CN106669653A - Catalyst for preparing ethyl methyl carbonate and preparation method of catalyst - Google Patents
Catalyst for preparing ethyl methyl carbonate and preparation method of catalyst Download PDFInfo
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- CN106669653A CN106669653A CN201611154827.3A CN201611154827A CN106669653A CN 106669653 A CN106669653 A CN 106669653A CN 201611154827 A CN201611154827 A CN 201611154827A CN 106669653 A CN106669653 A CN 106669653A
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- Prior art keywords
- catalyst
- active component
- solution
- methyl ethyl
- ethyl carbonate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004202 carbamide Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 31
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 7
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 7
- 125000004494 ethyl ester group Chemical group 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- -1 methyl ethyl carbonate ester Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- 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
Abstract
The invention discloses a catalyst for preparing ethyl methyl carbonate and a preparation method of the catalyst. In the catalyst, the mass of active components accounts for 0.6-25%, the mass of auxiliary metals accounts for 0.2-20%, and the balance is aluminum oxide, wherein the active components are at least one of PbO, ZnO, MgO, Fe2O3, CuO and CaO, and the auxiliary metals are at least one of La, Na, K, Sr and Ce. The catalyst is used for preparing ethyl methyl carbonate by urea alcoholysis, cannot cause environmental pollution when used for preparing ethyl methyl carbonate, and has cheap and easily-available raw materials, a simple process and suitability for industrialized production.
Description
Technical field
The invention belongs to the preparing technical field of methyl ethyl carbonate, it is related to a kind of catalysis for preparing methyl ethyl carbonate
Agent.The invention further relates to the preparation method of above-mentioned catalyst.
Background technology
Methyl ethyl carbonate is a kind of emerging Green Fine Chemical raw material, with the continuous expansion of application field, last decade
Carry out its research and development and have become one of focus of world's chemical research.Because methyl ethyl carbonate possesses methyl and ethyl simultaneously,
Have dimethyl carbonate, diethyl carbonate characteristic concurrently, can be reacted with alcohol, phenol, amine and ester etc., in being very important fine synthesis
Mesosome, while being also a kind of solvent of excellent lithium-ion battery electrolytes.Further, since methyl ethyl carbonate ester molecular structure is not
Symmetry, makes it also show obvious superiority in terms of as the solvent of paint, cellulose and resin etc., therefore also may be used
As extraordinary spices and the solvent of intermediate.
The prior synthesizing method of methyl ethyl carbonate is main with hypertoxic phosgene as raw material, then obtains carbonic acid first through alcoholysis and ammonolysis
Ethyl ester.The production technology is because operation is more, device is complicated, the hydrochloric acid of most severe corrosive is produced in production process, residual in product
Chlorine residue is difficult to remove, and environmental pressure increases, and phosgene has severe toxicity, is gradually replaced by non-phosgene at present.Non-phosgene
It is main to include oxidation carbonyl process and ester-interchange method.Oxidation carbonyl process it is not perfect, exist selectivity low, catalyst it is expensive,
The shortcomings of being difficult to operational control.And the problem that the ester-interchange method being widely adopted at present is present is that catalyst life is short, bar is reacted
Part is harsh, needs to add various organic solvents in course of reaction, brings very big difficulty to the later separation of product, virtually
Increase equipment investment expense and production is consumed.
Alcoholysis of urea, i.e., meet green chemical industry theory by the production method of methyl alcohol, ethanol and urea methyl ethyl carbonate,
Environmental pollution, process is simple are not resulted in, raw material is methyl alcohol cheap and easy to get, ethanol and urea, easily realizes large-scale production,
And if the method is combined the greenhouse effects and expand titanium dioxide that can mitigate that carbon dioxide brought to environment with the production of urea
The utilization of carbon.Therefore, from industrial application value and practicality, alcoholysis of urea synthesizing carbonate ester is with development prospect
One of process route.
