CN104785298B - A kind of solid base catalyst, preparation method and applications with metal-organic framework materials as carrier - Google Patents
A kind of solid base catalyst, preparation method and applications with metal-organic framework materials as carrier Download PDFInfo
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Abstract
The invention discloses a kind of solid base catalyst with metal-organic framework materials as carrier, can be used as the catalyst of ester exchange reaction.The solid base catalyst is prepared with metal-organic framework materials as carrier by the method such as wet impregnation and heat treatment, can catalyzed transesterification Synthesis of dimethyl carbonate in a mild condition.Solid base catalyst with metal-organic framework materials as carrier of the invention, it is made up of metal-organic framework materials carrier and basic component, described basic component is introduced by alkali presoma, and alkali presoma is 0.01~0.5 with the mass ratio of metal-organic framework materials:1.
Description
Technical field
The present invention relates to a kind of catalyst, preparation method and applications, more specifically to one kind with the organic bone of metal
Frame material is solid base catalyst, the preparation method and applications of carrier.
Background technology
Solid base catalyst is widely used in the production of petrochemical industry and fine chemicals, and it can be in relatively mild condition
Lower catalysis reaction miscellaneous, active high, selectivity is good, reaction condition is gentle, product is easily isolated, reusable edible
Many advantages, such as.Reaction process serialization can especially be made in process of production, strengthen the production capacity of equipment, application prospect ten
Divide wide.
In recent years, metal-organic framework materials have attracted extensively as a kind of novel hybrid inorganic-organic porous material
Research.This kind of material is the porous material being self-assembly of by different metal ions and organic ligand, and it has some special
Different architectural characteristic and very strong designability, adjustability.These unique advantages make metal-organic framework materials exist at present
The fields such as gas storage, adsorbing separation and catalysis have extraordinary application prospect.Specific to catalytic field, urged in many industry
During change, the metal-organic framework materials that can be applied to catalytic field can be divided into greatly three types：(1) with metal active position
The metal-organic framework materials of point；(2) metal-organic framework materials with reactive functional；(3) metal organic framework
Material is as catalyst carrier or serves as molecular reactor.Synthesized at first by F é rey professors seminar of Versailles, France university
Carry out Wa Xier framework materials (materials of institute Lavoisier frameworks, abbreviation MILs), because of its tool
There is the architectural feature of larger specific surface area and stabilization, can be used as a kind of carrier of preferable loaded catalyst.
Dimethyl carbonate (DMC) is a kind of environmental type chemical products for enjoying and paying close attention to both at home and abroad, because containing in its structure
There are methoxyl group and carbonyl, be expected to substitute the severe toxicity such as phosgene or carcinogenic substance occurs carbonylation, methylates and the reaction such as ester exchange is to make
Standby numerous important chemical products.Ester-interchange method is the important method of Synthesis of dimethyl carbonate, and its reaction condition is gentle, process is nontoxic
Method as great application prospect the features such as high with selectivity.Solid base catalyst is to realize that ester exchange synthesizes the core of DMC
Technology, therefore, the exploitation of new and effective catalyzed by solid base agent material receives much concern.
Based on above mentioned problem, the solid base catalyst with metal-organic framework materials as carrier is prepared, and be applied to
The reaction of ester exchange Synthesis of dimethyl carbonate has important practical value.
The content of the invention
It is an object of the invention to provide a kind of solid base catalyst with metal-organic framework materials as carrier, can conduct
The catalyst of ester exchange reaction.The solid base catalyst with metal-organic framework materials as carrier, by wet impregnation and heat treatment
Prepared etc. method, can catalyzed transesterification Synthesis of dimethyl carbonate in a mild condition.
It is another object of the present invention to provide the preparation method of above-mentioned solid base catalyst；The present invention is also provided simultaneously
Application of the solid base catalyst in ester exchange reaction.
The purpose of the present invention is achieved through the following technical solutions：
Solid base catalyst with metal-organic framework materials as carrier of the invention, it is by metal-organic framework materials
Carrier and basic component are constituted, and described basic component is introduced by alkali presoma, alkali presoma and metal-organic framework materials
Mass ratio is 0.01~0.5:1.
The above-mentioned solid base catalyst of the present invention, its further technical scheme is that described metal-organic framework materials are carried
Body is that model MIL-100, MIL-101, MIL-53, MIL-47, MIL-96, MIL-110 or MIL-68 carry out Wa Xier skeletons
Material.
