CN106748781A - 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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- CN106748781A CN106748781A CN201611057992.7A CN201611057992A CN106748781A CN 106748781 A CN106748781 A CN 106748781A CN 201611057992 A CN201611057992 A CN 201611057992A CN 106748781 A CN106748781 A CN 106748781A
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- Prior art keywords
- calcium
- magnesium
- methyl ethyl
- ethyl carbonate
- composite oxide
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- 239000011575 calcium Substances 0.000 title claims abstract description 52
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000011777 magnesium Substances 0.000 title claims abstract description 33
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 31
- 239000004411 aluminium Substances 0.000 title claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 17
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 15
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 230000036571 hydration Effects 0.000 claims abstract description 3
- 238000006703 hydration reaction Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 22
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 150000005682 diethyl carbonates Chemical class 0.000 description 10
- 150000005686 dimethyl carbonates Chemical class 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 229910003023 Mg-Al Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- -1 Magnesium aluminate Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052566 spinel group Inorganic materials 0.000 description 2
- QDMGKUOANLJICG-UHFFFAOYSA-N [Mg].[N+](=O)(O)[O-] Chemical compound [Mg].[N+](=O)(O)[O-] QDMGKUOANLJICG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GYBZGRWAJICXKI-UHFFFAOYSA-N diethyl carbonate;ethanol Chemical compound CCO.CCOC(=O)OCC GYBZGRWAJICXKI-UHFFFAOYSA-N 0.000 description 1
- GVQPPWPRLCJJOG-UHFFFAOYSA-N dimethyl carbonate;ethyl methyl carbonate Chemical compound COC(=O)OC.CCOC(=O)OC GVQPPWPRLCJJOG-UHFFFAOYSA-N 0.000 description 1
- GUNDKLAGHABJDI-UHFFFAOYSA-N dimethyl carbonate;methanol Chemical compound OC.COC(=O)OC GUNDKLAGHABJDI-UHFFFAOYSA-N 0.000 description 1
- UILXAFGEPVTJKG-UHFFFAOYSA-N ethanol ethyl methyl carbonate Chemical compound C(C)O.C(OC)(OCC)=O UILXAFGEPVTJKG-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A kind of method that calcium and magnesium aluminium composite oxide catalyzes and synthesizes methyl ethyl carbonate, synthesized under the catalytic action of calcium and magnesium aluminium composite oxide as raw material with dimethyl carbonate and diethyl carbonate and obtain methyl ethyl carbonate, it is characterized in that, the calcium and magnesium aluminium composite oxide is that 2~8 h products therefroms are calcined at 400~600 DEG C with calcium and magnesium aluminum hydrotalcite, and the general structure of the calcium and magnesium aluminum hydrotalcite is：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 is hydration number, 1≤m≤8.The method that the present invention is provided has advantages below：Catalyst preparation process is simple, and cheap, the high income of product, catalyst is easily isolated and with good repeat performance.
Description
Technical field
Method the present invention relates to catalyze and synthesize methyl ethyl carbonate, more particularly to a kind of calcium and magnesium aluminium composite oxide catalysis is closed
Into the method for methyl ethyl carbonate.
Background technology
Methyl ethyl carbonate is a kind of environment-friendly asymmetric organic carbonate, is mainly used as organic synthesis intermediate and molten
Agent, particularly as the solvent of electrolyte in lithium ion battery.Compared with conventional lithium ion battery electrolyte solvent, methyl ethyl carbonate
The advantage of ester is the energy density and discharge capacity that can improve battery, lifts security performance, is increased the service life, and with good
Good low temperature performance etc..
According to the difference using raw material, the synthetic route of EMC mainly has following three：(1), methylchloroformate and ethanol ester
Exchange process；(2), dimethyl carbonate and ethanol ester-interchange method；(3), dimethyl carbonate and diethyl carbonate ester-interchange method.Route
（1）Middle raw material methylchloroformate toxicity is larger, and reacts the HCl of by-product severe corrosive, therefore is progressively eliminated.Route（2）'s
The azeotropic systems such as dimethyl carbonate-methanol, diethyl carbonate-ethanol, methyl ethyl carbonate-ethanol can be formed in product, is produced
The difficulty of thing separating-purifying is very high.Meanwhile, solvent for lithium is very strict to the content requirement of alcohols（Jia Chun≤
0.032 mg/ml, Yi Chun≤0.029 mg/ml）.Above-mentioned reason makes route（2）Application be restricted.Route（3）It is in recent years
Carry out methyl ethyl carbonate synthetic route of greatest concern, its advantage is that reaction raw materials and product can be electrolysed as lithium ion battery
Matter solvent, therefore just be can be used directly without separating, three kinds of ratios of ester of electrolyte solvent requirement can be by raw material proportioning
And control the degree that reaction is carried out to adjust.