The content of the invention
It is an object of the invention to provide a kind of catalyst for preparing methyl ethyl carbonate.The catalyst can be by urine
Plain alcoholysis method prepares methyl ethyl carbonate, therefore does not result in environmental pollution using the catalyst preparation methyl ethyl carbonate, and
And the process is simple of the catalyst is prepared, raw material is cheap and easy to get.
Preparation method the present invention also aims to provide above-mentioned catalyst.
The purpose of the present invention is achieved through the following technical solutions：
This catalyst for preparing methyl ethyl carbonate, the quality accounting of active component is 0.6- in the catalyst
25%, the quality accounting of promoter metal is 0.2-20%, and remaining is aluminum oxide；Wherein active component be PbO, ZnO, MgO,
Fe2O3, at least one in CuO or CaO；Wherein promoter metal is at least one in La, Na, K, Sr or Ce.
Further, the features of the present invention is also resided in：
Wherein the specific surface area of catalyst is 100-300m2/ g, specific pore volume is 0.1-1.6cm2/ L, aperture is
Another technical scheme of the invention is that the preparation method of above-mentioned catalyst is comprised the following steps：
Step 1, is pre-processed using the mixed gas of alkaline gas and nitrogen to aluminum oxide, obtains solid carrier；
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；Active component
It is 0.5-8 with the mass ratio of promoter metal：1；Wherein active component is PbO, ZnO, MgO, Fe2O3, in CuO or CaO at least one
Kind；Wherein promoter metal is at least one in La, Na, K, Sr or Ce；
Step 3, to hydrochloric acid, nitric acid, sulfuric acid or acetic acid is added in the solution obtained in step 2, the PH for adjusting solution is 2-
4, obtain reaction solution；
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier in step 1, then carries out heat to it
After treatment, the catalyst for preparing methyl ethyl carbonate is obtained.
Further, the features of the present invention is also resided in：
The detailed process pre-processed wherein in step 1 is, under the atmosphere of alkaline gas and the mixed gas of nitrogen,
300-600 DEG C, by alumina treatment 2-8h under conditions of 0.1-0.5MPa, then it is calcined 4-10h at 400-800 DEG C.
Alkaline gas wherein in step 1 are NH3, and NH3With N2Mol ratio be 1:2-8.
The detailed process being heat-treated wherein in step 4 is to be heated to 40-90 DEG C, stirs 1-10h；Then in 100-
4-10h is dried in the environment of 150 DEG C；Finally 4-12h is calcined at 400-600 DEG C.
The beneficial effects of the invention are as follows, catalyst of the invention can prepare methyl ethyl carbonate by alcoholysis of urea, and
The catalyst using excessive infusion process, simple to operate, easily realize by preparation process, is adapted to industrialized production.
Large chemicals is using the raw material of catalyst Catalysts of Preparing Methyl Ethyl Carbonate of the invention, it is cheap and easy to get,
Price is relatively low, and production cost can be so greatly lowered；The accessory substance of whole reaction only has ammonia simultaneously, and it is utilized in recovery ammonia
Afterwards, whole process almost three-waste free discharge, i.e., economic and environment-friendly, and remarkable benefit；Anhydrous generation during simultaneous reactions, it is to avoid
The separation problem for the treatment of methyl alcohol, ethanol, methyl ethyl carbonate and water.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment：
The invention provides a kind of catalyst for preparing methyl ethyl carbonate, the quality of active component is accounted in the catalyst
Than being 0.6-25%, active component is PbO, ZnO, MgO, Fe2O3, in CuO or CaO any one or a few；The matter of promoter metal
Amount accounting be 0.2-20%, promoter metal be La, Na, K, Sr or Ce in any one or a few；Remaining is aluminum oxide.This is urged
The specific surface area of agent is 100-300m2/ g, specific pore volume is 0.1-1.6cm2/L, and aperture is
Present invention also offers the preparation method of above-mentioned catalyst, comprise the following steps：
Step 1 takes spherical alumina support, alumina support it is a diameter ofThen using alkaline gas and
The mixed gas of nitrogen are pre-processed to aluminum oxide, and detailed process is, the use of mol ratio is 1:The NH of 2-83And N2Mixed gas
At 300-600 DEG C, to alumina treatment 2-8h under conditions of 0.1-0.5MPa, 4-10h then is calcined at 400-800 DEG C, obtained
To solid carrier.