The above-mentioned solid base catalyst of the present invention, its further technical scheme can also be that described alkali presoma is nitre
In sour lithium, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and corresponding acetate
One or more composition.
The preparation method of the above-mentioned solid base catalyst of the present invention, it is comprised the following steps：
(1) wet impregnation method is used, first by the dissolving of alkali presoma in deionized water, metal-organic framework materials, room is added
After 12~24h of the lower stirring of temperature, it is evaporated in 50~80 DEG C of water-baths, 4~8h is dried in 80~100 DEG C of baking ovens, obtains mixture；
(2) heat treating process is used, in atmosphere of inert gases, mixture obtained in activation step (1), soak time is 1
~4h, is allowed to produce basic sites, obtains the solid base catalyst with metal-organic framework materials as carrier.
The preparation method of the above-mentioned solid base catalyst of the present invention, its further technical scheme is described alkali presoma
It is lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and corresponding acetic acid
One or more compositions in salt, alkali presoma is 0.01~0.5 with the mass ratio of metal-organic framework materials:1.
The preparation method of the above-mentioned solid base catalyst of the present invention, its further technical scheme can also be described gold
Category organic framework material carrier is model MIL-100, MIL-101, MIL-53, MIL-47, MIL-96, MIL-110 or MIL-
68 carry out Wa Xier framework materials.
The preparation method of the above-mentioned solid base catalyst of the present invention, its further technical scheme can also be described lazy
Property gas be helium, argon gas or nitrogen；The activation temperature of heat treating process is 200~500 DEG C.
The above-mentioned solid base catalyst of the present invention can be applied in ester exchange reaction；Further technical scheme be
The application in dimethyl carbonate is prepared as raw material with ethylene carbonate and methyl alcohol.
The above-mentioned solid base catalyst of the present invention with ethylene carbonate and methyl alcohol as raw material prepare dimethyl carbonate should
With mainly including the following steps that：Ethylene carbonate, methyl alcohol and solid base catalyst are put into three-neck flask, ethylene carbonate and
The mol ratio of methyl alcohol is 1:5, catalyst amount is the 0.2~5% of material benzenemethanol quality, and reaction temperature is 60~80 DEG C, pressure
It is normal pressure, 0.5~4h is reacted under the conditions of being refluxed, is centrifugally separating to obtain dimethyl carbonate.
The present invention compared with prior art, has the advantages that：
(1) it is carrier that solid base catalyst prepared by the present invention uses metal-organic framework materials i.e. MILs materials first,
The alkali presoma being supported on carrier is activated so as to prepare a kind of new solid base catalyst by being heat-treated.The method knot
The feature of metal-organic framework materials specific surface area higher and larger pore passage structure is closed, basic active position is reached high on carrier
Degree dispersion, while activation temperature is relatively low, improves catalysis activity.
(2) the invention provides a kind of method for preparing catalyst of simple energy-conservation.On the one hand, due to metal organic framework material
The high charge density that the metal ion enriched in material duct can be formed, the decomposition temperature of alkali presoma can be substantially reduced, so that
The tedious steps in catalyst preparation process can be reduced；On the other hand, the reduction of alkali presoma decomposition temperature can reduce the energy
Consumption, so as to also achieve the effect of energy-conservation.
(3) solid base catalyst prepared by the present invention catalyzed transesterification can particularly synthesize under relatively mild environment
Dimethyl carbonate, catalytic effect is ideal, and running cost is low.
Specific embodiment
Present invention specific examples below son explanation, but the present invention is not limited to following embodiments, before and after not departing from
In the range of the objective, change is included in technical scope of the invention.
Embodiment 1
Weigh the NaNO of 0.2g3Dissolving in deionized water, adds the metal organic framework material of 0.8g under stirring
Material MIL-100, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens, will obtain
Sample be placed in U-tube and be passed through nitrogen and activate 2h in 350 DEG C, so as to by NaNO3Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 32.0%.
Embodiment 2
Weigh the LiNO of 0.1g3Dissolving in deionized water, adds the metal organic framework material of 0.9g under stirring
Material MIL-96, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, then 8h is dried in 100 DEG C of baking ovens, by what is obtained
Sample is placed in U-tube and is passed through nitrogen and activates 2h in 300 DEG C, so as to by LiNO3Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 20.1%.
