CN104774148A - Method used for preparing high-purity ethyl methyl carbonate - Google Patents
Method used for preparing high-purity ethyl methyl carbonate Download PDFInfo
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- CN104774148A CN104774148A CN201410011106.1A CN201410011106A CN104774148A CN 104774148 A CN104774148 A CN 104774148A CN 201410011106 A CN201410011106 A CN 201410011106A CN 104774148 A CN104774148 A CN 104774148A
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Abstract
The invention relates to a synthetic method of ethyl methyl carbonate (EMC), and specifically relates to a method used for catalyzing dimethyl carbonate and diethyl carbonate with a solid super base so as to synthesize ethyl methyl carbonate. According to the method, the solid super base is taken as a catalyst; and high-selectivity catalyzing of dimethyl carbonate and diethyl carbonate is carried out; so that ethyl methyl carbonate is obtained via synthesis; the molar ratio of dimethyl carbonate to diethyl carbonate is 0.25-4:1; reaction temperature is lower than 150 DEG C; reaction is carried out at normal pressure; reaction time ranges from 1 to 3h; and catalyst amount accounts for 1 to 5% of the weight of the raw materials. The solid super base is taken as the catalyst; reaction time is short; selectivity is high; and EMC products with a purity required by lithium ion battery electrolyte can be obtained via simple distillation. Activity of the catalyst is high; and recycling of the catalyst after reaction can be realized.
Description
Technical field
The present invention relates to the synthetic method of Methyl ethyl carbonate, utilize solid super basic catalyst catalyzed carbon dimethyl phthalate and the transesterification Catalysts of Preparing Methyl Ethyl Carbonate of diethyl carbonate specifically.
Background technology
Methyl ethyl carbonate (Ethyl Methyl Carbonate is called for short EMC) is a kind of broad-spectrum asymmetric carbon ester compound, main as solvent and organic synthesis intermediate.It is emphasized that it is found that EMC is used as the solvent of lithium ion battery electrolyte in recent years, the ionic conductivity of lithium ion conduction can be significantly improved, improve energy density and the loading capacity of battery, more can improve safety performance and increase the service life, and there is good low temperature use properties etc.But lithium-ion battery electrolytes is very high to purity requirement, impurity often produces significant impact (industry forum to chemical property, 9 phases in 2003, lithium-ion battery electrolytes, Liao Hongying, Cheng Baoying, Hao Zhiqiang), the price of EMC and the requirement of purity is limited to its application, therefore developing one and can reduce production cost and put forward highly purified synthetic method, is that EMC is able to widely used key.
Up to now, the synthetic method of EMC mainly contains three kinds: phosgenation, oxidation carbonylation method and ester-interchange method.Phosgenation relates to hypertoxic reactant phosgene, is eliminated gradually.Contain the mixture of multiple carbonic ether and alcohols in the product of oxidation carbonylation method, can azeotropic system be formed, product separation purification difficult.Therefore, ester-interchange method is the most feasible method of current synthesis of high purity carbonic acid methyl ethyl ester.
In the research of Synthesis of Ethyl Methyl Carbonate by Transesterification, it is more that EMC is synthesized in the transesterify being raw material with methylcarbonate (DMC) and ethanol.But EMC selectivity is lower in this method product, there is multiple azeotropic system (methyl alcohol and DMC, ethanol and DMC, ethanol and EMC) in product, separating technology is complicated, adds facility investment and running cost simultaneously.And the generation of azeotropic system is avoided with the ester-interchange method that DMC and diethyl carbonate (DEC) are raw material.The reaction equation of DMC and DEC transesterify synthesis EMC is as follows:
H
3COCOOCH
3+H
3CH
2COCOOCH
2CH
3→2H
3COCOOCH
2CH
3
JP2000281630(Hasegawa Kaisuaki, Inaba Masashi, Production ofasymmetric dialkyl catbonate JP:2000281630,2000) with IIIB family metal oxides such as the lanthanum of load, actinium, scandium, yttriums for catalyzer, at 50-200 DEG C, under 0-1.96MPa, carry out transesterification reaction, EMC yield reaches 45%.But such catalyzer is very high to the purity requirement of reaction raw materials, total chlorinity must lower than 10ppm, and especially content of inorganic chlorine must, lower than 1ppm, be difficult to realize in the industrial production of reality.
