CN106748782B - A kind of method of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing Methyl Ethyl Carbonate - Google Patents
A kind of method of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing Methyl Ethyl Carbonate Download PDFInfo
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- CN106748782B CN106748782B CN201611057993.1A CN201611057993A CN106748782B CN 106748782 B CN106748782 B CN 106748782B CN 201611057993 A CN201611057993 A CN 201611057993A CN 106748782 B CN106748782 B CN 106748782B
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- lanthanum
- methyl ethyl
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- ethyl carbonate
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
Abstract
A kind of method of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing Methyl Ethyl Carbonate, it is synthesized under the catalytic action of magnalium lanthanium complex oxide using dimethyl carbonate and diethyl carbonate as raw material and obtains methyl ethyl carbonate, it is characterized in that, the magnalium lanthanium complex oxide is to roast 2~8 h products therefroms at 400~600 DEG C with magnesium aluminium lanthanum houghite, the general structure of the magnesium aluminium lanthanum houghite are as follows: Mg2+ 1‑x‑yAl3+ xLa3+ y(OH)2(CO3 2‑)(x+y)/2·mH2O, wherein 0.2≤x+y≤0.5,1≤x/y≤9, m are hydration number, 1≤m≤8.Method provided by the invention has the advantage that catalyst preparation process is simple, and production cost is low, 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 magnesium aluminium lanthanum composite oxide catalytic closes
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 of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing 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 of a kind of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing Methyl Ethyl Carbonate provided by the invention, with dimethyl carbonate
It is synthesized under the catalytic action of magnalium lanthanium complex oxide with diethyl carbonate for raw material and obtains methyl ethyl carbonate, feature exists
In the magnalium lanthanium complex oxide is to roast 2~8 h products therefroms, institute at 400~600 DEG C with magnesium aluminium lanthanum houghite
State the general structure of magnesium aluminium lanthanum houghite are as follows: Mg2+ 1-x-yAl3+ xLa3+ y(OH)2(CO3 2-)(x+y)/2·mH2O, wherein 0.2≤
X+y≤0.5,1≤x/y≤9, m are hydration number, 1≤m≤8.
Further, the magnesium aluminium lanthanum houghite preparation process comprising steps of
(1) according to Mg in magnesium aluminium lanthanum houghite composition2+、Al3+And La3+The ratio between amount of substance, by magnesium salts, aluminium salt and lanthanum
Salt is made into mixing salt solution in proportion, wherein [Mg2+The mol/L of]=0.5~2.0；
(2) according to n (OH-)/[n(Mg2+)+n(Al3+)+n(La3+)]=1.4~2.2, n (CO3 2-)/[n(Al3+)+n(La3 +)]=1.2~1.8 ratio, by Na2CO3Mixed ammonium/alkali solutions are made into NaOH, and are made mixed in mixed ammonium/alkali solutions and step (1)
It is identical to close salting liquid volume；
(3) above two solution is flowed in reactor by identical speed double, is mixed in 20~90 DEG C of temperature ranges anti-
0.5~4 h is answered, pH of mixed=9~11 is kept to be dehydrated sediment in 80~150 DEG C of 4~20 h of crystallization, washing to filtrate
PH=7~8, obtained solid are the magnesium aluminium lanthanum houghite of powder shaped after drying, crushing.
Further, the magnesium salts in the step (1) is magnesium chloride, magnesium nitrate or magnesium sulfate, and aluminium salt is aluminium chloride, nitric acid
Aluminium or aluminum sulfate, lanthanum salt are lanthanum chloride, lanthanum nitrate or lanthanum 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 magnalium lanthanium complex 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.
