CN116535382A - Method for catalytic conversion of carbon dioxide by using ionic liquid - Google Patents
Method for catalytic conversion of carbon dioxide by using ionic liquid Download PDFInfo
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- CN116535382A CN116535382A CN202310055572.9A CN202310055572A CN116535382A CN 116535382 A CN116535382 A CN 116535382A CN 202310055572 A CN202310055572 A CN 202310055572A CN 116535382 A CN116535382 A CN 116535382A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 83
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 60
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 150000002924 oxiranes Chemical class 0.000 claims description 6
- CSGQJHQYWJLPKY-UHFFFAOYSA-N CITRAZINIC ACID Chemical compound OC(=O)C=1C=C(O)NC(=O)C=1 CSGQJHQYWJLPKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- BXHCJLRTXPHUGH-UHFFFAOYSA-N 2-oxo-1h-pyridine-4-carboxylic acid Chemical compound OC(=O)C=1C=CNC(=O)C=1 BXHCJLRTXPHUGH-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 2
- MRXPNWXSFCODDY-UHFFFAOYSA-N 2-methyl-2-phenyloxirane Chemical compound C=1C=CC=CC=1C1(C)CO1 MRXPNWXSFCODDY-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 3
- 231100000086 high toxicity Toxicity 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- -1 carbonate compound Chemical class 0.000 description 9
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 7
- 229940018557 citraconic acid Drugs 0.000 description 7
- 238000004445 quantitative analysis Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 2
- DEZDKWLZZLEVST-UHFFFAOYSA-N tetrabutyl(hydroxy)-$l^{5}-phosphane Chemical compound CCCCP(O)(CCCC)(CCCC)CCCC DEZDKWLZZLEVST-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 description 1
- CSGQJHQYWJLPKY-UHFFFAOYSA-M 2-hydroxy-6-oxo-1h-pyridine-4-carboxylate Chemical compound OC1=CC(C([O-])=O)=CC(=O)N1 CSGQJHQYWJLPKY-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0289—Sulfur
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
Abstract
The application discloses a method for catalytically converting carbon dioxide by using ionic liquid, belongs to the field of catalytic chemistry, and solves the problems of low conversion efficiency, poor environmental friendliness and high toxicity in the prior art. The technical scheme of the application includes that ionic liquid is used as a catalyst to catalyze the synthesis reaction of synthesizing carbonic ester from carbon dioxide and epoxy compound; the ionic liquid consists of a cation and an anion, and the structural formula of the anion and the cation is as follows：
Description
Technical Field
The invention relates to a method for catalytically converting carbon dioxide by using ionic liquid, belonging to the field of catalytic chemistry.
Background
Carbon dioxide is the main gas causing global climate warming, and with the development of steel, electric power and chemical industry, the carbon dioxide emission is gradually increased, so that the global climate warming, the greenhouse effect exacerbation and the like are caused. The increased carbon dioxide emissions can also cause sea level to rise, glaciers to melt, threaten the survival of wild animals, and even affect the balance of the ecosystem. The traditional technology for converting carbon dioxide has the defects of high cost, harsh reaction conditions and the like, so that how to green color temperature and convert carbon dioxide become a problem to be solved in the 21 st century.
Carbon dioxide can be used for synthesizing carbonate compounds, wherein the carbon dioxide reacts with epoxide under the action of a catalyst to generate the carbonate compounds, the carbonate compounds can be used in a plurality of fields such as electrochemistry, phosgene substitutes, preservatives and the like, and the preparation of the carbonate compounds by using the carbon dioxide is an ideal method for consuming and converting the carbon dioxide.
The traditional method for preparing carbonic ester adopts alcohol or phenols to react with phosgene, and the phosgene has high toxicity. In the prior art, the ionic liquid is used for synthesizing and catalyzing the carbonate compound, such as a method for synthesizing the cyclic carbonate by catalyzing carbon dioxide by using the eutectic ionic liquid disclosed in CN201910343393.9, namely, the eutectic ionic liquid is used for synthesizing and catalyzing the carbonate compound, but in the technical scheme, the eutectic ionic liquid and a product are not easy to separate, the eutectic structure of the eutectic ionic liquid is easy to be damaged, and the eutectic ionic liquid is difficult to recycle.
