CN106748782A - 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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- lanthanum
- methyl ethyl
- magnesium
- ethyl carbonate
- magnesium aluminium
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- 239000011777 magnesium Substances 0.000 title claims abstract description 34
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 29
- UZQSJWBBQOJUOT-UHFFFAOYSA-N alumane;lanthanum Chemical compound [AlH3].[La] UZQSJWBBQOJUOT-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 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
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 229910001051 Magnalium Inorganic materials 0.000 claims abstract description 20
- 238000002360 preparation method Methods 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
- 239000002994 raw material Substances 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
- 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
- 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
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 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
- 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
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 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
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 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
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- -1 magnesium aluminium lanthanum class Chemical class 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
- 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
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 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
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 10
- 238000001816 cooling 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
- 238000001514 detection method Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000001228 spectrum 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052566 spinel group Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 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
- 238000009826 distribution Methods 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
- 238000004817 gas chromatography 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
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing Methyl Ethyl Carbonate, synthesized under the catalytic action of magnalium lanthanium complex oxide as raw material with dimethyl carbonate and diethyl carbonate and obtain methyl ethyl carbonate, it is characterized in that, the magnalium lanthanium complex oxide is that 2~8 h products therefroms are calcined at 400~600 DEG C with magnesium aluminium lanthanum houghite, and the general structure of the magnesium aluminium lanthanum houghite is：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 is hydration number, 1≤m≤8.The method that the present invention is provided has advantages below：Catalyst preparation process is simple, and low production cost, 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 magnesium aluminium lanthanum composite oxide catalytic 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 of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing 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 of a kind of magnesium aluminium lanthanum composite oxide catalytic Catalysts of Preparing Methyl Ethyl Carbonate that the present invention is provided, with dimethyl carbonate
Methyl ethyl carbonate is obtained for raw material synthesizes under the catalytic action of magnalium lanthanium complex oxide with diethyl carbonate, its feature exists
In the magnalium lanthanium complex oxide is that 2~8 h products therefroms, institute are calcined at 400~600 DEG C with magnesium aluminium lanthanum houghite
The general structure for stating magnesium aluminium lanthanum houghite is：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 is hydration number, 1≤m≤8.
Further, the preparation process of the magnesium aluminium lanthanum houghite includes step：
（1）Mg in being constituted according to magnesium aluminium lanthanum houghite2+、Al3+And La3+The ratio between amount of material, magnesium salts, aluminium salt and lanthanum salt are pressed
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 mixed ammonium/alkali solutions and step（1）In salt-mixture
Liquor capacity is identical；
（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
~4 h, keep pH of mixed=9~11, in 80~150 DEG C of h of crystallization 4~20, sediment are dehydrated, and washing to filtrate pH=7~
8, gained solid is the magnesium aluminium lanthanum houghite of powder shaped after drying, crushing.
Further, the step（1）In magnesium salts be magnesium chloride, magnesium nitrate or magnesium sulfate, aluminium salt be aluminium chloride, nitric acid
Aluminium or aluminum sulfate, lanthanum salt are lanthanum chloride, lanthanum nitrate or lanthanum sulfate.
Further, the ratio between amount of material of the dimethyl carbonate and diethyl carbonate is 0.25~4：1.
Further, the magnalium lanthanium complex 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.
Magnesium aluminium lanthanum composite oxide catalysts involved in the present invention are fired by magnesium aluminium lanthanum houghite and prepare；Due to
Appropriate rare-earth elements of lanthanum is introduced in skeleton, makes the base strength at the surface alkalinty center of magnalium lanthanium complex oxide and alkali density
It is above traditional Mg-Al composite oxide；Additionally, the surface alkalinty central distribution of magnalium lanthanium complex oxide is uniform.It is a large amount of strong
The activated centre of alkalescence can promote the quick generation of dimethyl carbonate and diethyl carbonate ester exchange reaction.The skill that the present invention is provided
Art scheme has advantages below：The activity of catalyst is high, good, the high income of product of selectivity；The low cost of catalyst, with product
Easily separated, repeat performance is excellent.
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：0.3mol magnesium chlorides, 0.12mol aluminium chloride and 0.03mol lanthanum chlorides 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,
0.5 h is reacted, in 90 DEG C of h of crystallization 15；Through filtering, washing after dry, pulverize, obtains magnesium aluminium lanthanum houghite Mg2+ 2/3Al3 + 4/15La3+ 1/15(OH)2(CO3 2-)1/6·4H2O；Gained magnesium aluminium lanthanum houghite is calcined 6 h at 400 DEG C, magnesium aluminium lanthanum is obtained final product and is answered
Close oxide.
