CN106748781B - A kind of method that calcium and magnesium aluminium composite oxide catalyzes and synthesizes methyl ethyl carbonate - Google Patents
A kind of method that calcium and magnesium aluminium composite oxide catalyzes and synthesizes methyl ethyl carbonate Download PDFInfo
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- CN106748781B CN106748781B CN201611057992.7A CN201611057992A CN106748781B CN 106748781 B CN106748781 B CN 106748781B CN 201611057992 A CN201611057992 A CN 201611057992A CN 106748781 B CN106748781 B CN 106748781B
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- C—CHEMISTRY; METALLURGY
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
A kind of method that calcium and magnesium aluminium composite oxide catalyzes and synthesizes methyl ethyl carbonate, it is synthesized under the catalytic action of calcium and magnesium aluminium composite oxide using dimethyl carbonate and diethyl carbonate as raw material and obtains methyl ethyl carbonate, it is characterized in that, the calcium and magnesium aluminium composite oxide is to roast 2~8 h products therefroms at 400~600 DEG C with calcium and magnesium aluminum hydrotalcite, the general structure of the calcium and magnesium aluminum hydrotalcite are as follows: Ca2+ xMg2+ yAl3+ 1‑x‑y(OH)2(CO3 2‑)(1‑x‑y)/2·mH2O, wherein 0.5≤x+y≤0.8,0.25≤x/y≤4, m are hydration number, 1≤m≤8.Method provided by the invention has the advantage that catalyst preparation process is simple, cheap, the high income of product, and catalyst is easily isolated and has good repeat performance.
Description
Technical field
The present invention relates to the method for catalyzing and synthesizing methyl ethyl carbonate, in particular to a kind of calcium and magnesium aluminium composite oxide catalysis is closed
At the method for methyl ethyl carbonate.
Background technique
Methyl ethyl carbonate is a kind of environmental-friendly asymmetric organic carbonate, is mainly used as organic synthesis intermediate and molten
Agent is especially used as the solvent of electrolyte in lithium ion battery.Compared with conventional lithium ion battery electrolyte solvent, methyl ethyl carbonate
The advantages of ester, is that the energy density and discharge capacity of battery can be improved, promotes security performance, prolong the service life, and has good
Good low temperature service performance etc..
According to the difference for using raw material, the synthetic route of EMC mainly has following three: (1), methylchloroformate and ethyl alcohol ester
Exchange process；(2), dimethyl carbonate and ethyl alcohol ester-interchange method；(3), dimethyl carbonate and diethyl carbonate ester-interchange method.Route
(1) raw material methylchloroformate is more toxic in, and reacts the HCl of by-product strong corrosive, therefore be gradually eliminated.Route (2)
It will form the azeotropic systems such as dimethyl carbonate-methanol, diethyl carbonate-ethyl alcohol, methyl ethyl carbonate-ethyl alcohol in reaction product, produce
The difficulty of object separating-purifying is very high.Meanwhile solvent for lithium (Jia Chun very strict to the content requirement of alcohols≤
0.032 mg/ml, Yi Chun≤0.029 mg/ml).Above-mentioned reason is restricted the application of route (2).Route (3) is in recent years
Carry out methyl ethyl carbonate synthetic route of greatest concern, its advantages are that reaction raw materials and product can be used as lithium ion battery electrolysis
Matter solvent, there is no need to separate just to can be used directly, the ratio for three kinds of esters that electrolyte solvent requires can pass through raw material proportioning
And control reacts the degree of progress to adjust.
