CN108043463B - High-performance catalyst for carbon dioxide recycling and preparation method thereof - Google Patents
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Abstract
The invention discloses a high-performance catalyst for carbon dioxide recycling and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving a rigid monomer with amino, a rigid monomer with aldehyde and an emulsion stabilizer in a polar organic solvent, then dropwise adding a non-polar organic solvent, stirring to form a high internal phase emulsion, heating, reacting, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking in a metal ion aqueous solution for 18-24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide. The preparation method is simple, the raw materials are cheap and easy to obtain, the high-performance catalyst for recycling carbon dioxide can efficiently catalyze the cycloaddition reaction of carbon dioxide and epoxy monomers, and the preparation cost is low.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a high-performance catalyst for recycling carbon dioxide and a preparation method thereof.
Background
With the development of economy, the demand for fossil fuels, coal and natural gas has increased day by day, which results in a large amount of carbon dioxide being discharged into the air and causes serious environmental problems such as greenhouse effect. Carbon dioxide, because of its readily available, renewable, and low toxicity characteristics, is one of the most common sources of single carbon and is widely used in chemical synthesis. Therefore, the exploration of a high-efficiency and low-cost carbon dioxide catalytic technology for preparing and synthesizing valuable chemical raw materials has important value and is widely concerned by scholars at home and abroad. Among chemical products, carbonates such as propylene carbonate, ethylene chlorocarbonate, propylene chlorocarbonate, etc. are important carbon dioxide conversion products. The lithium ion battery electrolyte has the characteristics of high boiling point, high flash point, high polarity, low vapor pressure, environmental friendliness and the like, and is commonly used for lithium ion battery electrolytes, polymerization medium solvents and the like.
In earlier studies, homogeneous catalytic reactions of carbon dioxide and propylene oxide were generally carried out using small molecule catalysts of the Salen class with metal central ions. The method is limited in that the small molecular catalyst is difficult to separate and regenerate after reaction. On the other hand, the adsorption performance of the small molecular catalyst to carbon dioxide is poor, so that the catalytic activity of the small molecular catalyst is limited. In recent years, in domestic and foreign research, scholars adopt organic or inorganic microporous materials containing metal centers, such as MOF, molecular sieves and other materials, as heterogeneous catalysts. Compared with the Salen small molecular catalyst, the heterogeneous catalyst can be directly separated from the product by filtration, centrifugation and the like. However, these heterogeneous catalysts are inefficient and costly to prepare.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-performance catalyst for recycling carbon dioxide.
The second purpose of the invention is to provide a preparation method of the high-performance catalyst for carbon dioxide resource utilization.
The technical scheme of the invention is summarized as follows:
a preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
according to the mass ratio of 1: 0.4-1.6: 1.5-4.5: 5-13, dissolving a rigid monomer with amino, a rigid monomer with aldehyde and an emulsion stabilizer in a polar organic solvent, and dropwise adding a non-polar organic solvent, wherein the volume ratio of the polar organic solvent to the non-polar organic solvent is 1: 3-5, stirring to form a high internal phase emulsion, heating to 140 ℃ and 170 ℃, reacting for 72-96 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking in a metal ion aqueous solution for 18-24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
Preferably, the rigid monomer bearing an amino group is melamine, p-phenylenediamine, trimesamine or biphenyldiamine.
Preferably, the rigid monomer with an aldehyde group is paraformaldehyde, terephthalaldehyde, trimeldehyde or biphenyldicarboxaldehyde.
Preferably, the emulsion stabilizer is
The type F127 is a mixture of a plurality of types,
p123 type or
Model F68.
Preferably, the polar organic solvent is dimethylformamide, dimethylacetamide or dimethylsulfoxide.
Preferably, the non-polar organic solvent is petroleum ether, IsoparTMG or IsoparTMM。
Preferably, the metal ion is zinc, cobalt, copper or iron.
The high-performance catalyst for carbon dioxide recycling prepared by the method.
