CN104072377A - Method for synthesizing linear carbonic ester through exchange reaction of cyclic carbonate and alcohol ester - Google Patents
Method for synthesizing linear carbonic ester through exchange reaction of cyclic carbonate and alcohol ester Download PDFInfo
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- CN104072377A CN104072377A CN201410287727.2A CN201410287727A CN104072377A CN 104072377 A CN104072377 A CN 104072377A CN 201410287727 A CN201410287727 A CN 201410287727A CN 104072377 A CN104072377 A CN 104072377A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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Abstract
The invention relates to reaction to synthesize linear carbonic ester by catalyzing cyclic carbonate by taking cerium oxide with high specific surface as a catalyst. According to the reaction, the cerium oxide with high specific surface (50-180m<2>g<-1>) is taken as the catalyst, the cyclic carbonate and alcohol are taken as raw materials, the reaction temperature is 70-160 DEG C, the reaction time is 2-12 hours, the selectivity of the linear carbonic ester is 73-99%, the yield of the linear carbonic ester is 23-84%, and the catalyst can particularly effectively catalyze ethylene carbonate. Compared with a conventional ordinary catalyst for catalysis reaction, the catalyst, namely, the cerium oxide with high specific surface has the advantages of convenient recycling, high catalysis, good repeated use effect and the like.
Description
Technical field
The invention belongs to heterogeneous catalysis field, be specifically related to a kind of method of preparing linear carbonate taking high specific surface cerium as catalyst cyclic carbonate and alcohol transesterification reaction.
Background technology
With methylcarbonate, the linear carbonate that diethyl carbonate is representative is the important chemical intermediate of a class.Due to its low toxicity, can be used as the substitute of methyl-sulfate photoreactive gas, can be used for alkylation and carbonylation reaction simultaneously.In addition, linear carbonate or a kind of good organic solvent, and can be used as additive and be used for improving the octane value of gasoline.The industrial traditional method of preparing linear carbonate mainly contains phosgenation and oxidative carbonylation of methanol method.Phosgenation has severe toxicity to be eliminated gradually.Oxidative carbonylation of methanol method, taking methyl alcohol, carbon monoxide and oxygen as raw material, is a kind of clean production technique, lower but this method is prepared the productive rate of linear carbonate, and carbon monoxide is a kind of explosive, hypertoxic gas, has potential safety hazard.By contrast, ester-interchange method is a kind of novel production process of production of linear carbonic ether, and it is taking cyclic carbonate and alcohols as raw material, by transesterification reaction obtain (as shown in the formula).
Almost low toxicity of this reaction raw materials.In addition, by product ethylene glycol or propylene glycol are also important chemical reagents.Therefore be, clean, a continuable route with cyclic carbonate ester and alcohol ester-interchange method synthetic thread type carbonic ether.
At present, a lot of for the catalyst system of this transesterification reaction, what its activity was the highest is ionic liquid.The people such as He Liangnian (Dimethyl carbonate synthesis catalyzed by DABCO-derived basic ionic liquids via transesterification of ethylene carbonate with methanol, Tetrahedron Letters, 2010,51:2931 – 2934) use alkali ionic liquid [C
4dABCO] OH as catalyzer the transesterification reaction for NSC 11801 (10mmol) and methyl alcohol (150mmol), catalyst levels 18.7mg, after 70 DEG C of reaction 6h, the transformation efficiency of NSC 11801 is 90%, and the productive rate of methylcarbonate is 81%.(the alkali ionic liquid catalyzed carbon vinyl acetate methyl alcohol transesterify Synthesis of dimethyl carbonate such as Ma Chengming, Speciality Petrochemicals, 2012,6:58 – 62) using 1-butyl-3-Methylimidazole oxyhydroxide as catalyzer for the transesterification reaction of methylcarbonate and methyl alcohol, at reaction times 4h, temperature is 67 DEG C, catalyzer 0.3g, alcohol ester is than under the condition for 10:1, and the transformation efficiency of NSC 11801 and the selectivity of methylcarbonate are respectively up to 88.5% and 90.3%.Zhang Suojiang etc. (Chinese patent CN102126957A) are in 100mL stainless steel cauldron, add catalyzer butyl pyridinium chloride 1.2mmol, NSC 11801 10.5g (0.12mol) and methyl alcohol 38mL (0.96mol), closed reactor, 140 DEG C of temperature of reaction, pressure is 0.3MPa, reaction 1h, ethylene carbonate ester conversion rate is 72%, the selectivity of methylcarbonate is 99%.
