CN106588659A - Method for synthesizing methyl ethyl carbonate under catalysis of roasted-state hydrocalumite - Google Patents
Method for synthesizing methyl ethyl carbonate under catalysis of roasted-state hydrocalumite Download PDFInfo
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- CN106588659A CN106588659A CN201611057990.8A CN201611057990A CN106588659A CN 106588659 A CN106588659 A CN 106588659A CN 201611057990 A CN201611057990 A CN 201611057990A CN 106588659 A CN106588659 A CN 106588659A
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- hydrocalumite
- ethyl methyl
- methyl carbonate
- catalyzing
- carbonate
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- 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 23
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 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
- 239000000047 product Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 230000008569 process 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [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
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 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 1
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 150000005682 diethyl carbonates Chemical class 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- -1 magnesium aluminate Chemical class 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
- 239000002585 base 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
- 238000001228 spectrum Methods 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910003023 Mg-Al Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052566 spinel group Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 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
- 238000001914 filtration Methods 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
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 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
- 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
- 238000004064 recycling Methods 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
- 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
- B01J23/007—Mixed salts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing methyl ethyl carbonate under catalysis of roasted-state hydrocalumite. The methyl ethyl carbonate is synthesized from dimethyl carbonate and diethyl carbonate which serve as raw materials under the catalytic action of the roasted-state hydrocalumite. The general structural formula of the hydrocalumite is as follows: Ca<2+>1-xAl<3+>x(OH)2(CO3<2->)x/2.mH2O, wherein x is greater than or equal to 0.2 and less than or equal to 0.5, and m is the number of crystal water and is greater than or equal to 1 and less than or equal to 8. The roasted-state hydrocalumite is a product obtained by roasting hydrocalumite at the temperature of 400 to 600 DEG C for 2 to 8 hours. The method provided by the invention has the following advantages: the catalyst preparation process is simple, the cost is low, and the yield of a product is high; and the catalyst is easy to separate and high in reusability.
Description
Technical field
The present invention relates to the method for catalyzing and synthesizing Ethyl methyl carbonate, more particularly to a kind of roasting state hydrocalumite is catalyzed and synthesized
The method of Ethyl methyl carbonate.
Background technology
Ethyl methyl carbonate is a kind of eco-friendly asymmetric organic carbonate, is mainly used as organic synthesis intermediate and molten
Agent, the solvent particularly as electrolyte in lithium ion battery.Compared with conventional lithium ion battery electrolyte solvent, methyl ethyl carbonate
The advantage of ester is to improve the energy density and discharge capacity of battery, lifts security performance, increases the service life, and is had 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, Ethyl methyl 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 Ethyl methyl 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 can be used directly without the need for separating, the ratio of three kinds of esters that electrolyte solvent is required can pass through proportioning raw materials
And the control degree that carries out of reaction is adjusting.
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.2003, Shen Zhenlu etc.（Catalysis Letters, 2003, 91, 63-67）It was found that solid base MgO
There is higher catalysis activity to above-mentioned reaction.2007, Chen Ying etc.（University Of Tianjin's journal, 2007,40,285-288）Send out
When now with Mg-Al metal composite oxides as catalyst, it is 1 in the ratio of dimethyl carbonate and the amount of the material of diethyl carbonate：
1,103 DEG C of reaction temperature, under conditions of time 4h, the yield of Ethyl methyl carbonate is 45.8%.As a result Mg-Al composition metals are shown
The catalysis activity of oxide has much room for improvement, and needs the longer response time just make reaction be close to balance.2010, Jia Mingjun etc.
（Journal of Molecular Catalysis A: Chemical, 2010, 327, 32–37）Etc. developing mesoporous carbon
The MgO catalyst of NC-2 loads, 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 is 49.3%.2014, Wang Jun etc.（Catalysis Letters, 2014, 144, 1602-1608）Using
Gas evaporation revulsion is prepared for the magnesium aluminate spinels catalysis material with meso-hole structure, in 5 wt% of catalyst amount, reaction
103 DEG C of temperature, under conditions of 0.5 h of time, the yield of Ethyl methyl carbonate is 49.0%.
Although the MgO/NC-2 adopted in prior art can promote reaction in the short period of time 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, develop a kind of tool
The heterogeneous catalysiss material for having high activity, high stability, preparation process simple, cheap and being easily isolated remains 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 roasting state hydrocalumite catalyzes and synthesizes Ethyl methyl carbonate, the method
Involved catalyst preparation process is simple, cheap, it is easy to separate and with good repeat performance, the receipts of product
Rate is high.