The invention has the advantages that:
the preparation method is simple, the raw materials are cheap and easy to obtain, the high-performance catalyst for recycling carbon dioxide can efficiently catalyze the cycloaddition reaction of carbon dioxide and epoxy monomers, and the preparation cost is low.
Drawings
Fig. 1 is a photograph of the morphology of the high-performance catalyst for carbon dioxide recycling prepared in example 1. Wherein a is a scanning electron microscope photograph thereof, and b and c are high-resolution transmission electron microscope photographs.
Detailed Description
The following examples will help to understand the present invention, but do not limit the contents of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
according to the mass ratio of 1: 0.43: 4.1: 11.6 ratio of melamine, paraformaldehyde and
dissolving the F127 type emulsion stabilizer in dimethyl sulfoxide (DMSO), and adding Isopar dropwiseTMM, DMSO and IsoparTMThe volume ratio of M is 1: 3.3, stirring to form a high internal phase emulsion, heating to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L zinc chloride aqueous solution for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide, wherein the figure is 1.
As can be seen from the figure, the a diagram shows that the structure has a large number of macroporous structures, while the b diagram shows that mesoporous channels exist in the pore walls of the structure. The grid structure in the graph c indicates that a large number of micropore structures exist in the material. The structure is formed by polymerizing a monomer with amino and a monomer with aldehyde groups through Schiff base reaction.
The high-performance catalyst for carbon dioxide resource characterization comprises the following steps:
adding 16.5mg of high-performance catalyst for recycling carbon dioxide, 0.414mg of tetrabutylammonium bromide and 15mL of propylene oxide into a 25mL reaction kettle, introducing carbon dioxide into the reaction kettle, and pressurizing to 2 MPa. The reaction was carried out at 100 ℃ for 30 min. After the reaction is finished, 1,2, 2-tetrachloroethane with the same volume is added into the product liquid as an internal standard solvent, the components of the mixed liquid are represented by a liquid nuclear magnetic resonance spectrometer (NMR), and the conversion rate and TOF of the reaction are calculated according to the peak intensity of the product and the internal standard solvent. In the reaction, the dosage of the propylene oxide catalyst per gram is 0.75mg, the conversion rate of the propylene carbonate is 79.2 percent, and the TOF value is as high as 18430.
The following examples and comparative examples were all measured by this method.
Comparative example 1
According to the mass ratio of 1: 0.43: 4.1: 11.6 ratio of melamine, paraformaldehyde and
dissolving an F127 type emulsion stabilizer in dimethyl sulfoxide (DMSO), heating to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L zinc chloride aqueous solution for 24 hours, filtering, and drying the solid.
The conversion of propylene carbonate was found to be 37.5% and the TOF value was 5431.
Example 2
The preparation method of the high-performance catalyst for carbon dioxide resource utilization comprises the following steps:
mixing melamine, paraformaldehyde and formaldehyde according to the mass ratio of 1:1.6:4.5:13
Dissolving the F127 type emulsion stabilizer in dimethyl sulfoxide (DMSO), and adding Isopar dropwiseTMM, DMSO and IsoparTMThe volume ratio of M is 1: and 5, stirring to form a high internal phase emulsion, heating to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L zinc chloride aqueous solution for 18 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 68.1% with a TOF of 13451.
Example 3
The preparation method of the high-performance catalyst for carbon dioxide resource utilization comprises the following steps:
mixing melamine, paraformaldehyde and water according to the mass ratio of 1:0.4:1.5:5
Dissolving the F127 type emulsion stabilizer in dimethyl sulfoxide (DMSO), and adding Isopar dropwiseTMM, DMSO and IsoparTMThe volume ratio of M is 1: and 3, stirring to form a high internal phase emulsion, heating to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L zinc chloride aqueous solution for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 67.2% with a TOF of 13642.
