CN109821560A - A kind of catalyst of transesterification Synthesis of dimethyl carbonate and its application - Google Patents
A kind of catalyst of transesterification Synthesis of dimethyl carbonate and its application Download PDFInfo
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- CN109821560A CN109821560A CN201910075447.8A CN201910075447A CN109821560A CN 109821560 A CN109821560 A CN 109821560A CN 201910075447 A CN201910075447 A CN 201910075447A CN 109821560 A CN109821560 A CN 109821560A
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Abstract
The invention discloses a kind of catalyst of transesterification Synthesis of dimethyl carbonate, including alkali metal fluoride and metal oxide, the alkali metal fluoride is carried on the metal oxide, and the mass ratio of the alkali metal fluoride and the metal oxide is 1:1-20.In the present invention, using metal oxide as carrier, alkali metal fluoride is supported on carrier, active component alkali metal fluosilicate hydrochlorate in the supported solid catalyst has stronger alkalinity, conducive to ester exchange reaction, the catalytic efficiency of catalyst is improved, shortens the reaction time.
Description
Technical field
The invention belongs to solid base catalyst technical fields, and in particular to a kind of catalysis of transesterification Synthesis of dimethyl carbonate
The application of agent and the catalyst in Synthesis of dimethyl carbonate.
Background technique
Dimethyl carbonate (DMC) has developed one of most rapid green chemical since being 20th century.Itself it is multifunctional
Group determines that it can react with a variety of organic compounds such as alcohol, phenol, amine, ester and amino alcohol.It can be also as having simultaneously
The substitute of malicious dimethyl suflfate and phosgene, and due to high oxygen content (53%) and octane number (105), it can be used as gasoline
Additive.
The method for synthesizing DMC mainly has phosgenation, ester-interchange method, oxidation carbonylation method, alcoholysis of urea at this stage
With some novel methods.Since the yield of ester-interchange method is high, reaction condition is substantially nontoxic corrosion-free, more mildly, while can be with
Coproduction ethylene glycol, therefore be a valuable synthetic method.
The custom catalysts of existing synthesis of dimethyl carbonate via transesterification include soluble alkali metal hydroxide, alcohol
The homogeneous catalysts such as salt, alkali carbonate, organic base and alkaline earth oxide, soda acid composite catalyst etc. are heterogeneous
Catalyst.Homogeneous catalyst is not easy to product separation, reuses difficult.
The existing many reports of heterogeneous catalyst catalyzed transesterification Synthesis of dimethyl carbonate, patent 200310109693 are public
The composite catalyst of a kind of calcirm-fluoride and zirconium oxide is opened, it is 120 DEG C in reaction temperature that catalyst preparation process is complicated, reaction
The yield of dimethyl carbonate ester reaches 97% after 48h.When carrying out ester exchange reaction using the catalyst, the reaction time is long, instead
The temperature answered is high.
Patent 201510700289.2 disclose it is a kind of by MgO-Supported in being catalyzed ethylene carbonate on graphene oxide
The catalyst is applied in Synthesis of dimethyl carbonate, dimethyl carbonate by the solid catalyst of transesterification Synthesis of dimethyl carbonate
Selectivity and yield are respectively 99.3%, 87.1%.
Patent 201610988571.x disclose it is a kind of in a high pressure reaction kettle, using ethylene carbonate and methanol as raw material,
Active carbon is the method for catalyst Synthesis of dimethyl carbonate, and ethylene carbonate and methanol molar ratio are 1:10, activated carbon dosage
20% (mass fraction for accounting for ethylene carbonate), pressure 0.3MPa react 8h at 160 DEG C, obtain the conversion ratio of ethylene carbonate
97%, dimethyl carbonate selectivity 99%.But the use condition of the catalyst is harsh, need to react under negative pressure and hot conditions,
Higher yield can be just obtained, limits the application of catalyst to a certain extent.
In conclusion the existing generally existing catalyst amount of solid catalyst for being applied to Synthesis of dimethyl carbonate it is big,
The problems such as catalytic efficiency is low, the reaction time is long constrains the use occasion of catalyst, limits the production effect of dimethyl carbonate
Rate.