Dimethyl carbonate is efficient with the key technology of diethyl carbonate ester exchange Catalysts of Preparing Methyl Ethyl Carbonate process route
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
Offer and report metallo-organic compound, alkali ionic liquid, load metal oxide, molecular sieve and metal-organic framework material
Etc. type catalyst., Shen Zhenlu etc. in 2003（Catalysis Letters, 2003, 91, 63-67）It was found that solid base MgO
There is catalysis activity higher to above-mentioned reaction., Chen Ying etc. in 2007（University Of Tianjin's journal, 2007,40,285-288）Hair
It is 1 in the ratio between the amount of material of dimethyl carbonate and diethyl carbonate when now with Mg-Al metal composite oxides as catalyst：
1,103 DEG C of reaction temperature, under conditions of time 4h, the yield of methyl ethyl carbonate is 45.8%.Result shows Mg-Al composition metals
The catalysis activity of oxide has much room for improvement, it is necessary to the reaction time more long can just make reaction close to balance., Jia Mingjun etc. in 2010
（Journal of Molecular Catalysis A: Chemical, 2010, 327, 32–37）Etc. developing mesoporous carbon
The MgO catalyst of NC-2 loads, in the wt% of catalyst amount 4,103 DEG C of reaction temperature, under conditions of the h of time 0.5, carbonic acid first
The yield of ethyl ester is that can reach 49.3%., Wang Jun etc. in 2014（Catalysis Letters, 2014, 144, 1602-
1608）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 the h of time 0.5, the yield of methyl ethyl carbonate is 49.0%.
Although the MgO/NC-2 for using in the prior art can in the short period of time promote reaction with magnesium aluminate spinels
Poised state is reached, but their preparation process is complicated, it is expensive, it is difficult to realize large-scale application.Therefore, a kind of tool is developed
The heterogeneous catalysis material for having high activity, high stability, preparation process simple, cheap and being easily isolated is still this area
Technical staff is badly in need of the technical problem for solving.
The content of the invention
It is an object of the invention 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 by method is simple, cheap, it is easy to separate and with good repeat performance, product
High income.
The method that a kind of calcium and magnesium aluminium composite oxide that the present invention is provided catalyzes and synthesizes methyl ethyl carbonate, with dimethyl carbonate
Methyl ethyl carbonate is obtained for raw material synthesizes under the catalytic action of calcium and magnesium aluminium composite oxide with diethyl carbonate, its feature exists
In the calcium and magnesium aluminium composite oxide is that 2~8h products therefroms, the calcium are calcined at 400~600 DEG C with calcium and magnesium aluminum hydrotalcite
The general structure of magnalium hydrotalcite is：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 is hydration number, 1≤m≤8.
Further, the preparation process of the calcium and magnesium aluminum hydrotalcite includes step：
（1）Ca in being constituted according to calcium and magnesium aluminum hydrotalcite2+、Mg2+And Al3+The ratio between amount of material, 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 step（1）In mixing salt solution volume phase
Together；
（3）During above two solution flowed into 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, in 80~150 DEG C of 4~20h of crystallization, sediment is dehydrated, and washs to filtrate pH=7~8,
Gained solid is the calcium and magnesium aluminum hydrotalcite of powder shaped after drying, crushing.
Further, the step（1）In calcium salt be calcium chloride, calcium nitrate or calcium sulfate, magnesium salts be magnesium chloride, nitric acid
Magnesium or magnesium sulfate, aluminium salt are aluminium chloride, aluminum nitrate or aluminum sulfate.
Further, the ratio between amount of material of the dimethyl carbonate and diethyl carbonate is 0.25~4：1.
Further, the calcium and magnesium aluminium composite oxide and the mass ratio of reaction raw materials are 0.5~3：100.
Further, the temperature of the catalytic reaction is 80~120 DEG C.
Further, the time of the catalytic reaction is 10~150 minutes.
Calcium and magnesium aluminium composite oxide catalyst involved in the present invention is fired by calcium and magnesium aluminum hydrotalcite and prepares；Due to bone
Appropriate calcium is introduced in frame, the base strength at the surface alkalinty center of calcium and magnesium aluminium composite oxide is aoxidized higher than Mg-Al composite
Thing；Additionally, 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 can then promote
The quick generation of dimethyl carbonate and diethyl carbonate ester exchange reaction.The technical scheme that the present invention is provided has advantages below：
The activity of catalyst is high, good, the high income of product of selectivity；With low cost, the reuse easily separated with product of catalyst
Excellent performance.