Example 4
The preparation method of the high-performance catalyst for carbon dioxide resource utilization comprises the following steps:
according to the mass ratio of 1: 0.43: 4.1: 11.6 ratio of melamine, paraformaldehyde and
dissolving the F127 type emulsion stabilizer in dimethyl sulfoxide (DMSO), and adding Isopar dropwiseTMM, DMSO and IsoparTMThe volume ratio of M is 1: and 3.3, stirring to form a high internal phase emulsion, heating to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in a 0.1mol/L aqueous solution of cobalt acetate for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 70.1% with a TOF of 14453.5.
Example 5
The preparation method of the high-performance catalyst for carbon dioxide resource utilization comprises the following steps:
according to the mass ratio of 1: 0.43: 4.1: 11.6 ratio of melamine, paraformaldehyde and
dissolving the F127 type emulsion stabilizer in dimethyl sulfoxide (DMSO), and adding Isopar dropwiseTMM, DMSO and IsoparTMThe volume ratio of M is 1: 3.3, stirring to formHeating the high internal phase emulsion to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L aqueous solution of copper chloride for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 63.1% with a TOF of 10571.
Example 6
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
according to the mass ratio of 1: 0.43: 4.1: 11.6 ratio of melamine, paraformaldehyde and
dissolving the F127 type emulsion stabilizer in dimethyl sulfoxide (DMSO), and adding Isopar dropwiseTMM, DMSO and IsoparTMThe volume ratio of M is 1: and 3.3, stirring to form a high internal phase emulsion, heating to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in a 0.1mol/L ferric chloride solution (the solvent of the ferric chloride solution is 0.1mol/L hydrochloric acid aqueous solution) for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 65.1% with a TOF of 11867.1.
Example 7
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
mixing melamine, terephthalaldehyde and benzene-dimethylformaldehyde according to the mass ratio of 1:1.6:3.7:11.6
Dissolving P123 type emulsion stabilizer in Dimethylacetamide (DMAC), and adding Isopar dropwiseTMM, DMAC and IsoparTMThe volume ratio of M is 1: 3.3 stirring to form a high internal phase emulsion, heating to 170 ℃ and reacting for 72 hours, using acetone, tetrahydrofuran, dichloroethane andwashing with water, filtering to obtain a solid, soaking the solid in 0.1mol/L aqueous solution of copper chloride for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 64.8% with a TOF of 10952.
Example 8
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
mixing melamine, terephthalaldehyde and benzene-dimethylformaldehyde according to the mass ratio of 1:1.6:3.7:11.6
Dissolving P123 type emulsion stabilizer in Dimethylacetamide (DMAC), and adding Isopar dropwiseTMG, DMAC and IsoparTMThe volume ratio of G is 1: 3.3, stirring to form a high internal phase emulsion, heating to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L aqueous solution of copper chloride for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 63.2% with a TOF of 10543.
Example 9
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
according to the mass ratio of 1: 0.43: 4.1: 11.6 ratio of melamine, terephthalaldehyde and
dissolving the F127 type emulsion stabilizer in dimethyl sulfoxide (DMSO), and adding Isopar dropwiseTMM, DMSO and IsoparTMThe volume ratio of M is 1: 3.3, stirring to form a high internal phase emulsion, heating to 170 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the white solid in 0.1mol/L zinc chloride aqueous solution for 24 hours, filtering, and drying the solid to obtain the product for carbon dioxideA humanized high performance catalyst.
The conversion of propylene carbonate was found to be 67.8% with a TOF of 14041.
Example 10
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
according to the mass ratio of 1:0.66:1.9:12.3, p-phenylenediamine, trimesic aldehyde and benzene are mixed
Dissolving an emulsion stabilizer of F68 type in Dimethylformamide (DMF), and dropwise adding petroleum ether, wherein the volume ratio of DMF to petroleum ether is 1: and 3.3, stirring to form a high internal phase emulsion, heating to 140 ℃, reacting for 96 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in a 0.1mol/L ferric chloride solution (the solvent of the ferric chloride solution is 0.1mol/L hydrochloric acid aqueous solution) for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 72.4% and the TOF was 15021.