Disclosure of Invention
The invention provides a method for catalytically converting carbon dioxide by using ionic liquid, which has the advantages of easy separation of ionic liquid and products, stable structure, recycling, mild condition, environment friendliness, high efficiency, low cost, high atom utilization rate and high practical application value.
In order to solve the technical problems, the technical scheme adopted by the invention is that the method for catalytically converting carbon dioxide by using ionic liquid is characterized by comprising the following steps of: using ionic liquid as a catalyst to catalyze the synthesis reaction of synthesizing carbonic ester by carbon dioxide and an epoxy compound; the ionic liquid is obtained by mixing and reacting hydroxide corresponding to cations and acid corresponding to anions;
the cationic structure of the ionic liquid is as follows:
the anionic structural formula of the ionic liquid is as follows:
optimally, the method for catalytically converting carbon dioxide by using ionic liquid comprises the step of preparing an epoxy compound with different substituents; the structural formula of the epoxy compound containing different substituents is as follows:
optimally, according to the method for catalytically converting carbon dioxide by using the ionic liquid, the ionic liquid is obtained by mixing and reacting citrazinic acid with tetrabutyl phosphonium hydroxide and then drying at 80 ℃ for 48 hours, or the ionic liquid is obtained by mixing and reacting 2-hydroxy-4-picolinic acid with tetrabutyl phosphonium hydroxide and then drying at 80 ℃ for 48 hours.
Optimally, according to the method for catalytically converting carbon dioxide by using the ionic liquid, the ionic liquid is prepared by stirring and mixing hydroxide corresponding to cations and acid corresponding to anions according to a molar ratio; in the stirring and mixing, the temperature is between 30 and 90 ℃, and the stirring and mixing time is 10 hours.
Preferably, in the method for catalytically converting carbon dioxide by using the ionic liquid, the molar ratio of the ionic liquid to the epoxide is 10 millimoles to 1 millimole to 10 millimoles to 2 millimoles.
Preferably, the above method for catalytic conversion of carbon dioxide using ionic liquid, wherein the reaction of the epoxy compound and the catalytic conversion of carbon dioxide into carbonate is carried out under constant temperature magnetic stirring.
Preferably, in the method for catalytically converting carbon dioxide by using the ionic liquid, the reaction time of catalytically converting the epoxy compound and the carbon dioxide into the carbonate by using the ionic liquid is 24 hours.
Preferably, in the method for catalytically converting carbon dioxide by using the ionic liquid, the reaction substrate used in the reaction of catalytically converting the epoxy compound and the carbon dioxide into the carbonate by using the ionic liquid is any one of ethylene oxide, propylene oxide, epichlorohydrin, bromopropane, decane oxide, 2-phenyl propylene oxide and cyclohexane oxide.
Preferably, in the method for catalytically converting carbon dioxide by using the ionic liquid, the reaction of catalytically converting the epoxy compound and the carbon dioxide into the carbonate by using the ionic liquid is performed at normal temperature and normal pressure.
In the technical scheme of the application, the method can make up for the defects of the current carbon dioxide conversion technology, the ionic liquid and the product are easy to separate, the operability is improved, and the method is favorable for practical popularization. And the ionic liquid has high stability, is not easy to damage, can be recycled, and has low cost and high utilization rate. And the scheme of the application is mild in condition, green and efficient.
Detailed Description
The technical features of the present invention are further described below in conjunction with specific embodiments.
Example 1
The invention provides a method for catalytically converting carbon dioxide by ionic liquid, wherein the reaction equation of epoxide containing different substituent groups and carbon dioxide to generate carbonic ester is as follows:
in this example, the specific steps of the reaction are:
1) Stirring and mixing hydroxide corresponding to cations and acid corresponding to anions according to a mole ratio under a certain condition, and drying to obtain ionic liquid;
2) The ionic liquid prepared in the step 1) is subjected to catalytic conversion of carbon dioxide under a certain condition;
3) And 2) obtaining the catalytic conversion efficiency by using the nuclear magnetic quantitative analysis method of the carbonic acid compound generated in the step 2).
More specifically, the method comprises the following steps:
in the step 1), the citraconic acid and the tetrabutyl phosphonium hydroxide with the molar ratio of 1:3 are added into a reaction bottle to be sealed, and then are mixed and stirred for 10 hours at 50 ℃ to form a mixture of the tetrabutyl phosphonium citraconic acid type ionic liquid and water.