Magnesium aluminium lanthanum composite oxide catalysts according to the present invention are fired by magnesium aluminium lanthanum houghite and are prepared；Due to
Suitable rare-earth elements of lanthanum is introduced in skeleton, makes the base strength and alkali density at the surface alkalinty center of magnalium lanthanium complex oxide
It is above traditional Mg-Al composite oxide；In addition, the surface alkalinty central distribution of magnalium lanthanium complex oxide is uniform.It is a large amount of strong
The activated centre of alkalinity can promote the quick generation of dimethyl carbonate Yu diethyl carbonate ester exchange reaction.Skill provided by the invention
Art scheme has the advantage that the activity of catalyst is high, good, the high income of product of selectivity；The cost of catalyst is low, with product
Easily separated, repeat performance is excellent.
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: 0.3 mol magnesium chloride, 0.12 mol aluminium chloride and 0.03 mol lanthanum 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=
9~11,0.5 h is reacted, in 90 DEG C of 15 h of crystallization；It is filtered, washs, after dry, pulverize, obtain magnesium aluminium lanthanum houghite Mg2 + 2/3Al3+ 4/15La3+ 1/15(OH)2(CO3 2-)1/6·4H2O；By gained magnesium aluminium lanthanum houghite in 400 DEG C of 6 h of roasting to get magnalium
Lanthanium complex oxide.
Embodiment 2
The preparation of catalyst: 0.4 mol magnesium nitrate, 0.05 mol aluminum nitrate and 0.05 mol lanthanum 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~
11,2 h are reacted, in 120 DEG C of crystallization 8h；It is filtered, washs, after dry, pulverize, obtain magnesium aluminium lanthanum houghite Mg2+ 0.8Al3 + 0.1La3+ 0.1(OH)2(CO3 2-)0.1·8H2O；By gained hydrocalumite in 500 DEG C of 4 h of roasting to get magnalium lanthanium complex oxide.
Embodiment 3
The preparation of catalyst: 0.2 mol magnesium sulfate, 0.18 mol aluminum sulfate and 0.02 mol lanthanum 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=
9~11,2 h are reacted, in 150 DEG C of 4 h of crystallization；It is filtered, washs, after dry, pulverize, obtain magnesium aluminium lanthanum houghite Mg2+ 0.5Al3+ 0.45La3+ 0.05(OH)2(CO3 2-)0.25·2H2O；Gained hydrocalumite is compound to get magnesium aluminium lanthanum in 600 DEG C of 2 h of roasting
Oxide.
Embodiment 4
By 0.1 mol dimethyl carbonate, the magnesium aluminium lanthanum 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 0.5 h, and cooling, centrifugation, liquid product uses
Gas chromatographic detection, product yield 51.9%.
Embodiment 5
By 0.1 mol dimethyl carbonate, the magnesium aluminium lanthanum 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 0.5 h, and cooling, centrifugation, liquid product uses
Gas chromatographic detection, product yield 50.7%.
Embodiment 6
By 0.1 mol dimethyl carbonate, the magnesium aluminium lanthanum 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 42.6%.
Embodiment 7
By 0.1 mol dimethyl carbonate, the magnesium aluminium lanthanum 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 0.5 h, and cooling, centrifugation, liquid product uses
Gas chromatographic detection, product yield 83.9%.
Embodiment 8
By 0.4 mol dimethyl carbonate, the magnesium aluminium lanthanum 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 0.5 h, and cooling, centrifugation, liquid product uses
Gas chromatographic detection, product yield 19.5%.
Embodiment 9
By 0.1 mol dimethyl carbonate, 0.1 mol diethyl carbonate and magnesium aluminium lanthanum prepared by 0.11 g embodiment 1 are compound
Oxide catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5 h, and cooling, centrifugation, liquid product is adopted
With gas chromatographic detection, product yield 41.6%.
Embodiment 10
By 0.1 mol dimethyl carbonate, the magnesium aluminium lanthanum 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 0.5 h, and cooling, centrifugation, liquid product uses
Gas chromatographic detection, product yield 51.0%.
Embodiment 11
By 0.1 mol dimethyl carbonate, the magnesium aluminium lanthanum 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 2.5 h, and cooling, centrifugation, liquid product uses gas
The detection of phase chromatography, product yield 46.2%.
