then carries out ester exchange reaction again with methanol and generates DMC, also obtains another kind of important chemicals glycol simultaneously.
At present can catalysis epoxidation thing and CO2The catalyst of cycloaddition reaction is numerous, such as alkali halide, alkaline-earth halide, organic base, quaternary ammonium salt, ionic liquid, solid base, transient metal complex, four tooth Schiff base metal complexes, molecular sieve, crown ether etc..The catalyst for ester exchange reaction reported has: alkali-metal hydroxide, alcoholates, carbonate, silicate, organic base, quaternary ammonium salt, quaternary alkylphosphonium salt, solid base, tetrafluoroborate etc..Less bibliographical information can by catalyst system and catalyzing compatible to carbonylation and ester exchange reaction.It is desirable to provide a kind of efficient composite catalyst system, by the ester exchange reaction of the carbonylation of two step method catalysis expoxy propane and carbon dioxide and Allyl carbonate and methanol.
Summary of the invention
It is an object of the invention to provide a kind of under relatively mild condition, high yield, highly selective are by expoxy propane, CO2It is the method that raw material prepares dimethyl carbonate joint production of propylene glycol by composite catalyst with methanol.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of method preparing dimethyl carbonate joint production of propylene glycol, it is characterised in that the method can include following two steps:
A () is at CO2Being raw material with expoxy propane, alkali metal salt halogenide is catalyst, when methanol is solvent, generates Allyl carbonate by cycloaddition reaction, and reaction equation is as follows:
B (), with alkali carbonate B for catalyst, carries out ester exchange reaction in the reactant liquor that step (a) obtains, generate dimethyl carbonate and propylene glycol, and reaction equation is as follows:
Wherein alkali halide A is at least one in sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, cesium chloride, cesium bromide and cesium iodide, and alkali carbonate B is at least one in potassium carbonate, lithium carbonate, sodium carbonate.
The mol ratio of alkali halide A and expoxy propane is 1:5-1:100, and alkali carbonate A introduces in step (a) and also can introduce in step (b), and the mol ratio of alkali carbonate A and expoxy propane is 1:5-1:100.The reaction condition of step (a) is reaction pressure is 0.1-3.0MPa, reaction temperature is 343-423K, response time is 0.5-8h, the mol ratio of expoxy propane and methanol is 1:3-1:20,0-96% in methanol adds in step (b), step (b) reaction condition is reaction temperature is 343-453K, and the response time is 0.5-5h.
Beneficial effects of the present invention
The present invention is without separating, and the ester exchange reaction of further catalysis Allyl carbonate and methanol generates dimethyl carbonate and propylene glycol, simultaneously, it is provided that catalyst system and catalyzing cost low, catalysis activity and selectivity is higher, has bigger prospects for commercial application.
Detailed description of the invention
Describe specific embodiment of the invention step in detail below by some embodiments, these embodiments should be used as scope of the invention restriction.
Embodiment 1
A (), in 200ml autoclave, is sequentially added into potassium iodide 4mmol, methanol 30mmol, expoxy propane 40mmol, enclosed high pressure reactor, it is filled with appropriate carbon dioxide under room temperature, heating autoclave is to 373K, and regulation of carbon dioxide pressure is to 1.0MPa, isothermal reaction 4h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 98%, and selectivity is 99%.
B () is in the reactant liquor of former autoclave, add methanol 120mmol, potassium carbonate 4mmol, closed reactor, heating autoclave is to 393K, reaction 2h, after reaction, autoclave is cooled to room temperature, after being decompressed to normal pressure, opens reactor, reactant liquor is carried out gas chromatographic analysis, the productivity of dimethyl carbonate and selectivity respectively 84% and 98%, the selectivity of propylene glycol is 96%.
Embodiment 2
A (), in 200ml autoclave, is sequentially added into sodium chloride 8mmol, methanol 30mmol, expoxy propane 40mmol, enclosed high pressure reactor, it is filled with appropriate carbon dioxide under room temperature, heating autoclave is to 403K, and regulation of carbon dioxide pressure is to 3.0MPa, isothermal reaction 8h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 92%, and selectivity is 99%.
B () is in the reactant liquor of former autoclave, add methanol 120mmol, potassium carbonate 8mmol, closed reactor, heating autoclave is to 423K, reaction 5h, after reaction, autoclave is cooled to room temperature, after being decompressed to normal pressure, opens reactor, reactant liquor is carried out gas chromatographic analysis, the productivity of dimethyl carbonate and selectivity respectively 86% and 98%, the selectivity of propylene glycol is 97%.
Embodiment 3
A (), in 200ml autoclave, is sequentially added into cesium iodide 4mmol, methanol 10mmol, expoxy propane 40mmol, enclosed high pressure reactor, it is filled with appropriate carbon dioxide under room temperature, heating autoclave is to 353K, and regulation of carbon dioxide pressure is to 1.0MPa, isothermal reaction 6h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 98%, and selectivity is 99%.