Embodiment 3
Weigh the Mg (CH of 0.38g3COO)2·4H2O dissolves the gold for adding 0.75g under stirring in deionized water
Category organic framework material MIL-68, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, is then dried in 100 DEG C of baking ovens
Dry 8h, the sample that will be obtained is placed in U-tube and is passed through nitrogen and activates 2h in 400 DEG C, so as to by Mg (CH3COO)2Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 35.2%.
Embodiment 4
Weigh the Ca (CH of 0.33g3COO)2·H2O dissolves the metal for adding 0.7g under stirring in deionized water
Organic framework material MIL-101, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, is then dried in 100 DEG C of baking ovens
8h, the sample that will be obtained is placed in U-tube and is passed through nitrogen and activates 2h in 250 DEG C, so as to by Ca (CH3COO)2Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 36.7%.
Embodiment 5
Weigh the CsNO of 0.2g3Dissolving in deionized water, adds the metal organic framework material of 0.8g under stirring
Material MIL-110, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens, will obtain
Sample be placed in U-tube and be passed through nitrogen and activate 2h in 400 DEG C, so as to by CsNO3Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 22.5%.
Embodiment 6
Weigh the KNO of 0.2g3Dissolving in deionized water, adds the metal-organic framework materials of 0.8g under stirring
MIL-100, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, then 8h is dried in 100 DEG C of baking ovens, by what is obtained
Sample is placed in U-tube and is passed through nitrogen and activates 2h in 400 DEG C, so as to by KNO3Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 29.2%.
Embodiment 7
Weigh the Ca (NO of 0.25g3)2Dissolving in deionized water, adds the organic bone of metal of 0.75g under stirring
Frame material MIL-53, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, and 8h is then dried in 100 DEG C of baking ovens, will
To sample be placed in U-tube and be passed through nitrogen and activate 2h in 350 DEG C, so as to by Ca (NO3)2Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 31.3%.
Embodiment 8
Weigh the CH of 0.31g3COOLi·2H2O dissolves in deionized water, adds the metal of 0.8g to have under stirring
Machine framework material MIL-47, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens,
The sample that will be obtained is placed in U-tube and is passed through nitrogen and activates 2h in 300 DEG C, so as to by CH3COOLi is decomposed.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 28.4%.
Embodiment 9
Weigh the Sr (NO of 0.4g3)2Dissolving in deionized water, adds the metal organic framework of 0.6g under stirring
Material MIL-68, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens, will obtain
Sample be placed in U-tube and be passed through nitrogen and activate 2h in 400 DEG C, so as to by Sr (NO3)2Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 30.3%.
Embodiment 10
Weigh the CH of 0.1g3COOK dissolves the metal organic framework for adding 0.9g under stirring in deionized water
Material MIL-101, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, and 8h is then dried in 100 DEG C of baking ovens, will
To sample be placed in U-tube and be passed through nitrogen and activate 2h in 450 DEG C, so as to by CH3COOK is decomposed.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 32.6%.
Embodiment 11
Weigh the Mg (NO of 0.17g3)2·6H2O dissolves in deionized water, adds the metal of 0.9g to have under stirring
Machine framework material MIL-96, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens,
The sample that will be obtained is placed in U-tube and is passed through nitrogen and activates 2h in 350 DEG C, so as to by Mg (NO3)2Decompose.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 21.3%.
Embodiment 12
Weigh the CH of 0.33g3COONa·3H2O dissolves in deionized water, adds the metal of 0.8g to have under stirring
Machine framework material MIL-96, is placed in 80 DEG C of water-baths after stirring 24h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens,
The sample that will be obtained is placed in U-tube and is passed through nitrogen and activates 2h in 300 DEG C, so as to by CH3COONa is decomposed.
By 16g methyl alcohol, in 8.7g ethylene carbonates and 0.08g catalyst addition flask, under normal pressure, 65 DEG C of stirring reactions
4h, is centrifuged supernatant liquor and using gas chromatographic analysis, and the yield of DMC is 23.7%.
