CN111548273B - Method for preparing dimethyl carbonate by using copper/cuprous oxide nanosheet catalyst to thermally catalyze methanol and carbon dioxide - Google Patents

Method for preparing dimethyl carbonate by using copper/cuprous oxide nanosheet catalyst to thermally catalyze methanol and carbon dioxide Download PDF

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CN111548273B
CN111548273B CN202010386703.8A CN202010386703A CN111548273B CN 111548273 B CN111548273 B CN 111548273B CN 202010386703 A CN202010386703 A CN 202010386703A CN 111548273 B CN111548273 B CN 111548273B
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stirring
copper
reaction
cuprous oxide
carbon dioxide
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CN111548273A (en
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张晓东
金森
谢毅
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University of Science and Technology of China USTC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/72—Copper
    • B01J35/40—
    • B01J35/61—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Abstract

The invention provides a method for generating dimethyl carbonate by using a copper/cuprous oxide nanosheet catalyst to thermally catalyze methanol and carbon dioxide, and belongs to the technical field of organic synthesis. The invention directly utilizes carbon dioxide and methanol to react in one pot to generate dimethyl carbonate by taking organic matters as solvent and copper/cuprous oxide nanosheets as catalyst at lower temperature and lower pressure. The method has the advantages of high atom utilization rate, environmental friendliness, simple reaction steps and low cost, and is suitable for large-scale production.

Description

Method for preparing dimethyl carbonate by using copper/cuprous oxide nanosheet catalyst to thermally catalyze methanol and carbon dioxide
Technical Field
The invention provides a method for generating dimethyl carbonate by using a copper/cuprous oxide nanosheet catalyst to thermally catalyze methanol and carbon dioxide, and belongs to the technical field of organic synthesis.
Background
As a major gas causing greenhouse effect, excessive carbon dioxide disturbs the balance of carbon cycle, water cycle and even the entire ecosystem of the earth environment. Thus, successful conversion of carbon dioxide to useful chemicals and fuels by fixed reactions using suitable catalysts can effectively reduce the deleterious effects on the ecosystem. Meanwhile, as a potential carbon resource for solving the problem of the shortage of energy and basic chemical raw materials, various organizations around the world, including national and international governments, establish some interesting cooperative projects for solving the problem of carbon dioxide. With technological advances, gaseous products such as carbon dioxide (CO), methane (CH4), ethylene (C2H2) or C1 liquids such as formic acid (HCOOH) have been well studied, and their obvious properties of low cost and unfavorable long-range mass transport have led to the idea of fixing carbon dioxide to more valuable long-carbon-chain high energy density products.
Dimethyl carbonate, as an important starting material and intermediate for organic synthesis, can be used as a carbonylation, methylation and carbonyl methylation reagent instead of toxic and harmful phosgene, dimethyl sulfate and methyl chloroformate due to the active functional groups such as carbonyl, methyl, methoxy and the like in the molecular structure. Because the dimethyl carbonate has the advantages of no toxicity, excellent environmental protection performance, wide application and the like, people have led to extensive research on the dimethyl carbonate. Compared with the traditional synthesis method, the direct synthesis of dimethyl carbonate by using the greenhouse gas carbon dioxide as a raw material and methanol through a catalytic reaction is more important for research.
Since the direct synthesis of dimethyl carbonate from carbon dioxide and methanol is positive in the range of 0.1MPa and 0-800 ℃, the direct synthesis is difficult to carry out thermodynamically, resulting in low conversion rate. The main reason for this is that the preparation of highly active catalysts has been the key to the reaction due to the high stability of carbon dioxide. At present, the catalysts used for synthesizing dimethyl carbonate by directly reacting carbon dioxide with methanol include alkoxy metal organic compounds, alkali metals, copper-based supported metal catalysts, transition metal oxides, and the like. Among them, the copper-based supported catalyst is limited in practical application due to severe reaction conditions, low conversion rate, and the like.
Disclosure of Invention
The invention aims to solve the problems of complex process, high energy consumption and the like of the existing copper-based catalyst applied to directly synthesizing dimethyl carbonate by using carbon dioxide and methanol. In order to achieve the purpose, the traditional copper-based catalyst is changed, cuprous oxide is introduced, activation energy is reduced in a heterojunction mode, the surface area of a sample is enlarged in a nanosheet mode, the temperature and pressure required by reaction are reduced, and the product conversion rate is improved.