A kind of roasting state hydrocalumite method for catalyzing and synthesizing Ethyl methyl carbonate that the present invention is provided, with dimethyl carbonate with
Diethyl carbonate synthesizes under the catalytic action of roasting state hydrocalumite for raw material and obtains Ethyl methyl carbonate, the hydrocalumite
General structure is：Ca2+ 1-xAl3+ x(OH)2(CO3 2-)x/2·mH2O, wherein, 0.2≤x≤0.5, m is hydration number, 1
≤ m≤8, the roasting state hydrocalumite be with hydrocalumite at 400～600 DEG C 2～8 hours products therefroms of roasting.
Further, the preparation process of the hydrocalumite includes step：
（1）According to Ca in hydrocalumite composition2+And Al3+Calcium salt, aluminium salt are made into salt-mixture molten by the amount proportioning of material in proportion
Liquid, 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(Al3+)]=1.4～2.2 ratio, will
Na2CO3Mixed ammonium/alkali solutions are made into NaOH, and make mixed ammonium/alkali solutions and step（1）In mixing salt solution volume it is identical；
（3）By above two solution by identical speed double fluid in reactor, the hybrid reaction 0.5 in 20～90 DEG C of temperature ranges
～4 hours, pH of mixed=10～12 are kept, in 80～150 DEG C of crystallization 4～20 hours, precipitate is dehydrated, is washed to filtrate
PH=7～8, are the hydrocalumite of powder shaped after gained solid drying, crushing.
Further, the step（1）In calcium salt be calcium chloride, calcium nitrate or calcium sulfate, aluminium salt be aluminum chloride, nitric acid
Aluminum or aluminum sulfate.
Further, the dimethyl carbonate and the ratio of the amount of the material of diethyl carbonate are 0.25～4：1.
Further, the roasting state hydrocalumite 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.
Roasting state hydrocalumite involved in the present invention has suitable base strength and high-specific surface area, and surface alkali density is high
And be evenly distributed.Active center with a large amount of suitable base strengths can then promote dimethyl carbonate anti-with diethyl carbonate ester exchange
The quick generation answered.The technical scheme that the present invention is provided has advantages below：With low cost, the activity height of catalyst, selectivity
It is good, reaction can be promoted to be rapidly achieved balance, catalyst is easily separated with product, and the repeat performance of catalyst is excellent.
Specific embodiment
Below the specific embodiment of the present invention is described in further detail.For those of skill in the art
For member, from detailed description of the invention, the above and other objects, features and advantages of the present invention will be evident that.
Embodiment 1
The preparation of catalyst：0.3 mol calcium chloride and 0.15 mol aluminum chloride are configured to into the water solution A of 300 mL；By 0.75
The sodium hydroxide of mol and 0.23 mol sodium carbonate are configured to the aqueous solution B of 300 mL；The condition for stirring in 40 DEG C of constant temperature and persistently
Under, solution A is added in 100 mL water with same speed with solution B, pH of mixed=10～12 are kept, is reacted 0.5 hour,
In 90 DEG C of crystallization 15 hours；Jing is filtered, washing, after dry, pulverize, obtains hydrocalumite Ca2+ 2/3Al3+ 1/3(OH)2
(CO3 2-)1/6·4H2O；By gained hydrocalumite in 400 DEG C of roastings 6 hours, roasting state hydrocalumite is obtained final product.
Embodiment 2
The preparation of catalyst：0.4 mol calcium nitrates and 0.1 mol aluminum nitrates are configured to into the water solution A of 800 mL；By 0.9
The sodium hydroxide of mol and 0.12 mol sodium carbonate are configured to the aqueous solution B of 800 mL；The condition for stirring in 20 DEG C of constant temperature and persistently
Under, solution A is added in 100 mL water with same speed with solution B, pH of mixed=10～12 are kept, is reacted 2 hours,
120 DEG C of crystallization 8 hours；Jing is filtered, washing, after dry, pulverize, obtains hydrocalumite Ca2+ 0.8Al3+ 0.2(OH)2(CO3 2-)0.1·
8H2O；By gained hydrocalumite in 500 DEG C of roastings 4 hours, roasting state hydrocalumite is obtained final product.