Specific embodiment
Specific embodiment of the invention is 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 will be evident that.
Embodiment 1
The preparation of catalyst：0.15mol calcium chloride, 0.15mol magnesium chlorides and 0.15mol aluminium chloride are configured to the water of 300 mL
Solution A；The NaOH of 0.75 mol and 0.23 mol sodium carbonate are configured to the aqueous solution B of 300 mL；In 40 DEG C of constant temperature and
Under conditions of lasting stirring, during solution A and solution B added into 100 mL water with same speed, pH of mixed=9~11 are kept,
Reaction 0.5h, in 90 DEG C of crystallization 15h；Through filtering, washing after dry, pulverize, obtains calcium and magnesium aluminum hydrotalcite Ca2+ 1/3Mg2+ 1/3Al3 + 1/3(OH)2(CO3 2-)1/6·4H2O；Gained calcium and magnesium aluminum hydrotalcite is calcined 6h at 400 DEG C, calcium and magnesium aluminium composite oxide is obtained final product.
Embodiment 2
The preparation of catalyst：0.08mol calcium nitrate, 0.32mol magnesium nitrates and 0.1mol aluminum nitrates are configured to the water of 800 mL
Solution A；The NaOH of 0.9 mol and 0.12 mol sodium carbonate are configured to the aqueous solution B of 800 mL；In 20 DEG C of constant temperature and hold
Under conditions of continuous stirring, during solution A and solution B added into 100mL water with same speed, pH of mixed=9~11 are kept, instead
2h is answered, in 120 DEG C of crystallization 8h；Through filtering, washing after dry, pulverize, obtains calcium and magnesium aluminum hydrotalcite Ca2+ 0.16Mg2+ 0.64Al3+ 0.2
(OH)2(CO3 2-)0.1·8H2O；Gained hydrocalumite is calcined 4h at 500 DEG C, calcium and magnesium aluminium composite oxide is obtained final product.
Embodiment 3
The preparation of catalyst：0.16mol calcium sulfate, 0.04mol magnesium sulfate and 0.2mol aluminum sulfate are configured to the water of 200 mL
Solution A；The NaOH of 0.56 mol and 0.18 mol sodium carbonate are configured to the aqueous solution B of 200 mL；In 90 DEG C of constant temperature and
Under conditions of lasting stirring, during solution A and solution B added into 100 mL water with same speed, pH of mixed=9~11 are kept,
Reaction 2h, in 150 DEG C of crystallization 4h；Through filtering, washing after dry, pulverize, obtains calcium and magnesium aluminum hydrotalcite Ca2+ 0.4Mg2+ 0.1Al3+ 0.5
(OH)2(CO3 2-)0.25·2H2O；Gained hydrocalumite is calcined 2h at 600 DEG C, calcium and magnesium aluminium composite oxide is obtained final product.
Embodiment 4
0.1mol dimethyl carbonates, the calcium and magnesium aluminium composite oxide that 0.1mol diethyl carbonates are prepared with 0.2g embodiments 1 are urged
Agent is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas-chromatography
Detection, product yield is 51.6%.
Embodiment 5
By 0.1 mol dimethyl carbonates, calcium and magnesium aluminium composite oxide prepared by 0.1 mol diethyl carbonates and 0.2 g embodiments 2
Catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas phase color
Spectrum detection, product yield is 50.2%.
Embodiment 6
By 0.1 mol dimethyl carbonates, calcium and magnesium aluminium composite oxide prepared by 0.1 mol diethyl carbonates and 0.2 g embodiments 3
Catalyst is added in reactor, opens stirring, is warming up to 103 DEG C, is reacted 15 minutes, and cooling, centrifugation, liquid product uses gas phase
Chromatogram detects that product yield is 43.1%.
Embodiment 7
0.1mol dimethyl carbonates, the calcium and magnesium aluminium composite oxide that 0.4mol diethyl carbonates are prepared with 0.2g embodiments 1 are urged
Agent is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas-chromatography
Detection, product yield is 85.5%.
Embodiment 8
0.4mol dimethyl carbonates, the calcium and magnesium aluminium composite oxide that 0.1mol diethyl carbonates are prepared with 0.2g embodiments 1 are urged
Agent is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas-chromatography
Detection, product yield is 20.9%.
Embodiment 9
0.1mol dimethyl carbonates, the calcium and magnesium aluminium composite oxide that 0.1mol diethyl carbonates are prepared with 0.11g embodiments 1 are urged
Agent is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas-chromatography
Detection, product yield is 42.5%.