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；It is wherein active
Component is PbO, ZnO, MgO, Fe2O3, in CuO or CaO any one or a few, during promoter metal is La, Na, K, Sr or Ce
Any one or a few, and active component and the mass ratio of promoter metal are 0.5-8：1.
Step 3, adds hydrochloric acid, nitric acid, sulfuric acid or acetic acid in the solution that will be obtained in step 2, the pH for adjusting solution is 2-
4, obtain reaction solution.
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier obtained in step 1, is heated to
40-90 DEG C, 1-10h is stirred, 4-10h is then dried in the environment of 100-150 DEG C；Finally 4- is calcined at 400-600 DEG C
12h, obtains the catalyst for preparing methyl ethyl carbonate.
The specific surface area of the catalyst for wherein being obtained in step 4 is 100-300m2/ g, specific pore volume is 0.1-1.6cm2/L,
Aperture is
Methyl ethyl carbonate can be prepared by alcoholysis of urea using the catalyst for obtaining in step 4, detailed process is：
It is in molar ratio 1：0.2-10：0.2-10 takes urea, methyl alcohol and ethanol, then to adding catalyst, catalyst in its mixture
Quality account for the 0.1-10% of reactant gross mass；120-260 DEG C is then heated to, 0.2-8h is reacted, reaction temperature is down to room
Wen Hou, is separated by filtration and obtains methyl ethyl carbonate.
Specific embodiment of the invention is：
Embodiment one
The detailed process of the catalyst for preparing methyl ethyl carbonate is：Choose a diameter ofBall-type γ~Al2O3Carry
Body, carrier is loaded at quartz reactor flat-temperature zone, and after being warming up to 450 DEG C, it is 1 that mol ratio is passed through under normal pressure:2.5 alkaline gas
Body NH3With inert gas N2Mixed gas, keep 4 hours, be subsequently placed in Muffle furnace, 580 DEG C be calcined 5 hours.
The Ce of La, 0.1g of the ZnO of PbO, 1.5g of 1.0g and 0.2g is added in distilled water, and is stirred and is added
Enter hydrochloric acid, the pH value for adjusting solution is 3.5.
Above-mentioned mixed solution is poured into the treated alumina supports of 82.0g, 80 DEG C is then heated to and is stirred 4 hours,
Dried 6 hours at 100 DEG C, be finally placed in 500 DEG C of roastings in Muffle furnace and obtain catalyst in 8 hours.
Embodiment two
The detailed process of the catalyst for preparing methyl ethyl carbonate is：Choose a diameter ofBall-type γ-Al2O3Carry
Body, carrier is loaded at quartz reactor flat-temperature zone, and after being warming up to 400 DEG C, it is 1 that normal pressure is passed through mol ratio:.2.9 alkaline gas
Body NH3With inert gas N2Mixed gas, keep 4.5 hours, be subsequently placed in Muffle furnace, 600 DEG C be calcined 5.5 hours.
The K of La, 0.1g of the CaO of PbO, 1.5g of 1.0g and 0.2g is added in distilled water, and is stirred and is added
Enter hydrochloric acid, the pH value for adjusting solution is 3.0.
Above-mentioned mixed solution is poured into the treated alumina supports of 85.0g, 80 DEG C is then heated to and is stirred 4 hours,
Dried 6 hours at 100 DEG C, be finally placed in 520 DEG C of roastings in Muffle furnace and obtain catalyst in 8 hours.