Specifically, the invention provides a method for synthesizing dimethyl carbonate by thermal catalysis, which comprises the following steps:
s1, adding a copper/cuprous oxide heterojunction nanosheet catalyst into an organic solvent, and violently stirring to obtain a mixed solution;
s2, adding methanol into the mixed solution obtained in the step S1, and introducing inert gas to obtain a reaction solution;
s3, transferring the reaction liquid obtained in the step S2 to a closed high-pressure kettle, and introducing pure carbon dioxide;
s4, under the stirring condition, keeping the carbon dioxide in the autoclave at the pressure of 0.1-10Mp, isolating air, and heating to the reaction temperature for reaction;
s5, centrifuging and taking supernatant to obtain a product;
wherein the copper/cuprous oxide heterojunction nanosheet catalyst is prepared by the following steps:
(1) adding an organic solvent into an alcohol solvent, and uniformly stirring to obtain a mixed solution;
(2) adding copper acetylacetonate and a surfactant into the mixed solution obtained in the step (1), and violently stirring to obtain a reaction solution;
(3) transferring the reaction liquid in the step (2) into a polytetrafluoroethylene reaction kettle, sealing, and heating to 100-200 ℃ to obtain a product;
(4) and washing, drying and grinding the product to obtain the copper/cuprous oxide heterojunction nanosheet catalyst.
In some embodiments, in step S1, the organic solvent includes cyclohexane, acetonitrile, n-hexane, benzene, and combinations thereof.
In some embodiments, in step S1, the ratio of copper/cuprous oxide nanosheet catalyst to organic solvent is from 0.002 to 0.1 g/mL.
In some embodiments, in steps S1 and S4, the stirring may be selected from magnetic stirring and mechanical stirring; preferably, the stirring rate is 100-.
In some embodiments, in step S2, the inert gas includes argon, nitrogen, and combinations thereof.
In some embodiments, in step S2, the volume ratio of methanol to the mixed solution is from 1:100 to 1: 10.
In some embodiments, in step S2, an inert gas is introduced at 20-80 mL/min.
In some embodiments, in step S3, the ratio of the volume of the reaction solution to the volume of the reaction vessel is from 1:1 to 1: 5.
In some embodiments, pure carbon dioxide is passed in step S3 at 50-150mL/min for 2-10 min.
In some embodiments, in step S4, the temperature increase is a temperature programmed; preferably, the temperature is raised to a reaction temperature of 80-160 ℃; preferably, the speed of temperature programming is 5-10 ℃/min; preferably, the reaction time is 8 to 24 hours.
In some embodiments, in step S5, centrifugation is performed at 10000-.
In some embodiments, in step (1), the organic solvent is selected from N, N-dimethylformamide, N-methylpyrrolidone, derivatives thereof, or any combination thereof.
In some embodiments, in step (1), the alcoholic solvent is selected from C1-6Alcohols, preferably methanol, ethanol and their derivatives or any combination thereof.
In some embodiments, in step (1), the volume ratio of alcoholic solvent to organic solvent is from 1:1 to 6: 1.
In some embodiments, in step (1), the stirring is performed using a magnetic stirrer at a rotation speed of 1000-4000r/min for a time period of 10 minutes to 1 hour.
In some embodiments, in step (2), the surfactant is cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, polyvinyl pyrrolidone, sodium oleate, or any combination thereof.
In some embodiments, in step (2), the molar ratio of copper acetylacetonate to surfactant is from 6:1 to 8: 1.
In some embodiments, in step (2), the stirring is performed using a magnetic stirrer at a rotation speed of 1000-4000r/min for a time period of 10 minutes to 1 hour.
In some embodiments, in step (3), the ratio of the volume of the reaction solution to the volume of the polytetrafluoroethylene reaction vessel is from 1:2 to 1: 4.
In some embodiments, in step (3), the warming is a temperature programmed to the reaction temperature; preferably, the heating rate is 5-10 ℃/min; preferably, the reaction time is 6 to 12 hours.
In some embodiments, in step (4), the washing is performed by washing with deionized water until the pH of the supernatant is 7, and then washing with absolute ethanol twice.
In some embodiments, in step (4), the drying is treatment at 60-80 ℃ for 8-24 hours.
The invention has the beneficial effects that: according to the invention, the copper/cuprous oxide nanosheet catalyst is used for directly synthesizing dimethyl carbonate from carbon dioxide and methanol, the reaction activity of the catalyst is enhanced in a heterojunction mode, and the contact area with a reactant is enhanced through the shape of the nanosheet, so that the practical application of the product is facilitated.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows a scanning electron microscopy analysis of the catalyst of example 1;
FIG. 2 shows a scanning electron microscopy analysis of the catalyst of example 2;
FIG. 3 shows a nuclear magnetic resonance carbon spectrum analysis of the product of example 3;
figure 4 shows a graph of nmr hydrogen spectroscopy analysis of the product of example 4.