The key technology of dimethyl carbonate and diethyl carbonate transesterification Catalysts of Preparing Methyl Ethyl Carbonate process route is efficiently
The exploitation of catalyst.In recent years, domestic and international research institution and large-scale lithium battery production firm begin to focus on research in this respect.Text
It offers and reports metallo-organic compound, alkali ionic liquid, load metal oxide, molecular sieve and metal-organic framework material
Etc. type catalysts.2003, Shen Zhenlu etc. (Catalysis Letters, 2003,91,63-67) discovery solid base MgO
To above-mentioned reaction catalytic activity with higher.2007, Chen Ying etc. (University Of Tianjin's journal, 2007,40,285-288) hair
It is 1 in the ratio between amount of substance of dimethyl carbonate and diethyl carbonate when now using Mg-Al metal composite oxide as catalyst:
1,103 DEG C of reaction temperature, under conditions of time 4h, the yield of methyl ethyl carbonate is 45.8%.The result shows that Mg-Al composition metal
The catalytic activity of oxide is to be improved, needs the longer reaction time that can just make to react close to balance.2010, Jia Mingjun etc.
(Journal of Molecular Catalysis A:Chemical, 2010,327,32-37) etc. develops mesoporous carbon
The MgO catalyst of NC-2 load, in 4 wt% of catalyst amount, 103 DEG C of reaction temperature, under conditions of 0.5 h of time, carbonic acid first
The yield of ethyl ester can reach 49.3%.2014, and Wang Jun etc. (Catalysis Letters, 2014,144,1602-
1608) the magnesium aluminate spinels catalysis material with meso-hole structure is prepared for using gas evaporation revulsion, in catalyst amount 5
Wt%, 103 DEG C of reaction temperature, under conditions of 0.5 h of time, the yield of methyl ethyl carbonate is 49.0%.
Although the MgO/NC-2 used in the prior art can promote to react in a relatively short period of time with magnesium aluminate spinels
Reach equilibrium state, but their preparation process is complicated, it is expensive, it is difficult to realize large-scale application.Therefore, a kind of tool is developed
Have that high activity, high stability, preparation process be simple, heterogeneous catalysis material cheap and be easily isolated is still this field
Technical staff's technical problem urgently to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of method that calcium and magnesium aluminium composite oxide catalyzes and synthesizes methyl ethyl carbonate, the party
Catalyst preparation process involved in method is simple, cheap, is easily isolated and has good repeat performance, product
High income.
The method that a kind of calcium and magnesium aluminium composite oxide provided by the invention catalyzes and synthesizes methyl ethyl carbonate, with dimethyl carbonate
It is synthesized under the catalytic action of calcium and magnesium aluminium composite oxide with diethyl carbonate for raw material and obtains methyl ethyl carbonate, feature exists
In the calcium and magnesium aluminium composite oxide is to roast 2~8h products therefrom, the calcium at 400~600 DEG C with calcium and magnesium aluminum hydrotalcite
The general structure of magnalium hydrotalcite are as follows: Ca2+ xMg2+ yAl3+ 1-x-y(OH)2(CO3 2-)(1-x-y)/2·mH2O, wherein 0.5≤x+y
≤ 0.8,0.25≤x/y≤4, m are hydration number, 1≤m≤8.
Further, the calcium and magnesium aluminum hydrotalcite preparation process comprising steps of
(1) according to Ca in calcium and magnesium aluminum hydrotalcite composition2+、Mg2+And Al3+The ratio between amount of substance, by calcium salt, magnesium salts and aluminium salt
It is made into mixing salt solution in proportion, wherein [Ca2+The mol/L of]=0.5~2.0；
(2) according to n (CO3 2-)/n(Al3+)=1.2~1.8, n (OH-)/[n(Ca2+)+n(Mg2+)+n(Al3+)]=1.4~
2.2 ratio, by Na2CO3Mixed ammonium/alkali solutions are made into NaOH, and make the mixing salt solution body in mixed ammonium/alkali solutions and step (1)
Product is identical；
(3) above two solution is flowed in reactor by identical speed double, is mixed in 20~90 DEG C of temperature ranges anti-
0.5~4h is answered, pH of mixed=9~11 is kept to be dehydrated sediment in 80~150 DEG C of 4~20h of crystallization, washing to filtrate pH=
7~8, obtained solid is the calcium and magnesium aluminum hydrotalcite of powder shaped after drying, crushing.