Embodiment 2
The preparation of catalyst：0.4mol magnesium nitrates, 0.05mol aluminum nitrates and 0.05mol lanthanum 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
2 h are answered, in 120 DEG C of crystallization 8h；Through filtering, washing after dry, pulverize, obtains magnesium aluminium lanthanum houghite Mg2+ 0.8Al3+ 0.1La3 + 0.1(OH)2(CO3 2-)0.1·8H2O；Gained hydrocalumite is calcined 4 h at 500 DEG C, magnalium lanthanium complex oxide is obtained final product.
Embodiment 3
The preparation of catalyst：0.2mol magnesium sulfate, 0.18mol aluminum sulfate and 0.02mol lanthanum sulfates 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,
2 h are reacted, in 150 DEG C of h of crystallization 4；Through filtering, washing after dry, pulverize, obtains magnesium aluminium lanthanum houghite Mg2+ 0.5Al3+ 0.45La3+ 0.05(OH)2(CO3 2-)0.25·2H2O；Gained hydrocalumite is calcined 2 h at 600 DEG C, magnesium aluminium lanthanum combined oxidation is obtained final product
Thing.
Embodiment 4
0.1mol dimethyl carbonates, the magnalium lanthanium complex 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 0.5 h, and cooling, centrifugation, liquid product uses gas phase color
Spectrum detection, product yield is 51.9%.
Embodiment 5
By 0.1 mol dimethyl carbonates, magnalium lanthanium complex 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 0.5 h, and cooling, centrifugation, liquid product uses gas phase
Chromatogram detects that product yield is 50.7%.
Embodiment 6
By 0.1 mol dimethyl carbonates, magnalium lanthanium complex 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 42.6%.
Embodiment 7
0.1mol dimethyl carbonates, the magnalium lanthanium complex 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 0.5 h, and cooling, centrifugation, liquid product uses gas phase color
Spectrum detection, product yield is 83.9%.
Embodiment 8
0.4mol dimethyl carbonates, the magnalium lanthanium complex 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 0.5 h, and cooling, centrifugation, liquid product uses gas phase color
Spectrum detection, product yield is 19.5%.
Embodiment 9
0.1mol dimethyl carbonates, the magnalium lanthanium complex 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 0.5 h, and cooling, centrifugation, liquid product uses gas phase color
Spectrum detection, product yield is 41.6%.
Embodiment 10
0.1mol dimethyl carbonates, the magnalium lanthanium complex 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 0.5 h, and cooling, centrifugation, liquid product uses gas phase color
Spectrum detection, product yield is 51.0%.
Embodiment 11
0.1mol dimethyl carbonates, the magnalium lanthanium complex 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 2.5 h, and cooling, centrifugation, liquid product uses gas-chromatography
Detection, product yield is 46.2%.
Embodiment 12
0.1mol dimethyl carbonates, the magnalium lanthanium complex 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 41.9%.
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 51.1%.
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, 0.5 h 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, magnalium lanthanium complex 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, magnesium aluminium lanthanum combined oxidation
The preparation process of thing catalyst is simple, low production cost.Therefore, technical scheme of 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 scope 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, be with diethyl carbonate with dimethyl carbonate
Raw material synthesizes under the catalytic action of magnalium lanthanium complex oxide and obtains methyl ethyl carbonate, it is characterised in that the magnesium aluminium lanthanum is answered
It is that 2~8 h products therefroms, the magnesium aluminium lanthanum houghite are calcined at 400~600 DEG C with magnesium aluminium lanthanum houghite to close oxide
General structure be：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 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 magnesium aluminium lanthanum class neatly
The preparation process of stone includes step：
（1）Mg in being constituted according to magnesium aluminium lanthanum houghite2+、Al3+And La3+The ratio between amount of material, magnesium salts, aluminium salt and lanthanum salt are pressed
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 mixed ammonium/alkali solutions and step（1）In salt-mixture
Liquor capacity is identical；
（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
~4 h, keep pH of mixed=9~11, in 80~150 DEG C of h of crystallization 4~20, sediment are dehydrated, and washing to filtrate pH=7~
8, gained solid is the magnesium aluminium lanthanum houghite 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
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 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 magnesium aluminium lanthanum 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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| CN107486193A (en) * | 2017-07-18 | 2017-12-19 | 福州大学化肥催化剂国家工程研究中心 | A kind of hydrogenation catalyst and preparation method thereof |
| CN112724017A (en) * | 2021-01-14 | 2021-04-30 | 吉林师范大学 | Method for synthesizing asymmetric organic carbonate at room temperature |
| 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 |
| 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107486193A (en) * | 2017-07-18 | 2017-12-19 | 福州大学化肥催化剂国家工程研究中心 | A kind of 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 |
| CN113797912B (en) * | 2020-06-12 | 2024-06-04 | 中国石油化工股份有限公司 | Aluminum-containing magnesium-lanthanum composite oxide and preparation method and application thereof |
| CN112724017A (en) * | 2021-01-14 | 2021-04-30 | 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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