Summary of the invention
It is an object of the present invention to: above-mentioned deficiency in the prior art is solved, a kind of transesterification carbonate synthesis is provided
The catalytic performance of the catalyst of dimethyl ester, the catalyst is excellent, and ester exchange reaction rate is high.
To achieve the goals above, the technical solution adopted by the present invention are as follows: a kind of transesterification Synthesis of dimethyl carbonate is urged
Agent, including alkali metal fluoride and metal oxide, the alkali metal fluoride are carried on the metal oxide, the alkali
The mass ratio of metal fluoride and the metal oxide is 1:1-20.
In catalyst of the invention, the mass ratio of alkali metal fluoride and the metal oxide is 1:1-20, preferably 1:
3-6, when being less than the ratio, the catalytic performance of catalyst is reduced, and is not able to satisfy the reaction requirement of Synthesis of dimethyl carbonate, and is worked as
When greater than the ratio, the amount of metal fluoride is more, will block the mesoporous of carrier, so that the catalytic performance of catalyst drops significantly
It is low.
More preferably, the mass ratio of the alkali metal fluoride and the metal oxide is 1:3-6.When alkali metal is fluorinated
When the ratio of object and metal oxide is 1:5, the catalytic performance of catalyst is best.
Further, the alkali metal fluoride is one of NaF, KF, LiF or a variety of mixing.
Further, the metal oxide is one of MgO, Al2O3, CaO or a variety of mixing.
More preferably, the alkali metal fluoride is LiF, and the metal oxide is CaO.LiF/CaO catalyst is urged
It is more excellent to change performance.
The typical preparation method of catalyst is as follows, but is not limited to this kind of method: by a certain amount of metal oxide and steaming
Distilled water is uniformly mixed, ultrasonic disperse 30-60min, wherein the mass ratio of metal oxide and the distilled water is 1:10-20；Again
The mass ratio of addition alkali metal fluoride, alkali metal fluoride and metal oxide is 1:1-20, wherein being best with 1:5；Magnetic
Power is stirred liquid 4-8h, is uniformly mixed, and dries, roasting.Drying temperature is 90-110 DEG C, and the maturing temperature is 300-
700 DEG C, calcining time 2-8h.
The present invention by the way that metal oxide dispersion is added in solvent in distilled water, then by alkali metal fluoride,
Under the conditions of distilled water is existing, alkali metal fluoride is loaded on an metal oxide, drying removal solvent, then passes through roasting,
In high-temperature calcination process, alkali metal fluoride and metal oxide form metal fluoride, alkali metal fluosilicate hydrochlorate, carbonation etc.,
Active centre as reaction；The alkalinity of alkali metal fluosilicate hydrochlorate is strong, can significantly improve the catalytic performance of catalyst, improves reaction
Rate shortens the reaction time.
In roasting process, be conducive to the formation of catalyst active center, improve the catalytic performance of catalyst.
More preferably, maturing temperature is 500 DEG C, and calcining time 4h is roasted under this condition, and obtained active component is most
It is more, so that the catalytic performance of catalyst is more excellent；When maturing temperature is lower than 500 DEG C but is greater than 300 DEG C, formed in roasting process
Active component is relatively smaller, and catalytic is declined, but still can catalyzed transesterification.When maturing temperature is higher than 500 DEG C but low
When 700 DEG C, in roasting process, catalyst is easier to gather, be sintered, and reduces catalytic performance, but still can catalytic transesterification it is anti-
It answers.
Under above-mentioned catalyst, using methanol and cyclic carbonate as raw material, make methanol and cyclic carbonate that transesterification occur
Synthesis of dimethyl carbonate, reaction temperature are 50-110 DEG C, reaction time 0.2-3h, the methanol and the cyclic carbonate
Molar ratio be 4-12:1.
Further, the cyclic carbonate is ethylene carbonate or propene carbonate.