Embodiment 3
The preparation of catalyst：0.2 mol calcium sulfate and 0.2 mol aluminum sulfate are configured to into the water solution A of 200 mL；By 0.56
The sodium hydroxide of mol and 0.18 mol sodium carbonate are configured to the aqueous solution B of 200 mL；The condition for stirring in 90 DEG C of constant temperature and persistently
Under, solution A is added in 100 mL water with same speed with solution B, pH of mixed=10～12 are kept, is reacted 4 hours,
150 DEG C of crystallization 4 hours；Jing is filtered, washing, after dry, pulverize, obtains hydrocalumite Ca2+ 0.5Al3+ 0.5(OH)2(CO3 2-)0.25·
2H2O；By gained hydrocalumite in 600 DEG C of roastings 2 hours, roasting state hydrocalumite is obtained final product.
Embodiment 4
0.1 mol dimethyl carbonate, the roasting state hydrocalumite that 0.1 mol diethyl carbonates are prepared with 0.2 g embodiments 1 are urged
During agent adds reactor, stirring is opened, 103 DEG C are warming up to, reacted 0.5 hour, cooling, centrifugation, liquid product adopt gas phase
Chromatograph detects that product yield is 51.3%.
Embodiment 5
0.1 mol dimethyl carbonate, the roasting state hydrocalumite that 0.1 mol diethyl carbonates are prepared with 0.2 g embodiments 2 are urged
During agent adds reactor, stirring is opened, 103 DEG C are warming up to, reacted 0.5 hour, cooling, centrifugation, liquid product adopt gas phase
Chromatograph detects that product yield is 50.7%.
Embodiment 6
0.1 mol dimethyl carbonate, the roasting state hydrocalumite that 0.1 mol diethyl carbonates are prepared with 0.2 g embodiments 3 are urged
During agent adds reactor, stirring is opened, 103 DEG C are warming up to, reacted 15 minutes, cooling, centrifugation, liquid product adopt gas phase color
Spectrum detection, product yield is 41.8%.
Embodiment 7
0.1 mol dimethyl carbonate, the roasting state hydrocalumite that 0.4 mol diethyl carbonates are prepared with 0.2 g embodiments 1 are urged
During agent adds reactor, stirring is opened, 103 DEG C are warming up to, reacted 0.5 hour, cooling, centrifugation, liquid product adopt gas phase
Chromatograph detects that product yield is 86.5%.
Embodiment 8
0.4 mol dimethyl carbonate, the roasting state hydrocalumite that 0.1 mol diethyl carbonates are prepared with 0.2 g embodiments 1 are urged
During agent adds reactor, stirring is opened, 103 DEG C are warming up to, reacted 0.5 hour, cooling, centrifugation, liquid product adopt gas phase
Chromatograph detects that product yield is 19.1%.
Embodiment 9
Roasting state hydrocalumite prepared by 0.1 mol dimethyl carbonate, 0.1 mol diethyl carbonates and 0.11 g embodiments 1
During catalyst adds reactor, stirring is opened, 103 DEG C are warming up to, reacted 0.5 hour, cooling, centrifugation, liquid product adopt gas
Phase chromatograph detects that product yield is 40.9%.
Embodiment 10
0.1 mol dimethyl carbonate, the roasting state hydrocalumite that 0.1 mol diethyl carbonates are prepared with 0.6 g embodiments 1 are urged
During agent adds reactor, stirring is opened, 103 DEG C are warming up to, reacted 0.5 hour, cooling, centrifugation, liquid product adopt gas phase
Chromatograph detects that product yield is 50.5%.
Embodiment 11
0.1 mol dimethyl carbonate, the roasting state hydrocalumite that 0.1 mol diethyl carbonates are prepared with 0.3 g embodiments 1 are urged
During agent adds reactor, stirring is opened, 80 DEG C are warming up to, reacted 2.5 hours, cooling, centrifugation, liquid product adopt gas phase color
Spectrum detection, product yield is 46.1%.