US6057062 (Hong Gan, Marcus J.Palazzo, Esther S.Takeuchi, Method for preparing nonaqueous electrochemical cells containingunsymmetric organic carbonates.US:6057062, 2000) catalyzer of two classes for DME and DEC transesterification preparation EMC is developed: electronics can be provided or nucleophilic reagent class catalyzer (alkyl or the aromatic base negatively charged ion of shared electron are provided, carbonyl compound, amino-complex), and the reductive agent (samarium diodide of electronics can be provided in reaction system, lithium, hydrolith etc.).Reaction is carried out usually under normal pressure, room temperature condition, and molecular balance generally needs more than 3 days.And catalyzer filters by adsorbing and crossing, the higher EMC product of purity is by distilling or extracting filtrate acquisition.
CN1394847(Shen Zhen land, Zhao Weijuan, Zhuo Guanglan, Jiang Xuanzhen, a kind of method preparing Methyl ethyl carbonate, CN1394847,2003) to be carried on the SnO on aluminum oxide
2, Ga
2o
3, MoO
3, ZrO
2, TiO
2, V
2o
5for catalyzer, under 50-200 DEG C of condition, carry out the transesterification reaction of DMC and DEC, the yield of reaction times 2-48h, EMC is only 44%, wherein catalyzer recoverable.
With Lewis acid, aluminum chloride, iron trichloride, titanium tetrachloride, zinc chloride etc. are catalyzer to CN101357889 (Zhou Gang, Zhou Tiancheng, a kind of preparation method of Methyl ethyl carbonate, CN1013578892007), the transesterification reaction of catalysis DMC and DEC.At 0-150 DEG C, reaction 0.5-5h, EMC yield reaches 55%, through air distillation, obtains the EMC product of purity more than 99.5%.Lewis acid catalyst used can recycle and reuse.But the lewis acidic application of chloride type can introduce organochlorine impurity in the product, preparing cell-grade EMC for later stage separation and purification increases difficulty.
CN101863771(Jing Tao, Tian Jingzhi, Deng Qigang, Zheng Yongjie, Ren Zhaoqi, a kind of synthetic method of Methyl ethyl carbonate, CN101863771,2009) with DMC and DEC for raw material, in batch still, use houghite solid catalyst, synthesis EMC.Be 100-130 DEG C in temperature of reaction, reaction mass proportioning is react under the condition of 0.5-2.5, and the yield of EMC can reach 59%, and the reaction times is 2-12h.Wherein houghite catalyzer is mixed by the solution of the nitrate solution of copper, zinc, magnesium, aluminium and NaOH and carbonate or NaOH and supercarbonate, and through stirring, crystallization, filters, distillation, washing, and filter cake is dried, and roasting, cooling is prepared from.But hydrotalcite catalyst preparation process is complicated, and maturing temperature is up to 900 DEG C.
CN101704751(monarch Jia Ming, Shi Jinghui, Liu Gang, State of Zhao is bright, Zhang Wenxiang, the synthetic method of Methyl ethyl carbonate, CN101704751,2009) with gac, carbonaceous molecular sieve, mesoporous carbon load Na
2o, K
2o, MgO, CaO, SrO, BaO solid base catalyst, the transesterification reaction of catalysis DMC and DEC in fixed bed and tank reactor, under 50-113 DEG C of condition, the yield of reaction times 4-10h, EMC reaches 47%.
In sum, there is the problems such as too high to ingredient requirement, the reaction times is long, transformation efficiency is undesirable, separation and purification of products difficulty is large in above mentioned catalyzer.
Summary of the invention
The object of the present invention is to provide a kind of with the method for solid super base catalyzed carbon dimethyl phthalate and diethyl carbonate synthesis of high purity carbonic acid methyl ethyl ester.