Detailed Description
The following describes embodiments of the present invention in detail. The embodiments described by referring to the drawings are exemplary only for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Example 1
The copper/cuprous oxide heterojunction nanosheet catalyst is prepared by the following steps:
(1) adding 30mL of N, N-dimethylformamide into 60mL of ethanol, and uniformly stirring to obtain a mixed solution of ethanol and N, N-dimethylformamide;
(2) adding 8mmol of copper acetylacetonate and 1mmol of hexadecyl trimethyl ammonium bromide into the mixed solution obtained in the step (1), and violently stirring for 30 minutes at the rotating speed of 1000r/min to obtain a reaction solution;
(3) transferring 50mL of the reaction solution obtained in the step (2) into a 50mL polytetrafluoroethylene reaction kettle, sealing, heating to 100 ℃ at a speed of 5 ℃/min, and reacting for 8 hours to obtain a product;
(4) washing with water and ethanol for 3 times respectively, drying in a vacuum oven at 60 ℃ for 12 hours, and crushing and dispersing in a mortar to obtain the copper/cuprous oxide heterojunction nanosheet catalyst.
The morphology, namely the Scanning Electron Microscope (SEM) analysis image, of the nanosheet catalyst powder is shown in FIG. 1. The obtained copper/cuprous oxide heterojunction nanosheet catalyst has only one shape and is in a nanosheet shape.
Example 2
The copper/cuprous oxide heterojunction nanosheet catalyst is prepared by the following steps:
(1) adding 10mL of N, N-dimethylformamide into 30mL of ethanol, and uniformly stirring to obtain a mixed solution of ethanol and N, N-dimethylformamide;
(2) adding 6mmol of copper acetylacetonate and 1mmol of hexadecyl trimethyl ammonium bromide into the mixed solution obtained in the step (1), and violently stirring for 30 minutes at the rotating speed of 1000r/min to obtain a reaction solution;
(3) transferring 50mL of the reaction solution obtained in the step (2) into a 50mL polytetrafluoroethylene reaction kettle, sealing, heating to 120 ℃ at the speed of 5 ℃/min, and reacting for 10 hours to obtain a product;
(4) washing with water and ethanol for 3 times respectively, drying in a vacuum oven at 60 ℃ for 12 hours, and crushing and dispersing in a mortar to obtain a copper/cuprous oxide heterojunction nanosheet catalyst;
the morphology, i.e. Scanning Electron Microscope (SEM) analysis, of the nanosheet catalyst powder is shown in fig. 2. Thus, only one morphology of the obtained oxygen vacancy-containing bismuth oxide nanosheet catalyst is nanosheet-shaped.
Example 3
The method for generating dimethyl carbonate by thermally catalyzing methanol and carbon dioxide comprises the following steps:
s1, adding 0.5g of copper/cuprous oxide heterojunction nanosheet catalyst (example 1) into 50ml of acetonitrile, and violently stirring to obtain a mixed solution;
s2, adding 0.5mL of methanol into the mixed solution obtained in the step S1, and introducing argon at a rate of 80mL/min to remove dissolved oxygen to obtain a reaction solution;
s3, transferring the reaction liquid in the step S2 to a 100mL closed autoclave, introducing pure carbon dioxide at a flow rate of 150mL/min, and continuing for 10min to remove upper air in the autoclave;
s4, under the stirring condition, keeping the pressure of carbon dioxide in the autoclave at 0.2Mp, isolating air, heating to 160 ℃, keeping for 12 hours, and centrifuging to obtain a supernatant to obtain a product.
The NMR analysis of the product is shown in FIG. 3, and it can be seen that the product obtained is dimethyl carbonate only, and the selectivity is 100%. This demonstrates that the method has good repeatability.
Example 4
The method for generating dimethyl carbonate by thermally catalyzing methanol and carbon dioxide comprises the following steps:
s1, adding 0.3g of copper/cuprous oxide heterojunction nanosheet catalyst (example 2) into 30ml of acetonitrile, and violently stirring to obtain a mixed solution;
s2, adding 0.5mL of methanol into the mixed solution obtained in the step S1, and introducing nitrogen at a rate of 20mL/min to remove dissolved oxygen to obtain a reaction solution;
s3, transferring the reaction liquid in the step S2 to a 100mL closed autoclave, introducing pure carbon dioxide at a flow rate of 50mL/min, and continuing for 2min to remove upper air in the autoclave;
s4, under the stirring condition, keeping the pressure of carbon dioxide in the autoclave at 0.1Mp, isolating air, heating to 150 ℃, keeping for 8 hours, centrifuging and taking supernatant to obtain a product.