Although the catalytic activity of ionic liquid is very high, still there are some problems.Because ionic liquid and catalystic converter system coexist in liquid phase, post catalyst reaction is difficult to reclaim.In addition, also there is report to use the transesterification reaction of solid material catalysis linear carbonates and alcohol.(the mesoporous solid base-catalyzed transesterification method Synthesis of dimethyl carbonate such as Wei Tong, petrochemical complex, 2002,12:959 – 962) by equi-volume impregnating, KOH is loaded in mesoporous carbon, at 120 DEG C, the molar ratio of propylene carbonate and methyl alcohol is 1:6, reacts 2h in autoclave, the transformation efficiency of propylene carbonate is 32.4%, and the yield of methylcarbonate is 29.1%.Sun Linbing etc. (Chinese patent CN102698811A) by immobilized trimethyl carbinol lithium to mesoporous SBA-15, be used for catalyzed transesterification, wherein methyl alcohol 20mL, NSC 11801 8.7076g, catalyzer 0.079g, 60 DEG C of reaction 4h in flask, the productive rate of methylcarbonate is 41.0%.(the Hydrotalcite-type materials as catalysts for the synthesis of dimethyl carbonate from ethylene carbonate and methanol such as Y.Watanabe, Microporous and Mesoporous Materials, 1998,22:399 – 407) with hydrotalcite-type materials Mg
2.5al-NO
3be used for transesterification reaction as catalyzer, NSC 11801 2.72g, methyl alcohol 3.96g, catalyst levels 89mg, back flow reaction 3h, the transformation efficiency of NSC 11801 is 70%, the yield of methylcarbonate is 58%.Although these solid catalysts have overcome reacted recovery problem, totally exist catalytic activity not high, the shortcomings such as poor stability.
Cerium oxide is a kind of broad-spectrum rare-earth oxide.At catalytic field, cerium oxide is mainly for the treatment of " triple effect " catalyzer of vehicle exhaust, and water gas shift reaction.Except energy catalytic oxidation, cerium oxide or a kind of typical Lewis base of planting, can some organic reactions of catalysis.On the other hand, the catalytic performance of cerium oxide has tight associated with its specific surface.Specific surface is larger, and the avtive spot being exposed is more, and final catalytic performance is higher.Up to now, do not report the transesterification reaction of coming catalysis cyclic carbonate and alcohol with high specific surface cerium.
Summary of the invention
The technical problem to be solved in the present invention is for problems such as the current preparation method's complexity for the catalyzer of cyclic carbonate and alcohol transesterification reaction, expensive, poor stabilities, provide a kind of catalytic activity and product yield higher, reaction finishes rear separation simply and reuses the transesterification reaction of effective catalyzer for cyclic carbonate and alcohol.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
(1) by high specific surface cerium (specific surface 50 – 180m
2g
-1) dry 1 – 2h in the baking oven of 100 DEG C of 60 –;
(2) get a certain amount of cerium oxide and be used for the transesterification reaction of catalysis cyclic carbonate and alcohol, wherein cyclic carbonate is 1:4 – 1:25 with the ratio of the molfraction of alcohol, and the consumption of high specific surface cerium is 0.3:25 – 3:25 with the ratio of the molfraction of cyclic carbonate;
(3) in normal pressure flask or autoclave, carry out the transesterification reaction of cyclic carbonate and alcohol, at 160 DEG C of 70 –, react 2 – 12h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final cyclic carbonate is 26 – 86%, and the selectivity of linear carbonate is 73 – 99%, and the productive rate of carbonic ether is 23 – 85%.