Further, the calcium salt in the step (1) is calcium chloride, calcium nitrate or calcium sulfate, and magnesium salts is magnesium chloride, nitric acid
Magnesium or magnesium sulfate, aluminium salt are aluminium chloride, aluminum nitrate or aluminum sulfate.
Further, the ratio between amount of substance of the dimethyl carbonate and diethyl carbonate is 0.25~4:1.
Further, the mass ratio of the calcium and magnesium aluminium composite oxide and reaction raw materials is 0.5~3:100.
Further, the temperature of the catalysis reaction is 80~120 DEG C.
Further, the time of the catalysis reaction is 10~150 minutes.
Calcium and magnesium aluminium composite oxide catalyst according to the present invention is fired by calcium and magnesium aluminum hydrotalcite and is prepared；Due to bone
Suitable calcium is introduced in frame, aoxidizes the base strength at the surface alkalinty center of calcium and magnesium aluminium composite oxide higher than Mg-Al composite
Object；In addition, the surface alkali density of calcium and magnesium aluminium composite oxide is high and is evenly distributed.The activated centre of a large amount of strong basicities then can promote
The quick generation of dimethyl carbonate and diethyl carbonate ester exchange reaction.Technical solution provided by the invention has the advantage that
The activity of catalyst is high, good, the high income of product of selectivity；Low in cost, the reuse easily separated with product of catalyst
It has excellent performance.
Specific embodiment
Specific embodiments of the present invention will be described in further detail below.For those of skill in the art
For member, from detailed description of the invention, above and other objects, features and advantages of the invention be will be evident.
Embodiment 1
The preparation of catalyst: 0.15 mol calcium chloride, 0.15 mol magnesium chloride and 0.15 mol aluminium chloride are configured to 300
The water solution A of mL；The sodium hydroxide of 0.75 mol and 0.23 mol sodium carbonate are configured to the aqueous solution B of 300 mL；In constant temperature
Under conditions of 40 DEG C and lasting stirring, solution A and solution B are added in 100 mL water with identical speed, keep pH of mixed=
9~11,0.5h is reacted, in 90 DEG C of crystallization 15h；It is filtered, washs, after dry, pulverize, obtain calcium and magnesium aluminum hydrotalcite Ca2+ 1/3Mg2 + 1/3Al3+ 1/3(OH)2(CO3 2-)1/6·4H2O；By gained calcium and magnesium aluminum hydrotalcite in 400 DEG C of roasting 6h to get calcium and magnesium aluminum composite oxide
Object.
Embodiment 2
The preparation of catalyst: 0.08 mol calcium nitrate, 0.32 mol magnesium nitrate and 0.1 mol aluminum nitrate are configured to 800
The water solution A of mL；The sodium hydroxide of 0.9 mol and 0.12 mol sodium carbonate are configured to the aqueous solution B of 800 mL；In constant temperature 20
DEG C and lasting stirring under conditions of, solution A and solution B are added in 100mL water with identical speed, keep pH of mixed=9~
11,2h is reacted, in 120 DEG C of crystallization 8h；It is filtered, washs, after dry, pulverize, obtain calcium and magnesium aluminum hydrotalcite Ca2+ 0.16Mg2+ 0.64Al3+ 0.2(OH)2(CO3 2-)0.1·8H2O；By gained hydrocalumite in 500 DEG C of roasting 4h to get calcium and magnesium aluminium composite oxide.
Embodiment 3
The preparation of catalyst: 0.16 mol calcium sulfate, 0.04 mol magnesium sulfate and 0.2 mol aluminum sulfate are configured to 200
The water solution A of mL；The sodium hydroxide of 0.56 mol and 0.18 mol sodium carbonate are configured to the aqueous solution B of 200 mL；In constant temperature
Under conditions of 90 DEG C and lasting stirring, solution A and solution B are added in 100 mL water with identical speed, keep pH of mixed=
9~11,2h is reacted, in 150 DEG C of crystallization 4h；It is filtered, washs, after dry, pulverize, obtain calcium and magnesium aluminum hydrotalcite Ca2+ 0.4Mg2 + 0.1Al3+ 0.5(OH)2(CO3 2-)0.25·2H2O；By gained hydrocalumite in 600 DEG C of roasting 2h to get calcium and magnesium aluminium composite oxide.