Example 11
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
according to the mass ratio of 1:1.16:3.2:12.5, respectively mixing trimesic triamine, biphenyldicarboxaldehyde and biphenyldicarbonyl formaldehyde
Dissolving the F127 type emulsion stabilizer in Dimethylformamide (DMF), and adding Isopar dropwiseTMG, DMF and IsoparTMThe volume ratio of G is 1: 3.3, stirring to form a high internal phase emulsion, heating to 160 ℃, reacting for 96 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L zinc chloride aqueous solution for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 71.1% with a TOF of 14935.1.
Example 12
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
according to the mass ratio of 1:0.6:1.5:6.5, mixing the biphenyl diamine, the trimesic aldehyde and the benzene
Dissolving P123 type emulsion stabilizer in Dimethylacetamide (DMAC), and adding Isopar dropwiseTMG, DMAC and IsoparTMThe volume ratio of G is 1: 3.3, stirring to form a high internal phase emulsion, heating to 150 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L zinc chloride aqueous solution for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 73.4% with a TOF of 15871.4.
Example 13
A preparation method of a high-performance catalyst for carbon dioxide recycling comprises the following steps:
according to the mass ratio of 1:0.6:1.5:6.5, mixing the biphenyl diamine, the trimesic aldehyde and the benzene
Dissolving P123 type emulsion stabilizer in Dimethylacetamide (DMAC), and adding Isopar dropwiseTMG, DMAC and IsoparTMThe volume ratio of G is 1: 3.3, stirring to form a high internal phase emulsion, heating to 140 ℃, reacting for 72 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking the solid in 0.1mol/L zinc chloride aqueous solution for 24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide.
The conversion of propylene carbonate was found to be 75.2% with a TOF of 16125.4.
Experiments prove that: the morphology photos of the high-performance catalysts for carbon dioxide recycling prepared in examples 2-13 are similar to the morphology photo of fig. 1.
Claims (6)
1. A preparation method of a high-performance catalyst for carbon dioxide recycling is characterized by comprising the following steps:
according to the mass ratio of 1: 0.4-1.6: 1.5-4.5: 5-13, dissolving a rigid monomer with amino, a rigid monomer with aldehyde and an emulsion stabilizer in a polar organic solvent, and dropwise adding a non-polar organic solvent, wherein the volume ratio of the polar organic solvent to the non-polar organic solvent is 1: 3-5, stirring to form a high internal phase emulsion, heating to 140 ℃ and 170 ℃, reacting for 72-96 hours, sequentially washing with acetone, tetrahydrofuran, dichloroethane and water, filtering to obtain a solid, soaking in a metal ion aqueous solution for 18-24 hours, filtering, and drying the solid to obtain the high-performance catalyst for recycling carbon dioxide;
the rigid monomer with amino is melamine, p-phenylenediamine, trimelamine or biphenyldiamine;
the rigid monomer with aldehyde group is paraformaldehyde, terephthalaldehyde, trimesic aldehyde or biphenyldicarboxaldehyde.
2. The method as set forth in claim 1, wherein said emulsion stabilizer is
The type F127 is a mixture of a plurality of types,
p123 type or
Model F68.
3. The method according to claim 1, wherein the polar organic solvent is dimethylformamide, dimethylacetamide or dimethylsulfoxide.
4. According to the claimsThe method of claim 1, wherein the non-polar organic solvent is petroleum ether or IsoparTMG or IsoparTMM。
5. The method of claim 1, wherein the metal ion is zinc, cobalt, copper or iron.
6. A high performance catalyst for carbon dioxide reclamation prepared by the process of any one of claims 1 to 5.
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| CN102430396A (en) * | 2011-09-16 | 2012-05-02 | 华东理工大学 | Synthetic method of spherical nitrogen-enriched micro-reticular resin for CO2 adsorption |
| CN105642256A (en) * | 2016-01-29 | 2016-06-08 | 江苏科技大学 | Hydrophobic resin oil adsorption material and preparation method |
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