The technical solution used in the present invention is for achieving the above object: employing solid super base is catalyzer, highly selective catalyzed carbon dimethyl phthalate and the transesterification Catalysts of Preparing Methyl Ethyl Carbonate of diethyl carbonate, the molar ratio of oxide spinel dimethyl ester and diethyl carbonate is 0.25-4:1, preferred 2-3:1, temperature of reaction 30-150 DEG C, preferred 60-120 DEG C, react under condition of normal pressure, reaction times 1-3h, catalyst levels is the 1-5% of raw material weight.Filter after esterification, separating liquid reaction product and solid super basic catalyst.Wherein, in liquid reacting product, Methyl ethyl carbonate is exclusive product, and content is higher than 45%.Liquid reacting product is again through rectifying separation, and intercept middle runnings, obtain the highly purified Methyl ethyl carbonate being applicable to lithium ion battery, purity can reach more than 99.99%, and yield is more than 35%.The lower boiling oxide spinel dimethyl ester that rectifying separation obtains, high boiling point oxide spinel diethyl ester all reuse; Solid super basic catalyst is recycling after being separated.
The present invention's solid super basic catalyst used is general formula is X
a(YOH)
bz
co
dshown load type metal-metal hydroxides; Wherein X is a kind of element in sodium, potassium; Y is a kind of element in sodium, potassium; Z is a kind of element in aluminium, silicon, magnesium, carbon; A, b, c and d are that X, YOH, Z and oxygen are relative to atomic fraction respectively; The valence mumber that a is 0.1-1.0, b be 0.1-0.2, c be 0-0.8, d is the Z element by general formula determine and the number consistent with it.Z
co
dfor support of the catalyst, the one in optional aluminum oxide, silicon oxide, magnesium oxide, each molecular sieve analog, gac, carrier can be Powdered or particulate state, for the ease of the recovery of catalyzer in suitability for industrialized production, preferred particulates shape carrier.Metal X in solid super basic catalyst general formula
acontent be the 1-10% of vehicle weight, metal hydroxides (YOH)
bcontent be the 5-30% of vehicle weight.
The active constituent of solid super basic catalyst is preferably Na-NaOH, Na-KOH, K-KOH or K-NaOH.
The preparation of solid super basic catalyst adopts the preparation of solid-state hybrid system, under stirring and nitrogen purging condition, carrier is slowly heated to 100-200 DEG C in a mixer, keeps 1-5h to carry out the water removing surface adsorption; Then be warming up to 200-400 DEG C and add NaOH or KOH, continue to stir 1-3h under nitrogen purging condition, fully react; At the same temperature and under nitrogen purging condition, add metal Na or metal K fast, stir 1-3h, obtain solid super basic catalyst.
The advantage that the present invention has: the present invention adopts solid super base as catalyzer, and the reaction times is short, and selectivity is high, can obtain the EMC product of the purity requirement that can meet lithium-ion battery electrolytes through simple distillation process.The activity of the catalyzer simultaneously adopted is high, and the recyclable recycling of reacted catalyzer.
In reaction product of the present invention, Methyl ethyl carbonate is exclusive product, and through distilation, the purity of Methyl ethyl carbonate reaches 99.99-99.995%.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the invention is not restricted to following specific embodiment.
Embodiment 1:
Solid super base Na-NaOH/ γ-Al
2o
3preparation: add 100 grams of γ-Al in a kettle.
2o
3, under the condition of violent stirring and nitrogen purging, be heated to 200 DEG C, remove carrier surface planar water.Be warming up to 300 DEG C, under violent stirring and nitrogen purging condition, add 25 grams of NaOH, keep 3h.Afterwards, add 8 grams of sodium Metal 99.5s fast, continue stirring 3 hours.Cooling obtains solid super base Na-NaOH/ γ-Al
2o
3catalyzer.
DMC and DEC transesterify synthesis EMC: add 152 grams of DMC and 100 gram DEC(DMC and DEC mol ratio 2:1 in a kettle .), the super basic catalyst of above-mentioned preparation 5 grams.Slowly be warming up to 90 DEG C, reaction 1h.Filtering separation catalyzer and product liquid.Product liquid is through stratographic analysis, and discovery EMC is exclusive product, and yield is 45%.Filtering separation catalyzer is stayed in reactor and is continued to use.