Embodiment 4
By 0.1 mol dimethyl carbonate, the calcium and magnesium aluminium composite oxygen of 0.1 mol diethyl carbonate and the preparation of 0.2 g embodiment 1
Compound catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas
The detection of phase chromatography, product yield 51.6%.
Embodiment 5
By 0.1 mol dimethyl carbonate, the calcium and magnesium aluminium composite oxygen of 0.1 mol diethyl carbonate and the preparation of 0.2 g embodiment 2
Compound catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas
The detection of phase chromatography, product yield 50.2%.
Embodiment 6
By 0.1 mol dimethyl carbonate, the calcium and magnesium aluminium composite oxygen of 0.1 mol diethyl carbonate and the preparation of 0.2 g embodiment 3
Compound catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 15 minutes, cooling, and centrifugation, liquid product uses
Gas chromatographic detection, product yield 43.1%.
Embodiment 7
By 0.1 mol dimethyl carbonate, the calcium and magnesium aluminium composite oxygen of 0.4 mol diethyl carbonate and the preparation of 0.2 g embodiment 1
Compound catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas
The detection of phase chromatography, product yield 85.5%.
Embodiment 8
By 0.4 mol dimethyl carbonate, the calcium and magnesium aluminium composite oxygen of 0.1 mol diethyl carbonate and the preparation of 0.2 g embodiment 1
Compound catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas
The detection of phase chromatography, product yield 20.9%.
Embodiment 9
By 0.1 mol dimethyl carbonate, the calcium Mg-Al composite of 0.1 mol diethyl carbonate and the preparation of 0.11 g embodiment 1
Oxide catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses
Gas chromatographic detection, product yield 42.5%.
Embodiment 10
By 0.1 mol dimethyl carbonate, the calcium and magnesium aluminium composite oxygen of 0.1 mol diethyl carbonate and the preparation of 0.6 g embodiment 1
Compound catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas
The detection of phase chromatography, product yield 50.8%.
Embodiment 11
By 0.1 mol dimethyl carbonate, the calcium and magnesium aluminium composite oxygen of 0.1 mol diethyl carbonate and the preparation of 0.3 g embodiment 1
Compound catalyst is added in reactor, opens stirring, is warming up to 80 DEG C, reacts 2.5h, and cooling, centrifugation, liquid product uses gas
The detection of phase chromatography, product yield 48.3%.
Embodiment 12
By 0.1 mol dimethyl carbonate, the calcium and magnesium aluminium composite oxygen of 0.1 mol diethyl carbonate and the preparation of 0.4 g embodiment 1
Compound catalyst is added in reactor, opens stirring, is warming up to 120 DEG C, reacts 10 minutes, cooling, and centrifugation, liquid product uses
Gas chromatographic detection, product yield 43.7%.
Embodiment 13
Circulation by catalyst used in embodiment 4, without any processing after being separated by filtration, for next batch
Reaction, the reaction condition and detection method of circular response are same as Example 4, and after being recycled 10 times, product yield is
50.6%。
Comparative example
By 0.1 mol dimethyl carbonate, 0.1 mol diethyl carbonate and 0.2 g Mg-Al composite oxide catalyst are added
In reactor, stirring is opened, is warming up to 103 DEG C, reacts 0.5h, cooling, centrifugation, liquid product uses gas chromatographic detection, produces
Object yield is 36.4%.