Embodiment 12
0.1 mol dimethyl carbonate, the roasting state hydrocalumite that 0.1 mol diethyl carbonates are prepared with 0.4 g embodiments 1 are urged
During agent adds reactor, stirring is opened, 120 DEG C are warming up to, reacted 10 minutes, cooling, centrifugation, liquid product adopt gas phase color
Spectrum detection, product yield is 45.6%.
Embodiment 13
By the catalyst after used in embodiment 4, without any process 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 50.2%.
Comparative example
By 0.1 mol dimethyl carbonate, 0.1 mol diethyl carbonates and 0.2 g roasting state magnesium aluminum-hydrotalcites catalyst add anti-
In answering device, stirring is opened, 103 DEG C are warming up to, reacted 0.5 hour, cooling, centrifugation, liquid product adopt gas chromatographic detection, produced
Thing yield is 36.4%.
According to embodiment 4-13 and the result of comparative example, roasting state hydrocalumite according to the present invention synthesizes carbon to ester exchange
The reaction of sour methyl ethyl ester is urged better than conventional roasting state magnesium aluminum-hydrotalcite with very excellent catalytic performance, its catalysis activity
There is not the phenomenon that activity is decreased obviously Jing after 10 times are reused in agent.Additionally, the system of roasting state hydrocalumite catalyst
Standby process is simple, low raw-material cost.Therefore, technical scheme according to the present invention is suitable for industrial applications.
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 the scope of the claims of the present invention.
Claims (7)
1. a kind of method that roasting state hydrocalumite catalyzes and synthesizes Ethyl methyl carbonate, with dimethyl carbonate and diethyl carbonate as original
Material synthesis under the catalytic action of roasting state hydrocalumite obtains Ethyl methyl carbonate, it is characterised in that the knot of the hydrocalumite
Structure formula is：Ca2+ 1-xAl3+ x(OH)2(CO3 2-)x/2·mH2O, wherein, 0.2≤x≤0.5, m is hydration number, 1≤
M≤8, the roasting state hydrocalumite be with hydrocalumite at 400～600 DEG C 2～8 hours products therefroms of roasting.
2. the method for catalyzing and synthesizing Ethyl methyl carbonate according to claim 1, it is characterised in that the system of the hydrocalumite
Standby process includes step：
（1）According to Ca in hydrocalumite composition2+And Al3+Calcium salt, aluminium salt are made into salt-mixture molten by the ratio of the amount of material in proportion
Liquid, 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(Al3+)]=1.4～2.2 ratio, will
Na2CO3Mixed ammonium/alkali solutions are made into NaOH, and make mixed ammonium/alkali solutions and step（1）In mixing salt solution volume it is identical；
（3）By above two solution by identical speed double fluid in reactor, the hybrid reaction 0.5 in 20～90 DEG C of temperature ranges
～4 hours, pH of mixed=10～12 are kept, in 80～150 DEG C of crystallization 4～20 hours, precipitate is dehydrated, is washed to filtrate
PH=7～8, are the hydrocalumite of powder shaped after gained solid drying, crushing.
3. the method for catalyzing and synthesizing Ethyl methyl carbonate according to claim 2, it is characterised in that the step（1）In
Calcium salt is calcium chloride, calcium nitrate or calcium sulfate, and aluminium salt is aluminum chloride, aluminum nitrate or aluminum sulfate.
4. the method for catalyzing and synthesizing Ethyl methyl carbonate according to claim 1, it is characterised in that the dimethyl carbonate with
The ratio of the amount of the material of diethyl carbonate is 0.25～4：1.
5. the method for catalyzing and synthesizing Ethyl methyl carbonate according to claim 1, it is characterised in that the roasting state water aluminum calcium
Stone is 0.5～3 with the mass ratio of reaction raw materials：100.
6. the method for catalyzing and synthesizing Ethyl methyl carbonate according to claim 1, it is characterised in that the temperature of the catalytic reaction
Spend for 80～120 DEG C.
7. the method for catalyzing and synthesizing Ethyl methyl carbonate according to claim 1, it is characterised in that the catalytic reaction when
Between be 10～150 minutes.
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