Embodiment 12
By 0.1 mol dimethyl carbonate, the magnesium aluminium lanthanum 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 41.9%.
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
51.1%。
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 0.5 h, 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, magnalium lanthanium complex 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, magnesium aluminium lanthanum combined oxidation
The preparation process of object catalyst is simple, and production cost is low.Therefore, technical solution of the present invention is suitable for industrial applications.
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 of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing Methyl Ethyl Carbonate, is with dimethyl carbonate and diethyl carbonate
Raw material synthesizes under the catalytic action of magnalium lanthanium complex oxide and obtains methyl ethyl carbonate, which is characterized in that the magnesium aluminium lanthanum is multiple
Closing oxide is to roast 2~8 h products therefroms at 400~600 DEG C with magnesium aluminium lanthanum houghite, the magnesium aluminium lanthanum houghite
General structure are as follows: Mg2+ 1-x-yAl3+ xLa3+ y(OH)2(CO3 2-)(x+y)/2·mH2O, wherein 0.2≤x+y≤0.5,1≤
X/y≤9, 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 magnesium aluminium lanthanum class neatly
The preparation process of stone comprising steps of
(1) according to Mg in magnesium aluminium lanthanum houghite composition2+、Al3+And La3+The ratio between amount of substance presses magnesium salts, aluminium salt and lanthanum salt
Ratio is made into mixing salt solution, wherein [Mg2+The mol/L of]=0.5~2.0；
(2) according to n (OH-)/[n(Mg2+)+n(Al3+)+n(La3+)]=1.4~2.2, n (CO3 2-)/[n(Al3+)+n(La3+)] =
1.2~1.8 ratio, by Na2CO3Mixed ammonium/alkali solutions are made into NaOH, and make the salt-mixture in mixed ammonium/alkali solutions and step (1)
Liquor capacity is identical；
(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
~4 h keep pH of mixed=9~11 to be dehydrated sediment in 80~150 DEG C of 4~20 h of crystallization, and washing to filtrate pH=7~
8, obtained solid is the magnesium aluminium lanthanum houghite 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)
Magnesium salts be magnesium chloride, magnesium nitrate or magnesium sulfate, aluminium salt be aluminium chloride, aluminum nitrate or aluminum sulfate, lanthanum salt be lanthanum chloride, lanthanum nitrate or
Lanthanum 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 magnesium aluminium lanthanum 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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| CN107486193B (en) * | 2017-07-18 | 2020-09-08 | 福州大学化肥催化剂国家工程研究中心 | Hydrogenation catalyst and preparation method thereof |
| CN113797912A (en) * | 2020-06-12 | 2021-12-17 | 中国石油化工股份有限公司 | Aluminum-containing magnesium-lanthanum composite oxide and preparation method and application thereof |
| CN112724017B (en) * | 2021-01-14 | 2022-09-20 | 吉林师范大学 | Method for synthesizing asymmetric organic carbonate at room temperature |
| CN116272946A (en) * | 2023-01-19 | 2023-06-23 | 大连理工大学 | Zinc magnesium aluminum solid base catalyst, preparation method and method for preparing dimethyl carbonate by using zinc magnesium aluminum solid base catalyst |
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| US5760273A (en) * | 1995-10-25 | 1998-06-02 | Mitsubishi Chemical Corporation | Process for producing unsymmetrical chain carbonic acid ester |
| CN103172519A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院兰州化学物理研究所 | Synthetic method of methyl ethyl carbonate |
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| US5760273A (en) * | 1995-10-25 | 1998-06-02 | Mitsubishi Chemical Corporation | Process for producing unsymmetrical chain carbonic acid ester |
| CN103172519A (en) * | 2011-12-23 | 2013-06-26 | 中国科学院兰州化学物理研究所 | Synthetic method of methyl ethyl carbonate |
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