According to embodiment 4-13 with comparative example as a result, calcium and magnesium aluminium composite oxide of the present invention synthesizes transesterification
The reaction of methyl ethyl carbonate has very excellent catalytic performance, and catalytic activity is multiple better than the magnalium that prior art uses
Oxide is closed, catalyst the phenomenon that activity is decreased obviously does not occur after 10 times are reused.In addition, calcium and magnesium aluminum composite oxide
The preparation process of object catalyst is simple, low raw-material cost.Therefore, technical solution of the present invention is suitable for industrializing and answer
With.
It should be appreciated that although the present invention has carried out clear explanation by above embodiments, without departing substantially from the present invention
Spirit and its essence in the case where, person of ordinary skill in the field make in accordance with the present invention it is various it is corresponding variation and
Amendment, but these corresponding variations and modifications all should belong to scope of protection of the claims of the invention.
Claims (7)
1. a kind of method that calcium and magnesium aluminium composite oxide catalyzes and synthesizes methyl ethyl carbonate, is with dimethyl carbonate and diethyl carbonate
Raw material synthesizes under the catalytic action of calcium and magnesium aluminium composite oxide and obtains methyl ethyl carbonate, which is characterized in that the calcium and magnesium aluminium is multiple
Closing oxide is to roast 2~8h products therefrom at 400~600 DEG C with calcium and magnesium aluminum hydrotalcite, the knot of the calcium and magnesium aluminum hydrotalcite
Structure general formula are as follows: Ca2+ xMg2+ yAl3+ 1-x-y(OH)2(CO3 2-)(1-x-y)/2·mH2O, wherein 0.5≤x+y≤0.8,0.25≤
X/y≤4, m are hydration number, 1≤m≤8.
2. the method according to claim 1 for catalyzing and synthesizing methyl ethyl carbonate, which is characterized in that the calcium and magnesium aluminum hydrotalcite
Preparation process comprising steps of
(1) according to Ca in calcium and magnesium aluminum hydrotalcite composition2+、Mg2+And Al3+The ratio between amount of substance, by calcium salt, magnesium salts and aluminium salt press than
Example is made into mixing salt solution, wherein [Ca2+The mol/L of]=0.5~2.0；
(2) according to n (CO3 2-)/n(Al3+)=1.2~1.8, n (OH-)/[n(Ca2+)+n(Mg2+)+n(Al3+)]=1.4~2.2
Ratio, by Na2CO3Mixed ammonium/alkali solutions are made into NaOH, and make mixed ammonium/alkali solutions and the mixing salt solution volume phase in step (1)
Together；
(3) above two solution is flowed in reactor by identical speed double, the hybrid reaction 0.5 in 20~90 DEG C of temperature ranges
~4h keeps pH of mixed=9~11 to be dehydrated sediment in 80~150 DEG C of 4~20h of crystallization, washing to filtrate pH=7~8,
Obtained solid is the calcium and magnesium aluminum hydrotalcite of powder shaped after drying, crushing.
3. the method according to claim 2 for catalyzing and synthesizing methyl ethyl carbonate, which is characterized in that in the step (1)
Calcium salt be calcium chloride, calcium nitrate or calcium sulfate, magnesium salts be magnesium chloride, magnesium nitrate or magnesium sulfate, aluminium salt be aluminium chloride, aluminum nitrate or
Aluminum sulfate.
4. the method according to claim 1 for catalyzing and synthesizing methyl ethyl carbonate, which is characterized in that the dimethyl carbonate with
The ratio between amount of substance of diethyl carbonate is 0.25~4:1.
5. the method according to claim 1 for catalyzing and synthesizing methyl ethyl carbonate, which is characterized in that the calcium and magnesium aluminium composite oxygen
The mass ratio of compound and reaction raw materials is 0.5~3:100.
6. the method according to claim 1 for catalyzing and synthesizing methyl ethyl carbonate, which is characterized in that the temperature of the catalysis reaction
Degree is 80~120 DEG C.
7. the method according to claim 1 for catalyzing and synthesizing methyl ethyl carbonate, which is characterized in that it is described catalysis reaction when
Between be 10~150 minutes.
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