Embodiment three
The detailed process of the catalyst for preparing methyl ethyl carbonate is：Choose a diameter ofBall-type γ-Al2O3Carry
Body, carrier is loaded at quartz reactor flat-temperature zone, and after being warming up to 450 DEG C, it is 1 that normal pressure is passed through mol ratio:.3 alkaline gas
NH3With inert gas N2Mixed gas, keep 5 hours, be subsequently placed in Muffle furnace, 600 DEG C be calcined 5 hours.
The Sr of La, 0.1g of the CaO of ZnO, 1.8g of 1.0g and 0.1g is added in distilled water, and is stirred and is added
Enter sulfuric acid, the pH value for adjusting solution is 3.5.
Above-mentioned mixed solution is poured into the treated alumina supports of 82.0g, 80 DEG C is then heated to and is stirred 4 hours,
Dried 5 hours at 100 DEG C, be finally placed in 550 DEG C of roastings in Muffle furnace and obtain catalyst in 7 hours.
Example IV
The detailed process of the catalyst for preparing methyl ethyl carbonate is：Choose a diameter ofBall-type γ-Al2O3Carry
Body, carrier is loaded at quartz reactor flat-temperature zone, and after being warming up to 500 DEG C, it is 1 that normal pressure is passed through mol ratio:.4 alkaline gas
NH3With inert gas N2Mixed gas, keep 6 hours, be subsequently placed in Muffle furnace, 600 DEG C be calcined 6 hours.
The Ce of K, 0.1g of the MgO of ZnO, 2.0g of 1.0g and 0.1g is added in distilled water, and is stirred and is added
Enter acetic acid, the pH value for adjusting solution is 3.
Above-mentioned mixed solution is poured into the treated alumina supports of 75.0g, 80 DEG C is then heated to and is stirred 4 hours,
Dried 5 hours at 100 DEG C, be finally placed in 600 DEG C of roastings in Muffle furnace and obtain catalyst in 5 hours.
Embodiment five
The detailed process of the catalyst for preparing methyl ethyl carbonate is：Choose a diameter ofBall-type γ-Al2O3Carry
Body, carrier is loaded at quartz reactor flat-temperature zone, and after being warming up to 550 DEG C, it is 1 that normal pressure is passed through mol ratio:.2.5 alkaline gas
Body NH3With inert gas N2Mixed gas, keep 5 hours, be subsequently placed in Muffle furnace, 600 DEG C be calcined 6 hours.
By the Fe of ZnO, 1.0g of 1.0g2O3, 1.0g the Ce of La, 0.15g of PbO and 0.15g be added in distilled water,
And stir and add hydrochloric acid, the pH value for adjusting solution is 3.
Above-mentioned mixed solution is poured into the treated alumina supports of 90.0g, 80 DEG C is then heated to and is stirred 4 hours,
Dried 6 hours at 100 DEG C, be finally placed in 650 DEG C of roastings in Muffle furnace and obtain catalyst in 6 hours.
Embodiment six
The detailed process of the catalyst for preparing methyl ethyl carbonate is：Choose a diameter ofBall-type γ-Al2O3Carry
Body, carrier is loaded at quartz reactor flat-temperature zone, and after being warming up to 500 DEG C, it is 1 that normal pressure is passed through mol ratio:.2 alkaline gas
NH3With inert gas N2Mixed gas, keep 6 hours, be subsequently placed in Muffle furnace, 600 DEG C be calcined 6 hours.
The Na of Sr, 0.2g of the PbO of CaO, 1.0g of ZnO, 1.0g of 1.0g and 0.15g is added in distilled water, and
Nitric acid is stirred and adds, the pH value for adjusting solution is 3.5.
Above-mentioned mixed solution is poured into the treated alumina supports of 85.0g, 80 DEG C is then heated to and is stirred 4 hours,
Dried 6 hours at 100 DEG C, be finally placed in 650 DEG C of roastings in Muffle furnace and obtain catalyst in 6 hours.
Embodiment seven
The detailed process of the catalyst for preparing methyl ethyl carbonate is：Choose a diameter ofBall-type γ-Al2O3Carry
Body, carrier is loaded at quartz reactor flat-temperature zone, and after being warming up to 530 DEG C, it is 1 that normal pressure is passed through mol ratio:.3 alkaline gas
NH3With inert gas N2Mixed gas, keep 5 hours, be subsequently placed in Muffle furnace, 580 DEG C be calcined 5.5 hours.