Product liquid goes out lower boiling methylcarbonate through rectifying separation, returns reactor.Collect middle runnings (109-109.5 DEG C), obtain EMC product, yield 35%, purity can reach 99.995%.After rectifying terminates, high boiling liquid residuum, mainly diethyl carbonate, return reactor and continue to use.
Embodiment 2:
Solid super base Na-KOH/ γ-Al
2o
3preparation: add 100 grams of γ-Al in a kettle.
2o
3, under the condition of violent stirring and nitrogen purging, be heated to 200 DEG C, remove carrier surface planar water.Be warming up to 300 DEG C, under violent stirring and nitrogen purging condition, add 30 grams of KOH, keep 3h.Afterwards, add 8 grams of sodium Metal 99.5s fast, continue to stir 3h.Cooling obtains solid super base Na-KOH/ γ-Al
2o
3catalyzer.
DMC and DEC transesterify synthesis EMC: add 229 grams of DMC and 100 gram DEC(DMC and DEC mol ratio 3:1 in a kettle .), the super basic catalyst of above-mentioned preparation 5 grams.Slowly be warming up to 90 DEG C, reaction 1h.Filtering separation catalyzer and product liquid.Product liquid is through stratographic analysis, and discovery EMC is exclusive product, and yield is 48%.Filtering separation catalyzer is stayed in reactor and is continued to use.
Product liquid goes out lower boiling methylcarbonate through rectifying separation, returns reactor.Collect middle runnings (109-109.5 DEG C), obtain EMC product, yield 37%, purity can reach 99.99%.After rectifying terminates, high boiling liquid residuum, mainly diethyl carbonate, return reactor and continue to use.
Embodiment 3:
Solid super base K-KOH/ γ-Al
2o
3preparation: add 100 grams of γ-Al in a kettle.
2o
3, under the condition of violent stirring and nitrogen purging, be heated to 200 DEG C, remove carrier surface planar water.Be warming up to 300 DEG C, under violent stirring and nitrogen purging condition, add 30 grams of KOH, keep 3h.Afterwards, add 10 grams of potassium metals fast, continue to stir 3h.Cooling obtains solid super base K-KOH/ γ-Al
2o
3catalyzer.
DMC and DEC transesterify synthesis EMC: add 152 grams of DMC and 100 gram DEC(DMC and DEC mol ratio 2:1 in a kettle .), the super basic catalyst of above-mentioned preparation 3 grams.Slowly be warming up to 100 DEG C, react 1 hour.Filtering separation catalyzer and product liquid.Product liquid is through stratographic analysis, and discovery EMC is exclusive product, and yield is 50%.Filtering separation catalyzer is stayed in reactor and is continued to use.
Product liquid goes out lower boiling methylcarbonate through rectifying separation, returns reactor.Collect middle runnings (109-109.5 DEG C), obtain EMC product, yield 37%, purity can reach 99.995%.After rectifying terminates, high boiling liquid residuum, mainly diethyl carbonate, return reactor and continue to use.
Embodiment 4:
Solid super base K-KOH/ γ-Al
2o
3preparation: add 100 grams of γ-Al in a kettle.
2o
3, under the condition of violent stirring and nitrogen purging, be heated to 200 DEG C, remove carrier surface planar water.Be warming up to 400 DEG C, under violent stirring and nitrogen purging condition, add 25 grams of KOH, keep 3h.Afterwards, add 10 grams of potassium metals fast, continue to stir 3h.Cooling obtains solid super base K-KOH/ γ-Al
2o
3catalyzer.
DMC and DEC transesterify synthesis EMC: add 152 grams of DMC and 100 gram DEC(DMC and DEC mol ratio 2:1 in a kettle .), the super basic catalyst of above-mentioned preparation 5 grams.Slowly be warming up to 100 DEG C, react 3 hours.Filtering separation catalyzer and product liquid.Product liquid is through stratographic analysis, and discovery EMC is exclusive product, and yield is 50%.Filtering separation catalyzer is stayed in reactor and is continued to use.