As the explanation to technique scheme, the high specific surface cerium described in step of the present invention (1) is that this laboratory is made by oneself and obtained, and its specific surface area is 150 – 180m
2g
-1cerium oxide, this high specific surface cerium material need to be dried 1h in the baking oven of 80 DEG C.
As preferably cyclic carbonate of the present invention is NSC 11801 or propylene carbonate to of the present invention, wherein preferred NSC 11801; Described alcohol is low molecular methyl alcohol or ethanol, wherein particular methanol.
As limitation of the invention further, cyclic carbonate of the present invention is 1:10 with the ratio of the molfraction of alcohol, the ratio 0.3:25 – 0.6:25 of the consumption of high specific surface cerium and the molfraction of cyclic carbonate.
Temperature of reaction of the present invention is 160 DEG C of 70 –, and the reaction times is 2 – 12h, and wherein preferred temperature of reaction is 160 DEG C of 140 –, and the preferred reaction times is 2h.
Adopt after technique scheme, the present invention and conventional supported catalyst, ion exchange resin, the catalyzer such as ionic liquid are compared, and have the following advantages:
(1) cerium oxide is solid catalyst, after reaction finishes, after simple solid-liquid separation, can reuse.
(2) thermostability of cerium oxide (heat-resisting more than 400 DEG C) and reusability are better.
(3) catalytic activity and product yield are higher, and wherein the transformation efficiency of cyclic carbonate can reach 86%, and the selectivity of linear carbonate reaches as high as 99%, and the productive rate of carbonic ether is for reaching as high as 84%.
Embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the use for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
(1) by high specific surface cerium (180m
2g
-1) dry 1h in the baking oven of 80 DEG C;
(2) the high specific surface cerium of getting 0.6mmol is used for the transesterification reaction of catalyzed carbon vinyl acetate (25mmol) and methyl alcohol (250mmol);
(3) in autoclave, carry out the transesterification reaction of NSC 11801 and methyl alcohol, at 140 DEG C, react 2h;
(4) after reaction, centrifugation goes out catalyzer.Product is through gas chromatographic analysis, and the transformation efficiency of final NSC 11801 is 86%, and the selectivity of methylcarbonate is 98%, and the productive rate of methylcarbonate is 84%.
Embodiment 2
(1) by high specific surface cerium (180m
2g
-1) dry 1h in the baking oven of 80 DEG C;
(2) the high specific surface cerium of getting 1.2mmol is used for the transesterification reaction of catalyzed carbon vinyl acetate (25mmol) and methyl alcohol (250mmol);
(3) in normal pressure flask, carry out the transesterification reaction of NSC 11801 and methyl alcohol, at 70 DEG C, react 12h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final NSC 11801 is 61%, and the selectivity of methylcarbonate is 73%, and the productive rate of methylcarbonate is 44%.
Embodiment 3
(1) by high specific surface cerium (50m
2g
-1) dry 1h in the baking oven of 80 DEG C;
(2) the high specific surface cerium of getting 0.6mmol is used for the transesterification reaction of catalyzed carbon vinyl acetate (25mmol) and methyl alcohol (250mmol);
(3) in autoclave, carry out the transesterification reaction of NSC 11801 and methyl alcohol, at 140 DEG C of reaction 2h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final NSC 11801 is 64%, and the selectivity of methylcarbonate is 95%, and the productive rate of methylcarbonate is 61%.
Embodiment 4
(1) by high specific surface cerium (170m
2g
-1) dry 1h in the baking oven of 100 DEG C;
(2) the high specific surface cerium of getting 0.3mmol is used for the transesterification reaction of catalyzed carbon vinyl acetate (25mmol) and methyl alcohol (250mmol);
(3) in autoclave, carry out the transesterification reaction of NSC 11801 and methyl alcohol, at 140 DEG C of reaction 4h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final NSC 11801 is 50%, and the selectivity of methylcarbonate is 91%, and the productive rate of methylcarbonate is 46%.