Catalyst of the invention is applied in Synthesis of dimethyl carbonate, at 70-90 DEG C, the catalytic efficiency of catalyst
Height, ester exchange reaction rate is fast, and the time of Synthesis of dimethyl carbonate is short, the high conversion rate of cyclic carbonate, dimethyl carbonate choosing
Selecting property and high conversion rate.
By adopting the above-described technical solution, the beneficial effects of the present invention are:
(1) in the present invention, using metal oxide as carrier, alkali metal fluoride is supported on carrier, the support type is solid
Active component alkali metal fluosilicate hydrochlorate in body catalyst has stronger alkalinity, is conducive to ester exchange reaction, improves urging for catalyst
Change efficiency, shortens the reaction time.
(2) catalyst of the invention is applied in the synthesis of dimethyl carbonate, the mild condition of ester exchange reaction, reaction
Speed is fast, and the reaction time is short, the high conversion rate of cyclic carbonate, wherein to the good catalytic activity of dimethyl carbonate.
Specific embodiment
Embodiment 1:
Take KF/MgO catalyst 0.0176g, the methanol 51.2g and ethylene carbonate 17.6g addition that KF load capacity is 20%
Into 250ml round-bottomed flask, after 0.5 hour is stirred to react at 70 DEG C, product in bottle is taken to be tested and analyzed, analyzes result
Are as follows: ethylene carbonate ester conversion rate is 11.75%, and dimethyl carbonate selectivity and yield are respectively 97.62%, 11.47%.
Embodiment 2:
Take KF/CaO catalyst 0.0176g, the methanol 51.2g and ethylene carbonate 17.6g addition that KF load capacity is 20%
It into 250ml round-bottomed flask, is stirred to react at 70 DEG C 0.5 hour, product in bottle is taken to be tested and analyzed, analyze result are as follows:
Ethylene carbonate ester conversion rate is 62.62%, and dimethyl carbonate selectivity and yield are respectively 98.56%, 61.72%.
Embodiment 3:
Taking LiF load capacity is that 20% LiF/CaO catalyst 0.0176g, methanol 51.2g and ethylene carbonate 17.6g adds
Enter into 250ml round-bottomed flask, be stirred to react at 70 DEG C 0.5 hour, product in bottle is taken to be tested and analyzed, analyzes result
Are as follows: ethylene carbonate ester conversion rate is 72.08%, and dimethyl carbonate selectivity and yield are respectively 99.33%, 71.60%.
Embodiment 4:
Taking NaF load capacity is that 20% NaF/CaO catalyst 0.0176g, methanol 51.2g and ethylene carbonate 17.6g adds
Enter into 250ml round-bottomed flask, be stirred to react at 70 DEG C 0.5 hour, product in bottle is taken to be tested and analyzed, analyzes result
Are as follows: ethylene carbonate ester conversion rate is 61.74%, and dimethyl carbonate selectivity and yield are respectively 97.05%, 59.92%.
Embodiment 5:
Taking LiF load capacity is that 20% LiF/CaO catalyst 0.0176g, methanol 51.2g and ethylene carbonate 17.6g adds
Enter into 250ml round-bottomed flask, be stirred to react at 90 DEG C 0.5 hour, product in bottle is taken to be tested and analyzed, analyzes result
Are as follows: ethylene carbonate ester conversion rate is 72.93%, and dimethyl carbonate selectivity and yield are respectively 99.41%, 72.50%.
Embodiment 6:
Take LiF/CaO catalyst 0.0176g, the methanol 64g and ethylene carbonate 17.6g addition that LiF load capacity is 20%
It into 250ml round-bottomed flask, is stirred to react at 70 DEG C 0.5 hour, product in bottle is taken to be tested and analyzed, analyze result are as follows:
Ethylene carbonate ester conversion rate is 77.98%, and dimethyl carbonate selectivity and yield are respectively 99.97%, 77.96%.
Embodiment 7:
Take LiF/CaO catalyst 0.0176g, the methanol 64g and ethylene carbonate 17.6g addition that LiF load capacity is 20%
It into 250ml round-bottomed flask, is stirred to react at 70 DEG C 2 hours, product in bottle is taken to be tested and analyzed, analyze result are as follows: carbon
Vinyl acetate conversion ratio is 83.31%, and dimethyl carbonate selectivity and yield are respectively 93.71%, 78.07%.