Product liquid goes out lower boiling methylcarbonate through rectifying separation, returns reactor.Collect middle runnings (109-109.5 DEG C), obtain EMC product, yield 39%, purity can reach 99.995%.After rectifying terminates, high boiling liquid residuum, mainly diethyl carbonate, return reactor and continue to use.
Embodiment 5:
The preparation of solid super base Na-NaOH/MgO: add 100 grams of MgO in a kettle., under the condition of violent stirring and nitrogen purging, is heated to 100 DEG C, removes carrier surface planar water.Be warming up to 300 DEG C, under violent stirring and nitrogen purging condition, add 25 grams of NaOH, keep 3h.Afterwards, add 10 grams of metal Na fast, continue to stir 3h.Cooling obtains solid super base Na-NaOH/MgO catalyzer.
DMC and DEC transesterify synthesis EMC: add 229 grams of DMC and 100 gram DEC(DMC and DEC mol ratio 3:1 in a kettle .), the super basic catalyst of preparation 5 grams.Slowly be warming up to 120 DEG C, react 1 hour.Filtering separation catalyzer and product liquid.Product liquid is through stratographic analysis, and discovery EMC is exclusive product, and yield is 45%.Filtering separation catalyzer is stayed in reactor and is continued to use.
Product liquid goes out lower boiling methylcarbonate through rectifying separation, returns reactor.Collect middle runnings (109-109.5 DEG C), obtain EMC product, yield 35%, purity can reach 99.99%.After rectifying terminates, high boiling liquid residuum, mainly diethyl carbonate, return reactor and continue to use.
Embodiment 6:
The preparation of solid super base K-KOH/ gac: add 100 grams of gacs in a kettle., under the condition of violent stirring and nitrogen purging, is heated to 200 DEG C, removes carrier surface planar water.Be warming up to 400 DEG C, under violent stirring and nitrogen purging condition, add 30 grams of KOH, keep 3h.Afterwards, add 10 grams of potassium metals fast, continue to stir 3h.Cooling obtains solid super base K-KOH/ activated-carbon catalyst.
DMC and DEC transesterify synthesis EMC: add 152 grams of DMC and 100 gram DEC(DMC and DEC mol ratio 2:1 in a kettle .), the super basic catalyst of preparation 3 grams.Slowly be warming up to 120 DEG C, react 1 hour.Filtering separation catalyzer and product liquid.Product liquid is through stratographic analysis, and discovery EMC is exclusive product, and yield is 48%.Filtering separation catalyzer is stayed in reactor and is continued to use.
Product liquid goes out lower boiling methylcarbonate through rectifying separation, returns reactor.Collect middle runnings (109-109.5 DEG C), obtain EMC product, yield 38%, purity can reach 99.99%.After rectifying terminates, high boiling liquid residuum, mainly diethyl carbonate, return reactor and continue to use.
Embodiment 7: the recycling of solid super basic catalyst
DMC and DEC transesterify synthesis EMC: by 152 grams of DMC and 100 gram DEC(DMC and DEC mol ratio 2:1) add in the reactor that the solid super basic catalyst that embodiment 4 reclaims is housed.Slowly be warming up to 100 DEG C, react 3 hours.Filtering separation catalyzer and product liquid.Product liquid is through stratographic analysis, and discovery EMC is exclusive product, and yield is 48%.Filtering separation catalyzer is stayed in reactor and is continued to use.
Product liquid goes out lower boiling methylcarbonate through rectifying separation, returns reactor.Collect middle runnings (109-109.5 DEG C), obtain EMC product, yield 39%, purity can reach 99.995%.After rectifying terminates, high boiling liquid residuum, mainly diethyl carbonate, return reactor and continue to use.
Claims (10)
1. prepare the method for high-purity ethyl methyl carbonate for one kind, it is characterized in that: employing solid super base is catalyzer, highly selective catalyzed carbon dimethyl phthalate and the transesterification Catalysts of Preparing Methyl Ethyl Carbonate of diethyl carbonate, the molar ratio of oxide spinel dimethyl ester and diethyl carbonate is 0.25-4:1, temperature of reaction is lower than 150 DEG C, react under condition of normal pressure, reaction times 1-3h, catalyst levels is the 1-5% of raw material weight.