Embodiment 5
(1) by high specific surface cerium (150m
2g
-1) dry 1h in the baking oven of 80 DEG C;
(2) the high specific surface cerium of getting 0.6mmol is used for the transesterification reaction of catalyzed carbon vinyl acetate (50mmol) and ethanol (500mmol);
(3) in autoclave, carry out the transesterification reaction of NSC 11801 and ethanol, 160 DEG C of reaction 6h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final NSC 11801 is 79%, and the selectivity of methylcarbonate is 95%, and the productive rate of methylcarbonate is 75%.
Embodiment 6
(1) by high specific surface cerium (180m
2g
-1) dry 1h in the baking oven of 80 DEG C;
(2) the high specific surface cerium of getting 0.6mmol is used for the transesterification reaction of catalysis propylene carbonate (25mmol) and methyl alcohol (250mmol);
(3) in autoclave, carry out the transesterification reaction of propylene carbonate and methyl alcohol, 160 DEG C of reaction 6h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final propylene carbonate is 66%, and the selectivity of methylcarbonate is 99%, and the productive rate of methylcarbonate is 66%.
Embodiment 7
(1) by high specific surface cerium (180m
2g
-1) dry 1.5h in the baking oven of 60 DEG C.；
(2) the high specific surface cerium of getting 0.6mmol is used for the transesterification reaction of catalysis propylene carbonate (25mmol) and ethanol (100mmol);
(3) in autoclave, carry out the transesterification reaction of propylene carbonate and ethanol, 160 DEG C of reaction 6h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final propylene carbonate is 26%, and the selectivity of methylcarbonate is 88%, and the productive rate of methylcarbonate is 23%.
Embodiment 8
(1) by high specific surface cerium (180m
2g
-1) dry 2h in the baking oven of 80 DEG C.
(2) the high specific surface cerium of getting 0.6mmol is used for the transesterification reaction of catalysis propylene carbonate (25mmol) and ethanol (250mmol);
(3) in autoclave, carry out the transesterification reaction of propylene carbonate and ethanol, 160 DEG C of reaction 6h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final propylene carbonate is 34.2%, and the selectivity of methylcarbonate is 90%, and the productive rate of methylcarbonate is 31%.
Embodiment 9
(1) by high specific surface cerium (180m
2g
-1) dry 2h in the baking oven of 80 DEG C.
(2) the high specific surface cerium of getting 1.2mmol is used for the transesterification reaction of catalysis propylene carbonate (10mmol) and ethanol (250mmol);
(3) in autoclave, carry out the transesterification reaction of propylene carbonate and ethanol, 160 DEG C of reaction 6h;
(4) after reaction, centrifugation goes out catalyzer, and product is through gas chromatographic analysis, and the transformation efficiency of final propylene carbonate is 86%, and the selectivity of methylcarbonate is 97%, and the productive rate of methylcarbonate is 83%.
By the high specific surface cerium (180m using in embodiment 1
2g
-1) reuse, to test its reusable performance, concrete outcome is in table 1.
The repeat performance of table 1 high specific surface cerium catalyzed carbon vinyl acetate transesterify Synthesis of dimethyl carbonate
As can be seen from Table 1, after four times are reused, catalyzer still can remain on more than 83% the transformation efficiency of diethyl carbonate, and selectivity remains on 97%.Illustrate that this catalyzer has good reusability.
Taking above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, relevant staff can, not departing from the scope of this invention technological thought, carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to claim scope.
Claims (9)
1. the method for the synthetic linear carbonate of a cyclic carbonate and alcohol transesterification reaction, it is characterized in that the method is taking cyclic carbonate and alcohol as raw material, taking high specific surface cerium as catalyzer, synthetic linear carbonate under certain temperature of reaction and reaction times.
2. the method for the synthetic linear carbonate of a kind of cyclic carbonate according to claim 1 and alcohol transesterification reaction, is characterized in that described high specific surface cerium is that specific surface area is 50 – 180m
2g
-1cerium oxide, this high specific surface cerium material need to be dried 1 – 2h in the baking oven of 100 DEG C of 60 –.