Claims (9)
1. a kind of solid base catalyst with metal-organic framework materials as carrier, it is characterised in that the solid base catalyst be by
Metal-organic framework materials carrier and basic component are constituted, and described basic component is introduced by alkali presoma, alkali presoma and gold
The mass ratio for belonging to organic framework material is 0.01~0.5:1；Described metal-organic framework materials carrier is model MIL-
100th, MIL-101, MIL-53, MIL-47, MIL-96, MIL-110 or MIL-68 carry out Wa Xier framework materials；Described solid
The preparation method of base catalyst is comprised the following steps：
(1) wet impregnation method is used, first by the dissolving of alkali presoma in deionized water, metal-organic framework materials is added, at room temperature
After 12~24h of stirring, it is evaporated in 50~80 DEG C of water-baths, 4~8h is dried in 80~100 DEG C of baking ovens, obtains mixture；
(2) heat treating process is used, in atmosphere of inert gases, mixture obtained in activation step (1), soak time is 1~4h,
Activation temperature is 200~500 DEG C, is allowed to produce basic sites, obtains the catalyzed by solid base with metal-organic framework materials as carrier
Agent.
2. solid base catalyst according to claim 1, it is characterised in that described alkali presoma is lithium nitrate, nitric acid
One kind or several in sodium, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and corresponding acetate
Plant composition.
3. the preparation method of a kind of solid base catalyst as described in claim 1-2 is any, it is characterised in that including following step
Suddenly：
(1) wet impregnation method is used, first by the dissolving of alkali presoma in deionized water, metal-organic framework materials is added, at room temperature
After 12~24h of stirring, it is evaporated in 50~80 DEG C of water-baths, 4~8h is dried in 80~100 DEG C of baking ovens, obtains mixture；
(2) heat treating process is used, in atmosphere of inert gases, mixture obtained in activation step (1), soak time is 1~4h,
Activation temperature is 200~500 DEG C, is allowed to produce basic sites, obtains the catalyzed by solid base with metal-organic framework materials as carrier
Agent.
4. the preparation method of solid base catalyst according to claim 3, it is characterised in that described alkali presoma is nitre
In sour lithium, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and corresponding acetate
One or more compositions, the mass ratio of alkali presoma and metal-organic framework materials is 0.01~0.5:1.
5. the preparation method of the solid base catalyst according to claim 3 or 4, it is characterised in that the organic bone of described metal
Frame material carrier be model MIL-100, MIL-101, MIL-53, MIL-47, MIL-96, MIL-110 or MIL-68 come watt
Xi Er framework materials.
6. the preparation method of solid base catalyst according to claim 3, it is characterised in that described inert gas is helium
Gas, argon gas or nitrogen.
7. a kind of application of the solid base catalyst in ester exchange reaction as described in claim 1-2 is any.
8. application of the solid base catalyst according to claim 7 in ester exchange reaction, it is characterised in that be with carbon
Vinyl acetate and methyl alcohol prepare the application in dimethyl carbonate for raw material.
9. application of the solid base catalyst according to claim 8 in ester exchange reaction, it is characterised in that it is described
Mainly included the following steps that with the application that ethylene carbonate and methyl alcohol prepare dimethyl carbonate as raw material：By ethylene carbonate, first
Alcohol and solid base catalyst are put into three-neck flask, and the mol ratio of ethylene carbonate and methyl alcohol is 1:5, catalyst amount is raw material
The 0.2~5% of methanol quality, reaction temperature is 60~80 DEG C, and pressure is normal pressure, and 0.5~4h is reacted under the conditions of being refluxed, from
The isolated dimethyl carbonate of the heart.
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| CN105964300B (en) * | 2016-04-27 | 2018-08-14 | 三河市祥天电力工程有限公司 | A kind of Biodiesel esterification heterogeneous catalysis and preparation method thereof |
| CN106861668A (en) * | 2017-02-13 | 2017-06-20 | 杭州诚洁环保有限公司 | A kind of MgO/HC solid base catalysts and its catalysis ozone process the purposes and method of waste water |
| CN113019352A (en) * | 2021-03-16 | 2021-06-25 | 山东建筑大学 | Preparation method of embedded alkaline earth metal oxide solid base and application of embedded alkaline earth metal oxide solid base in biodiesel production |
| CN113101914A (en) * | 2021-04-14 | 2021-07-13 | 南京工业大学 | Preparation method of monatomic solid base catalyst with highly-dispersed and loss-resistant alkaline sites, product and application of monatomic solid base catalyst |
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