From the analysis result of embodiment 6 and embodiment 7, it can be concluded that, after ester exchange reaction 0.5h, ethylene carbonate is converted
Rate is 77.98%, and dimethyl carbonate selectivity and yield are respectively 99.97%, 77.96%, and reacts the analysis result after 2h
Difference is smaller, illustrates that in a relatively short period of time, ester exchange reaction tends to balance, the speed of ester exchange reaction is fast, and the reaction time is short.
Embodiment 8:
Taking LiF load capacity is that 20% LiF/CaO catalyst 0.204g, methanol 32g and propene carbonate 10.2g is added to
It in 250ml round-bottomed flask, is stirred to react at 90 DEG C 2 hours, product in bottle is taken to be tested and analyzed, analyze result are as follows: carbonic acid
Propylene ester conversion rate is 54.08%, and dimethyl carbonate selectivity and yield are respectively 98.83%, 53.45%.
Embodiment 9:
Taking LiF load capacity is that 20% LiF/CaO catalyst 0.204g, methanol 32g and propene carbonate 10.2g is added to
It in 250ml round-bottomed flask, is stirred to react at 90 DEG C 4 hours, product in bottle is taken to be tested and analyzed, analyze result are as follows: carbonic acid
Propylene ester conversion rate is 66.90%, and dimethyl carbonate selectivity and yield are respectively 98.47%, 65.88%.
Embodiment 10:
Taking LiF load capacity is that 20% LiF/CaO catalyst 0.0176g, methanol 76.8g and ethylene carbonate 17.6g adds
Enter into 250ml round-bottomed flask, be stirred to react at 70 DEG C 0.5 hour, product in bottle is taken to be tested and analyzed, analyzes result
Are as follows: ethylene carbonate ester conversion rate is 62.97%, and dimethyl carbonate selectivity and yield are respectively 96.19%, 60.47%.
Embodiment 11:
Taking LiF load capacity is that 20% LiF/CaO catalyst 0.0176g, methanol 38.4g and ethylene carbonate 17.6g adds
Enter into 250ml round-bottomed flask, be stirred to react at 70 DEG C 0.5 hour, product in bottle is taken to be tested and analyzed, analyzes result
Are as follows: ethylene carbonate ester conversion rate is 65.95%, and dimethyl carbonate selectivity and yield are respectively 99.01%, 65.30%.
Comparative experiments example 1:
Sodium methoxide 0.0176g, methanol 51.2g and ethylene carbonate 17.6g is taken to be added in 250ml round-bottomed flask, 70
It is stirred to react at DEG C 0.5 hour, product in bottle is taken to be tested and analyzed, analyze result are as follows: ethylene carbonate ester conversion rate is
48.88%, dimethyl carbonate selectivity and yield are respectively 96.11%, 46.99%.
From the result in above-described embodiment 1-11, it can be concluded that, catalyst provided by the invention, catalytic performance is good, is applied to
It is catalyzed cyclic carbonate and methanol reacts and generates dimethyl carbonate, the high conversion rate of cyclic carbonate, in a relatively short period of time,
It can get higher yield.Compared with sodium methoxide catalyst in the prior art, catalyst of the invention is applied in carbonate synthesis
In dimethyl ester, the high income of dimethyl carbonate, and catalyst and product are easily separated.
In other embodiments of the invention, catalyst can also be NaF/Al2O3,KF/Al2O3,LiF/Al2O3Etc. groups
It closes.
The effect of above-described embodiment indicates that essentiality content of the invention, but protection of the invention is not limited with this
Range.Those skilled in the art should understand that can with modification or equivalent replacement of the technical solution of the present invention are made,
Without departing from the essence and protection scope of technical solution of the present invention.
Claims (5)
1. a kind of catalyst of transesterification Synthesis of dimethyl carbonate, it is characterised in that: aoxidized including alkali metal fluoride and metal
Object, the alkali metal fluoride are carried on the metal oxide, the matter of the alkali metal fluoride and the metal oxide
Amount is than being 1:1-20.