3. the method for the synthetic linear carbonate of a kind of cyclic carbonate according to claim 1 and 2 and alcohol transesterification reaction, is characterized in that described high specific surface cerium is that specific surface area is 150 – 180m
2g
-1cerium oxide, this high specific surface cerium material need to be dried 1h in the baking oven of 80 DEG C.
4. the method for the synthetic linear carbonate of a kind of cyclic carbonate according to claim 1 and alcohol transesterification reaction, is characterized in that described cyclic carbonate is NSC 11801 or propylene carbonate.
5. the method for the synthetic linear carbonate of a kind of cyclic carbonate according to claim 1 and alcohol transesterification reaction, is characterized in that described alcohol is low molecular methyl alcohol or ethanol.
6. the method for the synthetic linear carbonate of a kind of cyclic carbonate according to claim 1 and alcohol transesterification reaction, it is characterized in that described cyclic carbonate is 1:4 – 1:25 with the ratio of the molfraction of alcohol, the consumption of high specific surface cerium is 0.3:25 – 3:25 with the ratio of the molfraction of cyclic carbonate.
7. according to the method for a kind of cyclic carbonate described in claim 1 or 6 and the synthetic linear carbonate of alcohol transesterification reaction, it is characterized in that described cyclic carbonate is 1:10 with the ratio of the molfraction of alcohol, the consumption of high specific surface cerium is 0.3:25 – 0.6:25 with the ratio of the molfraction of cyclic carbonate.
8. the method for the synthetic linear carbonate of a kind of cyclic carbonate according to claim 1 and alcohol transesterification reaction, is characterized in that described temperature of reaction is 160 DEG C of 70 –, and the reaction times is 2 – 12h.
9. according to the method for a kind of cyclic carbonate described in claim 1 or 8 and the synthetic linear carbonate of alcohol transesterification reaction, it is characterized in that described temperature of reaction is 160 DEG C of 140 –, the reaction times is 2h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588658A (en) * | 2016-11-18 | 2017-04-26 | 常州大学 | Method of synthesizing dimethyl carbonate |
| CN106076387B (en) * | 2016-06-14 | 2019-03-22 | 常州大学 | A kind of application of heterogeneous catalyst in cyclic carbonate and alcohol transesterification synthetic linear carbonic ester |
| CN109516917A (en) * | 2018-12-05 | 2019-03-26 | 沈阳工业大学 | A kind of method of synthesizing diethyl carbonate |
| CN114573918A (en) * | 2022-04-18 | 2022-06-03 | 珠海瑞杰包装制品有限公司 | High-barrier low-odor polyolefin composition and preparation method thereof |
| CN116078372A (en) * | 2023-04-06 | 2023-05-09 | 中国科学院过程工程研究所 | Catalyst for synthesizing cyclic carbonate, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0599287A1 (en) * | 1992-11-25 | 1994-06-01 | Nippon Shokubai Co., Ltd. | A process for preparing dialkyl carbonates |
-
2014
- 2014-06-24 CN CN201410287727.2A patent/CN104072377B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0599287A1 (en) * | 1992-11-25 | 1994-06-01 | Nippon Shokubai Co., Ltd. | A process for preparing dialkyl carbonates |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076387B (en) * | 2016-06-14 | 2019-03-22 | 常州大学 | A kind of application of heterogeneous catalyst in cyclic carbonate and alcohol transesterification synthetic linear carbonic ester |
| CN106588658A (en) * | 2016-11-18 | 2017-04-26 | 常州大学 | Method of synthesizing dimethyl carbonate |
| CN109516917A (en) * | 2018-12-05 | 2019-03-26 | 沈阳工业大学 | A kind of method of synthesizing diethyl carbonate |
| CN114573918A (en) * | 2022-04-18 | 2022-06-03 | 珠海瑞杰包装制品有限公司 | High-barrier low-odor polyolefin composition and preparation method thereof |
| CN116078372A (en) * | 2023-04-06 | 2023-05-09 | 中国科学院过程工程研究所 | Catalyst for synthesizing cyclic carbonate, preparation method and application thereof |
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