The nmr analysis of the product obtained is shown in fig. 4, and it can be seen that the product obtained is only dimethyl carbonate, with a selectivity of 100% and a yield of 32%. This demonstrates that the method has good repeatability.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (31)

1. A method for generating dimethyl carbonate by using a copper/cuprous oxide heterojunction nanosheet catalyst through thermocatalysis comprises the following steps:
s1, adding a copper/cuprous oxide heterojunction nanosheet catalyst into an organic solvent, and violently stirring to obtain a mixed solution;
s2, adding methanol into the mixed solution obtained in the step S1, and introducing inert gas to obtain a reaction solution;
s3, transferring the reaction liquid obtained in the step S2 to a closed high-pressure kettle, and introducing pure carbon dioxide;
s4, keeping the carbon dioxide in the autoclave at the pressure of 0.1-10MPa under the condition of stirring, isolating the air, heating to the reaction temperature for reaction,
s5, centrifuging and taking supernatant to obtain a product;
wherein the copper/cuprous oxide heterojunction nanosheet catalyst is prepared by the following steps:
(1) adding an organic solvent into an alcohol solvent, and uniformly stirring to obtain a mixed solution;
(2) adding copper acetylacetonate and a surfactant into the mixed solution obtained in the step (1), and violently stirring to obtain a reaction solution;
(3) transferring the reaction liquid in the step (2) into a polytetrafluoroethylene reaction kettle, sealing, and heating to 100-200 ℃ to obtain a product;
(4) and washing, drying and grinding the product to obtain the copper/cuprous oxide heterojunction nanosheet catalyst.
2. The method of claim 1, wherein in step S1, the organic solvent comprises cyclohexane, acetonitrile, n-hexane, benzene, or a combination thereof.
3. The method of claim 1, wherein in step S1, the ratio of the copper/cuprous oxide heterojunction nanosheet catalyst to the organic solvent is 0.002-0.1 g/mL.
4. The method of claim 1, wherein in step S1, the stirring is selected from magnetic stirring or mechanical stirring.
5. The method as claimed in claim 1, wherein in step S1, the stirring rate is 100-1000 r/min.
6. The method of claim 1, wherein in step S2, the inert gas comprises argon, nitrogen, or a combination thereof.
7. The method of claim 1, wherein in step S2, the volume ratio of methanol to the mixed solution is 1:100 to 1: 10.
8. The method of claim 1, wherein in step S2, the inert gas is introduced at 20-80 mL/min.
9. The method of claim 1, wherein in step S3, the ratio of the volume of the reaction solution to the volume of the reaction kettle is 1:1-1: 5.
10. The method as claimed in claim 1, wherein pure carbon dioxide is introduced at 50-150mL/min for 2-10min in step S3.
11. The method according to claim 1, wherein in step S4, the temperature rise is a temperature programmed rise.
12. The method of claim 1, wherein in step S4, the temperature is raised to a reaction temperature of 80-160 ℃.
13. The method of claim 1, wherein in step S4, the temperature programming rate is 5-10 ℃/min.
14. The method of claim 1, wherein in step S4, the reaction time is 8-24 hours.
15. The method of claim 1, wherein in step S4, the stirring is selected from magnetic stirring or mechanical stirring.
16. The method as claimed in claim 1, wherein the stirring rate is 100-.
17. The method as claimed in claim 1, wherein in step S5, centrifugation is performed at a rotation speed of 10000-.
18. The method according to claim 1, wherein in step (1), the organic solvent is selected from N, N-dimethylformamide, N-methylpyrrolidone, or any combination thereof.
19. The process according to claim 1, wherein in step (1), the alcoholic solvent is selected from C1-6An alcohol or any combination thereof.
20. The process according to claim 1, wherein in step (1), the alcoholic solvent is selected from methanol, ethanol or any combination thereof.
21. The method according to claim 1, wherein in step (1), the volume ratio of the alcohol solvent to the organic solvent is 1:1 to 6: 1.
22. The method as claimed in claim 1, wherein in step (1), the stirring is performed by using a magnetic stirrer at a rotation speed of 1000-.
23. The method of claim 1, wherein in step (2), the surfactant is cetyl trimethylammonium bromide, dodecyl trimethylammonium bromide, polyvinylpyrrolidone, sodium oleate, or any combination thereof.
24. The method of claim 1, wherein in step (2), the molar ratio of copper acetylacetonate to surfactant is from 6:1 to 8: 1.
25. The method as claimed in claim 1, wherein in step (2), the stirring is performed by using a magnetic stirrer at a rotation speed of 1000-.
26. The method of claim 1, wherein in step (3), the volume ratio of the reaction solution to the polytetrafluoroethylene reaction vessel is 1:2 to 1: 4.
27. The method of claim 1, wherein in step (3), the temperature increase is a temperature programmed to the reaction temperature.
28. The method as claimed in claim 1, wherein, in the step (3), the temperature rising rate is 5 to 10 ℃/min.
29. The method according to claim 1, wherein in step (3), the reaction time is 6 to 12 hours.
30. The method according to claim 1, wherein in the step (4), the washing is performed by washing with deionized water until the pH value of the supernatant is 7, and then washing with absolute ethyl alcohol twice.
31. The method according to claim 1, wherein in the step (4), the drying is a treatment at 60 to 80 ℃ for 8 to 24 hours.
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