The Ce of Sr, 0.1g of the MgO of CaO, 0.5g of PbO, 1.0g of 1.0g and 0.15g is added in distilled water, and
Nitric acid is stirred and adds, the pH value for adjusting solution is 3.5.
Above-mentioned mixed solution is poured into the treated alumina supports of 85.0g, 80 DEG C is then heated to and is stirred 4 hours,
Dried 5 hours at 100 DEG C, be finally placed in 600 DEG C of roastings in Muffle furnace and obtain catalyst in 5 hours.
Embodiment eight
The detailed process of the catalyst for preparing methyl ethyl carbonate is：Choose a diameter ofBall-type γ-Al2O3Carry
Body, carrier is loaded at quartz reactor flat-temperature zone, and after being warming up to 530 DEG C, it is 1 that normal pressure is passed through mol ratio:.3 alkaline gas
NH3With inert gas N2Mixed gas, keep 5 hours, be subsequently placed in Muffle furnace, 580 DEG C be calcined 5.5 hours.
The Ce of K, 0.15g of the CuO of CaO, 0.5g of PbO, 1.0g of 1.0g and 0.15g is added in distilled water, and
Acetic acid is stirred and adds, the pH value for adjusting solution is 3.
Above-mentioned mixed solution is poured into the treated alumina supports of 80.0g, 80 DEG C is then heated to and is stirred 4 hours,
Dried 5 hours at 100 DEG C, be finally placed in 600 DEG C of roastings in Muffle furnace and obtain catalyst in 5 hours.
Embodiment nine
Catalyst for preparing methyl ethyl carbonate specifically includes following steps：
Step 1 takes spherical alumina support, alumina support it is a diameter ofThen alkaline gas and nitrogen are used
Mixed gas aluminum oxide is pre-processed, detailed process is, the use of mol ratio is 1:7 NH3And N2Mixed gas are 500
DEG C, to alumina treatment 5h under conditions of 0.35MPa, 6h then is calcined at 500 DEG C, obtain solid carrier.
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；It is wherein active
Component is the mixture of PbO, ZnO, MgO and CaO, and promoter metal is the mixture of La, Na and Ce, and active component and auxiliary agent
The mass ratio of metal is 3：1.
Step 3, adds hydrochloric acid, nitric acid, sulfuric acid or acetic acid in the solution that will be obtained in step 2, the pH for adjusting solution is 3,
Obtain reaction solution.
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier obtained in step 1, is heated to
40 DEG C, 1h is stirred, then dry 5h in the environment of 120 DEG C；4h finally is calcined at 600 DEG C, is obtained for preparing carbonic acid first
The catalyst of ethyl ester.The specific surface area of the catalyst for wherein obtaining is 210m2/ g, specific pore volume is 0.8cm2/ L, aperture is
Embodiment ten
Catalyst for preparing methyl ethyl carbonate specifically includes following steps：
Step 1 takes spherical alumina support, alumina support it is a diameter ofThen alkaline gas and nitrogen are used
Mixed gas aluminum oxide is pre-processed, detailed process is, the use of mol ratio is 1:8 NH3And N2Mixed gas are 600
DEG C, to alumina treatment 2h under conditions of 0.1MPa, 4h then is calcined at 800 DEG C, obtain solid carrier.
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；It is wherein active
Component is PbO, ZnO, MgO and Fe2O3Mixture, its gross mass be 4g, promoter metal for 0.5g Na and K.
Step 3, adds hydrochloric acid in the solution that will be obtained in step 2, the pH for adjusting solution is 4, obtains reaction solution.
