CN104801348B - Solid base catalyst for transesterification and preparation method thereof - Google Patents
Solid base catalyst for transesterification and preparation method thereof Download PDFInfo
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- CN104801348B CN104801348B CN201510187866.2A CN201510187866A CN104801348B CN 104801348 B CN104801348 B CN 104801348B CN 201510187866 A CN201510187866 A CN 201510187866A CN 104801348 B CN104801348 B CN 104801348B
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Abstract
The invention discloses a solid base catalyst which adopts a metal organic framework material as a carrier, and is prepared through such methods as dipping, drying and activation. The solid base catalyst can be used as a catalyst for transesterification to catalyze the transesterification for the synthesis of dimethyl carbonate under a mild condition. The solid base catalyst for transesterification provided by the invention consists of a basic component and the carrier, namely the metal organic framework material, wherein the basic component is introduced by a basic precursor, and the mass ratio of the basic precursor to the metal organic framework material is (0.01-0.4):1.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, more specifically to a kind of consolidating for ester exchange reaction
Body base catalyst and preparation method thereof.
Background technology
Dimethyl carbonate (Dimethyl Carbonate, abbreviation DMC) is a kind of to enjoy the domestic and international environmental type paid close attention to
Chemical products, because containing methoxyl group and carbonyl, being expected to substitute the severe toxicity such as phosgene or carcinogenic substance generation carbonylation, methyl in its structure
Change and ester exchange etc. react to prepare numerous important chemical products.Its synthesis receives in recent years extensive attention with application.DMC
Synthetic route can be divided into following 5 kinds：Phosgenation, oxidative carbonylation of methanol method, ester-interchange method, methyl alcohol and CO2Direct synthesis technique,
Urea and Methanolysis method.Phosgenation is progressively eliminated due to raw material severe toxicity.The predominantly ester-interchange method of current commercial Application
And oxidative carbonylation of methanol method.Wherein, ester-interchange method is the gentle reaction of low heat release, is carried out in the liquid phase, the corrosion-free nothing of process
It is malicious, selective high and also simple in technological process, it is the method for great prospects for commercial application.
Industrial ester-interchange method is now mainly the methanol solution of sodium methoxide with catalyst, due to being homogeneous reaction, so instead
Should after the catalyst and product difficult separation and recycling, cause cost increase.Reinforcement and green with world's environmental consciousness
The development of chemistry, people increasingly pay attention to eco-friendly catalysis New Process, have as catalyst using solid base high living
Property, high selectivity, gently, product is easily isolated reaction condition, many advantages, such as can be recycled, so its research and development potentiality
Extensively had an optimistic view of.The exploitation so solid catalyst for being suitable for ester exchange reaction requires study.
Metal-organic framework materials are a kind of new materials for growing up in recent years, and it is by inorganic metal ion and contains
The porous material with infinite network structure that the multiple tooth organic ligand of nitrogen or oxygen is self-assembly of by coordination.Wherein,
(1) ZIFs series materials (zeolitic imidazolate frameworks) are a series of gold being combined into by Yaghi problems
Category organic framework material, it is the molecular sieve analog imidazoles coordination polymerization being complexed by metal ion and imidazoles or imdazole derivatives
Thing.This kind of material has similar topological structure to zeolite molecular sieve, but is different from zeolite molecular sieve again on architecture model, boils
Stone imidazate framework material is to replace the element silicon and aluminium element in traditional zeolite with zinc ion and cobalt ions etc., with imidazoles or miaow
Zole derivatives replace the porous material of oxygen composition.They all have preferable heat endurance and a chemical stability, and with it is traditional
Molecular sieve is compared, and it has yield higher, pore size and reconfigurable, the advantages of 26S Proteasome Structure and Function is varied.(2)PCNs
Series material (porous coordination networks) is synthesized by Zhou seminars of Midland, MI university.