Embodiment 10
0.1mol dimethyl carbonates, the calcium and magnesium aluminium composite oxide that 0.1mol diethyl carbonates are prepared with 0.6g embodiments 1 are urged
Agent is added in reactor, opens stirring, is warming up to 103 DEG C, reacts 0.5h, and cooling, centrifugation, liquid product uses gas-chromatography
Detection, product yield is 50.8%.
Embodiment 11
0.1mol dimethyl carbonates, the calcium and magnesium aluminium composite oxide that 0.1mol diethyl carbonates are prepared with 0.3g embodiments 1 are urged
Agent is added in reactor, opens stirring, is warming up to 80 DEG C, reacts 2.5h, and cooling, centrifugation, liquid product uses gas-chromatography
Detection, product yield is 48.3%.
Embodiment 12
0.1mol dimethyl carbonates, the calcium and magnesium aluminium composite oxide that 0.1mol diethyl carbonates are prepared with 0.4g embodiments 1 are urged
Agent is added in reactor, opens stirring, is warming up to 120 DEG C, is reacted 10 minutes, and cooling, centrifugation, liquid product uses gas phase color
Spectrum detection, product yield is 43.7%.
Embodiment 13
By the catalyst after use in embodiment 4, without any treatment after being separated by filtration, the circulation for next batch is anti-
Should, the reaction condition of circular response is same as Example 4 with detection method, and after recycling 10 times, product yield is 50.6%.
Comparative example
0.1mol dimethyl carbonates, 0.1mol diethyl carbonates are added into reactor with 0.2g Mg-Al composite oxides catalyst
In, stirring is opened, 103 DEG C are warming up to, 0.5h is reacted, cooling, centrifugation, liquid product uses gas chromatographic detection, product yield
It is 36.4%.
According to embodiment 4-13 and the result of comparative example, calcium and magnesium aluminium composite oxide of the present invention synthesizes to ester exchange
The reaction of methyl ethyl carbonate has very excellent catalytic performance, and its catalysis activity is answered better than the magnalium that prior art is used
Oxide is closed, catalyst does not have the phenomenon that activity is decreased obviously occur after being reused through 10 times.Additionally, calcium and magnesium aluminum composite oxide
The preparation process of thing catalyst is simple, low raw-material cost.Therefore, technical scheme of the present invention is suitable for industrializing and answers
With.
Although it should be appreciated that the present invention has carried out clear explanation by above example, but without departing substantially from the present invention
Spirit and its essence in the case of, person of ordinary skill in the field when can according to the present invention make it is various it is corresponding change and
Amendment, but these corresponding variations and modifications should all belong to scope 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, be with diethyl carbonate with dimethyl carbonate
Raw material synthesizes under the catalytic action of calcium and magnesium aluminium composite oxide and obtains methyl ethyl carbonate, it is characterised in that the calcium and magnesium aluminium is answered
It is that 2~8h products therefroms, the knot of the calcium and magnesium aluminum hydrotalcite are calcined at 400~600 DEG C with calcium and magnesium aluminum hydrotalcite to close oxide
Structure formula is：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 is hydration number, 1≤m≤8.
2. the method for catalyzing and synthesizing methyl ethyl carbonate according to claim 1, it is characterised in that the calcium and magnesium aluminum hydrotalcite
Preparation process include step：
（1）Ca in being constituted according to calcium and magnesium aluminum hydrotalcite2+、Mg2+And Al3+The ratio between amount of material, 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 step（1）In mixing salt solution volume phase
Together；
（3）During above two solution flowed into 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, in 80~150 DEG C of 4~20h of crystallization, sediment is dehydrated, and washs to filtrate pH=7~8,
Gained solid is the calcium and magnesium aluminum hydrotalcite of powder shaped after drying, crushing.
3. the method for catalyzing and synthesizing methyl ethyl carbonate according to claim 2, it is characterised in that the step（1）In
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 for catalyzing and synthesizing methyl ethyl carbonate according to claim 1, it is characterised in that the dimethyl carbonate with
The ratio between amount of material of diethyl carbonate is 0.25~4：1.
5. the method for catalyzing and synthesizing methyl ethyl carbonate according to claim 1, it is characterised in that the calcium and magnesium aluminium composite oxygen
Compound is 0.5~3 with the mass ratio of reaction raw materials：100.
6. the method for catalyzing and synthesizing methyl ethyl carbonate according to claim 1, it is characterised in that the temperature of the catalytic reaction
Spend is 80~120 DEG C.
7. the method for catalyzing and synthesizing methyl ethyl carbonate according to claim 1, it is characterised in that the catalytic reaction when
Between be 10~150 minutes.
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| CN115779883A (en) * | 2022-12-13 | 2023-03-14 | 新疆至臻化工工程研究中心有限公司 | Catalyst for directionally synthesizing alkyl carbonate from alkyl oxalate |
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