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier obtained in step 1, is heated to
90 DEG C, 1h is stirred, then dry 4h in the environment of 150 DEG C；4h finally is calcined at 600 DEG C, is obtained for preparing carbonic acid first
The catalyst of ethyl ester.The specific surface area of the catalyst for wherein obtaining is 100m2/ g, specific pore volume is 0.1cm2/ L, aperture is
Embodiment 11
Catalyst for preparing methyl ethyl carbonate specifically includes following steps：
Step 1 takes spherical alumina support, alumina support it is a diameter ofThen alkaline gas and nitrogen are used
Mixed gas aluminum oxide is pre-processed, detailed process is, the use of mol ratio is 1:2 NH3And N2Mixed gas are 300
DEG C, to alumina treatment 2h under conditions of 0.5MPa, 10h then is calcined at 400 DEG C, obtain solid carrier.
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；It is wherein active
Component is MgO, Fe2O3, CuO and CaO mixture, its quality be 3.5g, promoter metal for 1g Na, K, Sr and Ce mixing
Thing.
Step 3, adds nitric acid in the solution that will be obtained in step 2, the pH for adjusting solution is 4, obtains reaction solution.
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier obtained in step 1, is heated to
40 DEG C, 1h is stirred, then dry 10h in the environment of 100 DEG C；12h finally is calcined at 400 DEG C, is obtained for preparing carbonic acid
The catalyst of methyl ethyl ester.The specific surface area of the catalyst for wherein obtaining is 100m2/ g, specific pore volume is 0.1cm2/ L, aperture is
Embodiment 12
Catalyst for preparing methyl ethyl carbonate specifically includes following steps：
Step 1 takes spherical alumina support, alumina support it is a diameter ofThen alkaline gas and nitrogen are used
Mixed gas aluminum oxide is pre-processed, detailed process is, the use of mol ratio is 1:2 NH3And N2Mixed gas are 350
DEG C, to alumina treatment 4h under conditions of 0.3MPa, 6h then is calcined at 500 DEG C, obtain solid carrier.
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；It is wherein active
Component is PbO, ZnO, MgO, Fe2O3, CuO and CaO mixture, its gross mass is 3.6g, promoter metal is the La of 3g, Na, K,
Sr and Ce mixtures.
Step 3, adds sulfuric acid in the solution that will be obtained in step 2, the pH for adjusting solution is 2, obtains reaction solution.
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier obtained in step 1, is heated to
60 DEG C, 2h is stirred, then dry 5h in the environment of 120 DEG C；4h finally is calcined at 400 DEG C, is obtained for preparing carbonic acid first
The catalyst of ethyl ester.The specific surface area of the catalyst for wherein obtaining is 210m2/ g, specific pore volume is 1.6cm2/ L, aperture is
Embodiment 13
Catalyst for preparing methyl ethyl carbonate specifically includes following steps：
Step 1 takes spherical alumina support, alumina support it is a diameter ofThen alkaline gas and nitrogen are used
Mixed gas aluminum oxide is pre-processed, detailed process is, the use of mol ratio is 1:2 NH3And N2Mixed gas are 300
DEG C, to alumina treatment 8h under conditions of 0.5MPa, 10h then is calcined at 400 DEG C, obtain solid carrier.
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；It is wherein active
Component is the mixture of PbO, ZnO, CuO and CaO, and its gross mass is 2.6g, and promoter metal is the mixture of the La and Ce of 0.5g.
Step 3, adds acetic acid in the solution that will be obtained in step 2, the pH for adjusting solution is 2, obtains reaction solution.
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier obtained in step 1, is heated to
90 DEG C, 1h is stirred, then dry 4h in the environment of 150 DEG C；4h finally is calcined at 600 DEG C, is obtained for preparing carbonic acid first
The catalyst of ethyl ester.The specific surface area of the catalyst for wherein obtaining is 300m2/ g, specific pore volume is 1.6cm2/ L, aperture is
Embodiment 14
Catalyst for preparing methyl ethyl carbonate specifically includes following steps：
Step 1 takes spherical alumina support, alumina support it is a diameter ofThen alkaline gas and nitrogen are used
Mixed gas aluminum oxide is pre-processed, detailed process is, the use of mol ratio is 1:2 NH3And N2Mixed gas are 400
DEG C, to alumina treatment 3h under conditions of 0.1MPa, 8h then is calcined at 600 DEG C, obtain solid carrier.