Such material there is also larger difference due to properties such as the difference of organic ligand, duct, windows.(3) PCP series materials
(porous coordination polymers) is a series of metals being combined into by Kyoto Univ Japan's Kitagawa problems
Organic framework material.This series material meeting reversible structure and property for changing its skeleton during the different guest molecules of absorption
, there is " gate-opening " phenomenon in matter, and these characteristics the aspect such as sense in the selective absorption of gas, molecule potential application
Prospect.
Based on the problems referred to above, prepare the high-activity solid base catalyst with metal-organic framework materials as carrier, and by its
The reaction for being applied to ester exchange Synthesis of dimethyl carbonate has far-reaching application prospect and extensive economic results in society.
The content of the invention
It is an object of the invention to provide a kind of solid base catalyst, the solid base catalyst is with metal-organic framework materials
For carrier, by dipping, be dried, the method such as activation is prepared, can be used as the catalyst of ester exchange reaction, and can be gentle
Under the conditions of catalyzed transesterification Synthesis of dimethyl carbonate.
Further object is that providing the preparation method of above-mentioned solid base catalyst；Simultaneously the present invention is also provided
Application of the catalyst in ester exchange reaction.
The purpose of the present invention is achieved through the following technical solutions：
The solid base catalyst for ester exchange reaction of the present invention, it is by basic component and metal-organic framework materials
Carrier is constituted, and described basic component is introduced by alkali presoma, and alkali presoma is with the mass ratio of metal-organic framework materials
0.01～0.4:1.
The above-mentioned solid base catalyst of the present invention, its further technical scheme be described alkali presoma for lithium nitrate,
One kind in sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and corresponding acetate
Or several compositions.
The above-mentioned solid base catalyst of the present invention, its further technical scheme can also be described metallic organic framework
Material is the metallic organic framework ZIFs series materials of model ZIF-7, ZIF-8, ZIF-68 or ZIF-78；Or described gold
Category organic framework material be model PCN-13, PCN-14, PCN-11 or HKUST-1 metallic organic framework PCNs series materials and
PCP series materials.
The preparation method of the above-mentioned solid base catalyst of the present invention, it is comprised the following steps：Alkali presoma is adopted first
Wet impregnation method is introduced, that is, weigh alkali presoma and dissolve in a solvent, metal-organic framework materials is added under stirring, in room
After temperature 1～12h of lower stirring, it is evaporated in 60～90 DEG C of water-baths, 4～8h is dried in 80～120 DEG C of baking ovens, by the sample for obtaining
1～4h is activated in 200～500 DEG C of atmosphere of inert gases, is allowed to produce the solid that basic sites obtain for ester exchange reaction
Base catalyst.
The preparation method of the above-mentioned solid base catalyst of the present invention, its further technical scheme is described alkali presoma
For 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 0.01～0.4 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 is the metallic organic framework ZIFs series materials of model ZIF-7, ZIF-8, ZIF-68 or ZIF-78；Or
Metal-organic framework materials described in person are model PCN-13, PCN-14, PCN-11 or HKUST-1 metallic organic framework PCNs
Series material and PCP series materials.
The preparation method of the above-mentioned solid base catalyst of the present invention, its further technical scheme can also be described molten
Agent is one or more compositions in deionized water, absolute ethyl alcohol or absolute methanol；Described inert gas be helium, argon gas or
Nitrogen.
The above-mentioned solid base catalyst of the present invention can be applied in ester exchange reaction.
Application of the above-mentioned solid base catalyst of the present invention in ester exchange reaction, its further technical scheme be with
Ethylene carbonate and methyl alcohol prepare the application in dimethyl carbonate for raw material.
The present invention it is above-mentioned with ethylene carbonate and methyl alcohol as the application that raw material prepares dimethyl carbonate mainly include with
Lower step：Ethylene carbonate, methyl alcohol and solid base catalyst are put in three-neck flask, the mol ratio of ethylene carbonate and methyl alcohol
For 1:5, catalyst amount is the 0.2～5% of material benzenemethanol quality, and reaction temperature is 60～80 DEG C, and pressure is normal pressure, and backflow is stirred
0.5～4h is reacted under the conditions of mixing, dimethyl carbonate is centrifugally separating to obtain.