B () is in the reactant liquor of former autoclave, add methanol 150mmol, potassium carbonate 4mmol, closed reactor, heating autoclave is to 393K, reaction 3h, after reaction, autoclave is cooled to room temperature, after being decompressed to normal pressure, opens reactor, reactant liquor is carried out gas chromatographic analysis, the productivity of dimethyl carbonate and selectivity respectively 82% and 98%, the selectivity of propylene glycol is 97%.
Embodiment 4
A (), in 200ml autoclave, is sequentially added into potassium chloride 6mmol, methanol 30mmol, expoxy propane 40mmol, enclosed high pressure reactor, it is filled with appropriate carbon dioxide under room temperature, heating autoclave is to 413K, and regulation of carbon dioxide pressure is to 2.0MPa, isothermal reaction 1h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 94%, and selectivity is 99%.
B () is in the reactant liquor of former autoclave, add methanol 230mmol, potassium carbonate 4mmol, closed reactor, heating autoclave is to 443K, reaction 1h, after reaction, autoclave is cooled to room temperature, after being decompressed to normal pressure, opens reactor, reactant liquor is carried out gas chromatographic analysis, the productivity of dimethyl carbonate and selectivity respectively 88% and 98%, the selectivity of propylene glycol is 96%.
Embodiment 5
A (), in 200ml autoclave, is sequentially added into potassium bromide 5mmol, methanol 20mmol, expoxy propane 40mmol, enclosed high pressure reactor, it is filled with appropriate carbon dioxide under room temperature, heating autoclave is to 373K, and regulation of carbon dioxide pressure is to 1.5MPa, isothermal reaction 3h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 92%, and selectivity is 99%.
B () is in the reactant liquor of former autoclave, add methanol 140mmol, sodium carbonate 6mmol, closed reactor, heating autoclave is to 383K, reaction 4h, after reaction, autoclave is cooled to room temperature, after being decompressed to normal pressure, opens reactor, reactant liquor is carried out gas chromatographic analysis, the productivity of dimethyl carbonate and selectivity respectively 84% and 98%, the selectivity of propylene glycol is 98%.
Embodiment 6
A (), in 200ml autoclave, is sequentially added into cesium bromide 0.5mmol, methanol 20mmol, expoxy propane 40mmol, enclosed high pressure reactor, it is filled with appropriate carbon dioxide under room temperature, heating autoclave is to 373K, and regulation of carbon dioxide pressure is to 1.0MPa, isothermal reaction 8h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 99%, and selectivity is 99%.
B () is in the reactant liquor of former autoclave, add methanol 740mmol, potassium carbonate 4mmol, closed reactor, heating autoclave is to 393K, reaction 2h, after reaction, autoclave is cooled to room temperature, after being decompressed to normal pressure, opens reactor, reactant liquor is carried out gas chromatographic analysis, the productivity of dimethyl carbonate and selectivity respectively 88% and 98%, the selectivity of propylene glycol is 96%.
Embodiment 7
A (), in 200ml autoclave, is sequentially added into sodium iodide 4mmol, methanol 180mmol, expoxy propane 40mmol, enclosed high pressure reactor, it is filled with appropriate carbon dioxide under room temperature, heating autoclave is to 393K, and regulation of carbon dioxide pressure is to 1.5MPa, isothermal reaction 4h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 96%, and selectivity is 98%.
B () is in the reactant liquor of former autoclave, add lithium carbonate 6mmol, closed reactor, heating autoclave, to 423K, reacts 4h, after reaction, autoclave is cooled to room temperature, reactor is opened after being decompressed to normal pressure, reactant liquor is carried out gas chromatographic analysis, and the productivity of dimethyl carbonate and selectivity respectively 70% and 98%, the selectivity of propylene glycol is 97%.
Embodiment 8
A () is in 200ml autoclave, it is sequentially added into cesium chloride 1.5mmol, methanol 120mmol, potassium carbonate 4mmol, expoxy propane 40mmol, enclosed high pressure reactor, appropriate carbon dioxide it is filled with under room temperature, heating autoclave is to 383K, regulation of carbon dioxide pressure is to 1.5MPa, isothermal reaction 6h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 65%, selectivity is 98%, the productivity of dimethyl carbonate and selectivity respectively 27% and 98%, the selectivity of propylene glycol is 96%.
B () is in the reactant liquor of former autoclave, add methanol 40mmol, closed reactor, heating autoclave, to 393K, reacts 3h, after reaction, autoclave is cooled to room temperature, reactor is opened after being decompressed to normal pressure, reactant liquor is carried out gas chromatographic analysis, and the productivity of dimethyl carbonate and selectivity respectively 84% and 98%, the selectivity of propylene glycol is 96%.
Embodiment 9
A (), in 200ml autoclave, is sequentially added into sodium bromide 6mmol, methanol 20mmol, expoxy propane 40mmol, enclosed high pressure reactor, it is filled with appropriate carbon dioxide under room temperature, heating autoclave is to 373K, and regulation of carbon dioxide pressure is to 2.0MPa, isothermal reaction 3h, after reaction, autoclave is cooled to room temperature, open vent valve and be slowly decompressed to normal pressure, open reactor, reactant liquor is carried out gas chromatographic analysis, Allyl carbonate productivity is 97%, and selectivity is 98%.