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；It is wherein active
Component is MgO, Fe2O3, CuO and CaO mixture, its gross mass be 3.8g, promoter metal for 0.8g La, Na, K and Sr mix
Compound.
Step 3, adds nitric acid in the solution that will be obtained in step 2, the pH for adjusting solution is 3, obtains reaction solution.
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier obtained in step 1, is heated to
55 DEG C, 3h is stirred, then dry 5h in the environment of 120 DEG C；10h finally is calcined at 450 DEG C, is obtained for preparing carbonic acid first
The catalyst of ethyl ester.The specific surface area of the catalyst for wherein obtaining is 210m2/ g, specific pore volume is 1.2cm2/ L, aperture is
The above, is only presently preferred embodiments of the present invention, and any limitation is not done to the present invention, every according to invention skill
Any simple modification, change and equivalent structure change that art is substantially made to above example, still fall within the technology of the present invention
In the protection domain of scheme.
Claims (6)
1. a kind of catalyst for preparing methyl ethyl carbonate, it is characterised in that the quality accounting of active component in the catalyst
It is 0.6-25%, the quality accounting of promoter metal is 0.2-20%, and remaining is aluminum oxide；Wherein active component be PbO, ZnO,
MgO、Fe2O3, at least one in CuO or CaO；Wherein promoter metal is at least one in La, Na, K, Sr or Ce.
2. the catalyst for preparing methyl ethyl carbonate according to claim 1, it is characterised in that the ratio of the catalyst
Surface area is 100-300m2/ g, specific pore volume is 0.1-1.6cm2/ L, aperture is
3. a kind of preparation method of catalyst as claimed in claim 1, it is characterised in that comprise the following steps：
Step 1, is pre-processed using the mixed gas of alkaline gas and nitrogen to aluminum oxide, obtains solid carrier；
Step 2, by active component and promoter metal addition distilled water, solution is obtained after stirring；Active component with help
The mass ratio of agent metal is 0.5-8：1；Wherein active component is PbO, ZnO, MgO, Fe2O3, at least one in CuO or CaO；
Wherein promoter metal is at least one in La, Na, K, Sr or Ce；
Step 3, to hydrochloric acid, nitric acid, sulfuric acid or acetic acid is added in the solution obtained in step 2, the pH for adjusting solution is 2-4, is obtained
To reaction solution；
Step 4, the reaction solution that will be obtained in step 3 is added in the solid carrier in step 1, and then it is heat-treated
Afterwards, the catalyst for preparing methyl ethyl carbonate is obtained.
4. the preparation method of catalyst according to claim 3, it is characterised in that what is pre-processed in the step 1 is specific
Process is, under the atmosphere of alkaline gas and the mixed gas of nitrogen, at 300-600 DEG C, by oxygen under conditions of 0.1-0.5MPa
Change aluminium treatment 2-8h, be then calcined 4-10h at 400-800 DEG C.
5. the preparation method of catalyst according to claim 4, it is characterised in that the alkaline gas in the step 1 are
NH3, and NH3With N2Mol ratio be 1:2-8.
6. the preparation method of catalyst according to claim 3, it is characterised in that what is be heat-treated in the step 4 is specific
Process is to be heated to 40-90 DEG C, stirs 1-10h；Then 4-10h is dried in the environment of 100-150 DEG C；Finally exist
4-12h is calcined at 400-600 DEG C.
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| JPS5879958A (en) * | 1981-11-06 | 1983-05-13 | Mitsubishi Gas Chem Co Inc | Production of carbonic ester |
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| JPS5879958A (en) * | 1981-11-06 | 1983-05-13 | Mitsubishi Gas Chem Co Inc | Production of carbonic ester |
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