Invention compared with prior art has the advantages that：
The solid base catalyst for ester exchange reaction of the present invention is a kind of loaded catalyst, due to the organic bone of metal
Frame material mainly has good specific surface area and enriches including ZIFs series materials, PCNs series materials and PCP series materials
Pore structure, the catalyst basic component high degree of dispersion of preparation.In ester exchange reaction with ethylene carbonate and methyl alcohol as raw material system
In the reaction of standby dimethyl carbonate, under gentle reaction condition, activation temperature is relatively low, and the catalyst for obtaining shows well
Catalytic performance.Meanwhile, preparation method of the present invention is simple, environmental friendliness, economical and energy saving.
Specific embodiment
Present invention specific examples below son explanation, but the present invention is not limited to following embodiments, without departing from before and after
In the range of the objective, change is included in the technical scope of the present invention.
Embodiment 1
Weigh the LiNO of 0.3g3Dissolving in deionized water, adds the metallic organic framework material of 0.7g under stirring
Material HKUST-1, is placed in 80 DEG C of water-baths after stirring 6h 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 280 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 38.9%.
Embodiment 2
Weigh the Mg (NO of 0.17g3)2·6H2O is dissolved in absolute ethyl alcohol, adds the metal of 0.9g to have under stirring
Machine framework material ZIF-8, is placed in 80 DEG C of water-baths after stirring 6h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens, will
The sample for obtaining 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 17.9%.
Embodiment 3
Weigh the CH of 0.31g3COOLi·2H2O is dissolved in absolute methanol, adds the metal of 0.8g to have under stirring
Machine framework material PCN-14, is placed in 80 DEG C of water-baths after stirring 6h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens,
The sample for obtaining is placed in U-tube and is passed through nitrogen and is activated 2h in 300 DEG C, so as to by CH3COOLi decomposes.
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 Sr (NO of 0.1g3)2In being dissolved in absolute ethyl alcohol, the metallic organic framework of 0.9g is added under stirring
Material ZIF-8, is placed in 80 DEG C of water-baths after stirring 6h 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 350 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 18.5%.
Embodiment 5
Weigh the CH of 0.2g3COOK is dissolved in absolute ethyl alcohol, and the metallic organic framework of 0.8g is added under stirring
Material ZIF-68, is placed in 80 DEG C of water-baths after stirring 6h 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 300 DEG C, so as to by CH3COOK decomposes.
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 29.7%.
Embodiment 6
Weigh the LiNO of 0.1g3Dissolving in deionized water, adds the metallic organic framework material of 0.9g under stirring
Material PCN-13, is placed in 80 DEG C of water-baths after stirring 6h 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 250 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 15.3%.
Embodiment 7
Weigh the Ca (NO of 0.25g3)2In being dissolved in absolute methanol, the organic bone of metal of 0.75g is added under stirring
Frame material PCN-11, is placed in 80 DEG C of water-baths after stirring 6h 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 27.1%.
Embodiment 8
Weigh the CH of 0.33g3COONa·3H2O dissolves in deionized water, adds the metal of 0.8g to have under stirring
Machine framework material HKUST-1, is placed in 80 DEG C of water-baths after stirring 6h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens,
The sample for obtaining is placed in U-tube and is passed through nitrogen and is activated 2h in 300 DEG C, so as to by CH3COONa decomposes.
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 30.1%.
Embodiment 9
Weigh the Sr (NO of 0.1g3)2In being dissolved in absolute ethyl alcohol, the metallic organic framework of 0.9g is added under stirring
Material ZIF-7, is placed in 80 DEG C of water-baths after stirring 6h 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 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 12.8%.