2. by the method preparing high-purity ethyl methyl carbonate according to claim 1, it is characterized in that: in described lactate synthesis Methyl ethyl carbonate reaction, the molar ratio of oxide spinel dimethyl ester and diethyl carbonate is 2-3:1, temperature of reaction is lower than 150 DEG C, react under condition of normal pressure, reaction times 1-3h, catalyst levels is the 1-5% of raw material weight.
3. by the method preparing high-purity ethyl methyl carbonate described in claim 1 or 2, it is characterized in that: described lactate synthesis Methyl ethyl carbonate temperature of reaction 30-150 DEG C, react under condition of normal pressure, reaction times 1-3h, catalyst levels is the 1-5% of raw material weight.
4. by the method preparing high-purity ethyl methyl carbonate according to claim 3, it is characterized in that: described lactate synthesis Methyl ethyl carbonate temperature of reaction 60-120 DEG C, react under condition of normal pressure, reaction times 1-3h, catalyst levels is the 1-5% of raw material weight.
5. by the method preparing high-purity ethyl methyl carbonate described in claim 1,2 or 4, it is characterized in that: filter after described lactate synthesis, be separated to obtain liquid reacting product and solid super basic catalyst,
Wherein, liquid reacting product is the reaction product Methyl ethyl carbonate of highly selective, liquid reacting product obtains the highly purified Methyl ethyl carbonate being applicable to lithium ion battery through rectifying separation again, and the lower boiling oxide spinel dimethyl ester of rectifying separation acquisition, high boiling point oxide spinel diethyl ester all reuse;
Solid super basic catalyst is recycling after being separated.
6., by the method preparing high-purity ethyl methyl carbonate according to claim 1, it is characterized in that:
Described solid super basic catalyst is general formula is X
a(YOH)
bz
co
dshown load type metal-metal hydroxides; Wherein X is sodium or potassium element; Y is sodium or potassium element; Z is aluminium, silicon, magnesium or carbon; A, b, c and d are the relative atom mark of X, YOH, Z and oxygen respectively; The valence mumber that a is 0.1-1.0, b be 0.1-0.2, c be 0-0.8, d is the Z element by general formula determine and the number consistent with it.
7. by the method preparing high-purity ethyl methyl carbonate according to claim 6, it is characterized in that: carrier can be γ-Al
2o
3, SiO
2, MgO, each molecular sieve analog or gac.
8. by the method preparing high-purity ethyl methyl carbonate according to claim 6, it is characterized in that: the active constituent of described solid super basic catalyst is Na-NaOH, Na-KOH, K-KOH or K-NaOH.
9. by the method preparing high-purity ethyl methyl carbonate described in claim 6 or 8, it is characterized in that: metal X in solid super basic catalyst general formula
acontent be the 1-10% of vehicle weight, metal hydroxides (YOH)
bcontent be the 5-30% of vehicle weight.
10. by the method preparing high-purity ethyl methyl carbonate described in claim 6 or 8, it is characterized in that: the preparation of solid super basic catalyst adopts the preparation of solid-state hybrid system, under stirring and nitrogen purging condition, carrier is slowly heated to 100-200 DEG C in a mixer, keeps 1-5h to carry out the water removing surface adsorption; Then be warming up to 200-400 DEG C and add NaOH or KOH, continue to stir 1-3h under nitrogen purging condition, fully react; At the same temperature and under nitrogen purging condition, add metal Na or metal K fast, stir 1-3h, obtain solid super basic catalyst.
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| CN107445836A (en) * | 2017-07-20 | 2017-12-08 | 沈阳化工大学 | A kind of method that dimethyl carbonate prepares methyl ethyl carbonate with diethyl carbonate |
| CN107497463A (en) * | 2017-07-20 | 2017-12-22 | 沈阳化工大学 | A kind of method of preparing methyl ethyl carbonate by ester exchanging reaction |
| CN108033880A (en) * | 2017-12-20 | 2018-05-15 | 沈阳化工大学 | By the technique of 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production |
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