2. the catalyst of transesterification Synthesis of dimethyl carbonate according to claim 1, it is characterised in that: the alkali metal fluosilicate
Compound is one of NaF, KF, LiF or a variety of mixing.
3. the catalyst of transesterification Synthesis of dimethyl carbonate according to claim 1, it is characterised in that: the metal oxidation
Object is MgO, Al2O3, one of CaO or a variety of mixing.
4. a kind of application method of the catalyst of any transesterification Synthesis of dimethyl carbonate of claim 1-3, feature exist
In: using methanol and cyclic carbonate as raw material, under the catalyst, transesterification Synthesis of dimethyl carbonate, reaction temperature is
50-110 DEG C, reaction time 0.2-3h, the molar ratio of the methanol and the cyclic carbonate is 4-12:1.
5. the application method of the catalyst of transesterification Synthesis of dimethyl carbonate according to claim 4, it is characterised in that: institute
Stating cyclic carbonate is ethylene carbonate or propene carbonate.
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Cited By (7)
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| CN110302813A (en) * | 2019-07-24 | 2019-10-08 | 惠州宇新化工有限责任公司 | A kind of catalyst of synthesizing annular carbonate and its preparation method and application |
| CN111841587A (en) * | 2020-07-06 | 2020-10-30 | 浙江大学衢州研究院 | Solid base catalyst and preparation method thereof |
| CN112156797A (en) * | 2020-09-10 | 2021-01-01 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing dimethyl carbonate by ester exchange of cyclic carbonate and methanol, preparation method and application thereof |
| CN113509922A (en) * | 2021-07-13 | 2021-10-19 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing aliphatic carbonate and preparation method and application thereof |
| CN114230464A (en) * | 2021-12-27 | 2022-03-25 | 大连理工大学 | Method for preparing dimethyl carbonate by optimizing ethylene carbonate and methanol in high yield based on response surface method |
| CN114989015A (en) * | 2022-06-30 | 2022-09-02 | 华东师范大学 | Method for preparing dimethyl carbonate by ester exchange reaction catalyzed by inorganic salt |
| CN115466181A (en) * | 2022-09-05 | 2022-12-13 | 天津凯美特化工科技有限公司 | Method for producing dimethyl carbonate by ester exchange using long-acting catalyst |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110302813B (en) * | 2019-07-24 | 2022-08-16 | 惠州宇新化工有限责任公司 | Catalyst for synthesizing cyclic carbonate and preparation method and application thereof |
| CN111841587A (en) * | 2020-07-06 | 2020-10-30 | 浙江大学衢州研究院 | Solid base catalyst and preparation method thereof |
| CN112156797A (en) * | 2020-09-10 | 2021-01-01 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing dimethyl carbonate by ester exchange of cyclic carbonate and methanol, preparation method and application thereof |
| CN112156797B (en) * | 2020-09-10 | 2022-02-15 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing dimethyl carbonate by ester exchange of cyclic carbonate and methanol, preparation method and application thereof |
| CN113509922A (en) * | 2021-07-13 | 2021-10-19 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing aliphatic carbonate and preparation method and application thereof |
| CN114230464A (en) * | 2021-12-27 | 2022-03-25 | 大连理工大学 | Method for preparing dimethyl carbonate by optimizing ethylene carbonate and methanol in high yield based on response surface method |
| CN114989015A (en) * | 2022-06-30 | 2022-09-02 | 华东师范大学 | Method for preparing dimethyl carbonate by ester exchange reaction catalyzed by inorganic salt |
| CN114989015B (en) * | 2022-06-30 | 2023-09-26 | 华东师范大学 | Method for preparing dimethyl carbonate by catalyzing transesterification with inorganic salt |
| CN115466181A (en) * | 2022-09-05 | 2022-12-13 | 天津凯美特化工科技有限公司 | Method for producing dimethyl carbonate by ester exchange using long-acting catalyst |
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