Embodiment 10
Weigh the Mg (NO of 0.17g3)2·6H2O is dissolved in absolute methanol, adds the metal of 0.9g to have under stirring
Machine framework material ZIF-78, is placed in 80 DEG C of water-baths after stirring 6h is evaporated at room temperature, then dries 8h in 100 DEG C of baking ovens,
The sample for obtaining is placed in U-tube and is passed through nitrogen and is activated 2h in 400 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 13.7%.
Claims (6)
1. a kind of solid base catalyst for ester exchange reaction, it is characterised in that the solid base catalyst be by basic component and
Metal-organic framework materials carrier is constituted, and described basic component introduces by alkali presoma, alkali presoma and metallic organic framework
The mass ratio of material is 0.01～0.4:1；Described alkali presoma be lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate,
One or more compositions in magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and corresponding acetate；The organic bone of described metal
Frame material is the metallic organic framework ZIFs series materials of model ZIF-7, ZIF-8, ZIF-68 or ZIF-78；Or it is described
Metal-organic framework materials are model PCN-13, PCN-14, PCN-11 or HKUST-1 metallic organic framework PCNs series materials
And PCP series materials.
2. the preparation method of solid base catalyst according to claim 1, it is characterised in that comprise the following steps：First will
Alkali presoma is introduced using wet impregnation method, that is, weigh alkali presoma and dissolve in a solvent, adds metal organic under stirring
Framework material, after 1～12h is stirred at room temperature, is evaporated in 60～90 DEG C of water-baths, dry 4 in 80～120 DEG C of baking ovens～
8h, 1～4h is activated by the sample for obtaining in 200～500 DEG C of atmosphere of inert gases, is allowed to produce basic sites and is obtained for ester
The solid base catalyst of exchange reaction；Wherein described alkali presoma is lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, nitric acid
One or more compositions in caesium, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate and corresponding acetate, alkali presoma and metal
The mass ratio of organic framework material is 0.01～0.4:1；Described metal-organic framework materials be model ZIF-7, ZIF-8,
The metallic organic framework ZIFs series materials of ZIF-68 or ZIF-78；Or described metal-organic framework materials are models
PCN-13, PCN-14, PCN-11 or HKUST-1 metallic organic framework PCNs series materials and PCP series materials.
3. the preparation method of solid base catalyst according to claim 2, it is characterised in that described solvent is deionization
One or more compositions in water, absolute ethyl alcohol or absolute methanol；Described inert gas is helium, argon gas or nitrogen.
4. application of a kind of solid base catalyst as claimed in claim 1 in ester exchange reaction.
5. application of the solid base catalyst according to claim 4 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.
6. application of the solid base catalyst according to claim 5 in ester exchange reaction, it is characterised in that it is described
Mainly included the following steps that as the application that raw material prepares dimethyl carbonate with ethylene carbonate and methyl alcohol：By ethylene carbonate, first
Alcohol and solid base catalyst are put in 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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| CN109603802A (en) * | 2018-12-25 | 2019-04-12 | 开封中科新材料有限公司 | For by urea and the composite catalyst of methanol-fueled CLC dimethyl carbonate and its preparation method and application |
| CN112724017B (en) * | 2021-01-14 | 2022-09-20 | 吉林师范大学 | Method for synthesizing asymmetric organic carbonate at room temperature |
| 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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| CN102824924A (en) * | 2012-09-25 | 2012-12-19 | 南京工业大学 | Mesoporous solid strong alkali catalyst as well as preparation method and application thereof |
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| CN104185632A (en) * | 2012-02-28 | 2014-12-03 | 沙特基础工业公司 | Process for preparing carbonate and diol products |
| CN102824924A (en) * | 2012-09-25 | 2012-12-19 | 南京工业大学 | Mesoporous solid strong alkali catalyst as well as preparation method and application thereof |
| CN103920523A (en) * | 2014-05-07 | 2014-07-16 | 南京工业大学 | Method for preparing mesoporous solid strong alkali catalyst |
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