B () is in the reactant liquor of former autoclave, add methanol 150mmol, potassium carbonate 0.6mmol, closed reactor, heating autoclave is to 393K, reaction 8h, after reaction, autoclave is cooled to room temperature, after being decompressed to normal pressure, opens reactor, reactant liquor is carried out gas chromatographic analysis, the productivity of dimethyl carbonate and selectivity respectively 70% and 98%, the selectivity of propylene glycol is 96%.
Claims (7)
1. the method preparing dimethyl carbonate joint production of propylene glycol, it is characterised in that the method includes following two steps:
A () is at CO2Being raw material with expoxy propane, alkali halide is catalyst A, and reaction pressure is 0.1-3.0MPa, in 343-423K when, reacts 0.5-8h, when methanol is solvent, generates Allyl carbonate by cycloaddition reaction, and reaction equation is as follows:
B (), with alkali carbonate for catalyst B, in 343-453K when, is reacted 0.5-5h, is carried out ester exchange reaction in the reactant liquor that step (a) obtains, generate dimethyl carbonate and propylene glycol, reaction equation is as follows:
2. in accordance with the method for claim 1, it is characterised in that: alkali halide is one or more in sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, cesium chloride, cesium bromide or cesium iodide.
3. in accordance with the method for claim 1, it is characterised in that: alkali carbonate is one or more in potassium carbonate, lithium carbonate or sodium carbonate.
4. in accordance with the method for claim 1, it is characterised in that: in step (a), the mol ratio of alkali halide and expoxy propane is 1:5-1:100.
5. in accordance with the method for claim 1, it is characterised in that: the mol ratio of the expoxy propane being initially added in the amount of the alkali carbonate added in step (b) and step (a) is 1:5-1:100.
6. in accordance with the method for claim 1, it is characterised in that: in step (a), the mol ratio of expoxy propane and methanol is 1:0.5-1:3.
7. in accordance with the method for claim 1, it is characterised in that: in step (b), the addition of methanol adds gauge with methanol altogether, and mass percent is not higher than 98wt.%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101739A (en) * | 2017-12-19 | 2018-06-01 | 西安近代化学研究所 | The continuous method for preparing tri- fluoro- 1,2- propylene glycol of 3,3,3- |
| CN111875577A (en) * | 2020-08-25 | 2020-11-03 | 湖南亚王医药科技有限公司 | Preparation method of R-propylene carbonate |
| CN113321570A (en) * | 2021-07-14 | 2021-08-31 | 山东华安新材料有限公司 | Preparation method of 3,3, 3-trifluoro-1, 2-propanediol |
| CN114957010A (en) * | 2022-04-20 | 2022-08-30 | 上海交通大学 | Application of catalyst in synthesis of dimethyl carbonate and dihydric alcohol by alcohol exchange method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101036880A (en) * | 2007-03-09 | 2007-09-19 | 陕西师范大学 | Catalyst for synthesizing dimethyl carbonate and its preparing process |
| CN101092365A (en) * | 2007-06-29 | 2007-12-26 | 山东石大胜华化工股份有限公司 | Technical method for associated producing carbonic allyl ester, methyl carbonate, and propylene glycol |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101036880A (en) * | 2007-03-09 | 2007-09-19 | 陕西师范大学 | Catalyst for synthesizing dimethyl carbonate and its preparing process |
| CN101092365A (en) * | 2007-06-29 | 2007-12-26 | 山东石大胜华化工股份有限公司 | Technical method for associated producing carbonic allyl ester, methyl carbonate, and propylene glycol |
Non-Patent Citations (2)
| Title |
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| HONGYOU CUI ET AL: "One-pot Synthesis of Dimethyl Carbonate Using Ethylene Oxide, Methanol, and Carbon Dioxide under Supercritical Conditions", 《IND. ENG. CHEM. RES.》 * |
| JIN-QUAN WANG ET AL: "Synthesis of dimethyl carbonate from CO2 and ethylene oxide catalyzed by K2CO3-based salts in the presence of H2O", 《 GREEN CHEM.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101739A (en) * | 2017-12-19 | 2018-06-01 | 西安近代化学研究所 | The continuous method for preparing tri- fluoro- 1,2- propylene glycol of 3,3,3- |
| CN108101739B (en) * | 2017-12-19 | 2021-04-13 | 西安近代化学研究所 | Method for continuously preparing 3,3, 3-trifluoro-1, 2-propanediol |
| CN111875577A (en) * | 2020-08-25 | 2020-11-03 | 湖南亚王医药科技有限公司 | Preparation method of R-propylene carbonate |
| CN111875577B (en) * | 2020-08-25 | 2021-11-09 | 湖南亚王医药科技有限公司 | Preparation method of R-propylene carbonate |
| CN113321570A (en) * | 2021-07-14 | 2021-08-31 | 山东华安新材料有限公司 | Preparation method of 3,3, 3-trifluoro-1, 2-propanediol |
| CN114957010A (en) * | 2022-04-20 | 2022-08-30 | 上海交通大学 | Application of catalyst in synthesis of dimethyl carbonate and dihydric alcohol by alcohol exchange method |
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Application publication date: 20160629 |