And drying the mixture of the ionic liquid and water for 48 hours at 80 ℃ by using a vacuum drying oven to obtain the pure tetrabutyl phosphonium citrazinate ionic liquid.
In the step 2), 10 millimoles of 1, epoxy chloropropane and 1 millimole of the citraconic acid type ionic liquid and a magnet are added into a Schlenk glass three-way pipe, one end of the Shi Laike three-way pipe is connected with a circulating water type multipurpose vacuum pump to be washed 3 times, 0.1MPa of carbon dioxide is filled, after the reaction is carried out for 24 hours under the magnetic stirring condition of normal temperature and 1000 revolutions per minute, heating and stirring are stopped, cooling is carried out to the room temperature, and unreacted carbon dioxide is slowly discharged.
In the step 3), the nuclear magnetism quantitative analysis method is adopted to obtain the catalytic conversion efficiency of 90%.
Example 2
The specific steps of this embodiment include:
in the step 1), the citraconic acid and the tetrabutyl phosphonium hydroxide with the molar ratio of 1:3 are added into a reaction bottle to be sealed, and then are mixed and stirred for 10 hours at 50 ℃ to form a mixture of the tetrabutyl phosphonium citraconic acid type ionic liquid and water.
And drying the mixture of the ionic liquid and water for 48 hours at 80 ℃ by using a vacuum drying oven to obtain the pure tetrabutyl phosphonium citrazine salt ionic liquid.
In the step 2), 10 millimoles of 1, epoxy chloropropane and 1 millimole of the citraconic acid type ionic liquid and a magnet are added into a Schlenk glass three-way pipe, one end of the Shi Laike three-way pipe is connected with a circulating water type multipurpose vacuum pump to be washed 3 times, 0.1MPa of carbon dioxide is filled, after the reaction is carried out for 24 hours under the magnetic stirring condition of normal temperature and 1000 revolutions per minute, heating and stirring are stopped, cooling is carried out to the room temperature, and unreacted carbon dioxide is slowly discharged.
In the step 3), the catalytic conversion efficiency is 94% by adopting a nuclear magnetism quantitative analysis method.
Example 3
The specific steps of this embodiment include:
in the step 1), 2-hydroxy-4-picolinic acid and tetrabutyl phosphorus hydroxide with the molar ratio of 1:3 are added into a reaction bottle to be sealed, and then are mixed and stirred for 10 hours at 50 ℃ to form a mixture of tetrabutyl phosphorus citraconic acid type ionic liquid and water.
And drying the mixture of the ionic liquid and water for 48 hours at 80 ℃ by using a vacuum drying oven to obtain the pure tetrabutyl phosphonium citrazine salt ionic liquid.
In the step 2), 10 millimoles of 1, epoxy chloropropane and 1 millimole of the citraconic acid type ionic liquid and a magnet are added into a Schlenk glass three-way pipe, one end of the Shi Laike three-way pipe is connected with a circulating water type multipurpose vacuum pump to be washed 3 times, 0.1MPa of carbon dioxide is filled, after the reaction is carried out for 24 hours under the magnetic stirring condition of normal temperature and 1000 revolutions per minute, heating and stirring are stopped, cooling is carried out to the room temperature, and unreacted carbon dioxide is slowly discharged.
In the step 3), the nuclear magnetism quantitative analysis method is adopted to obtain the catalytic conversion efficiency of 84 percent.
Example 4
The specific steps of this embodiment include:
in the step 1), 2-hydroxy-4-picolinic acid and tetrabutyl phosphorus hydroxide aqueous solution with the molar ratio of 1:3 are added into a reaction bottle to be sealed, and then are mixed and stirred for 10 hours at 50 ℃ to form a mixture of tetrabutyl phosphorus citraconic acid type ionic liquid and water.
And drying the mixture of the ionic liquid and water for 48 hours at 80 ℃ by using a vacuum drying oven to obtain the pure tetrabutyl phosphonium citrazine salt ionic liquid.
In the step 2), 10 millimoles of 1, epoxy bromopropane and 1 millimole of the citrazinic acid type ionic liquid and a magnet are added into a Schlenk glass three-way pipe, one end of the Shi Laike three-way pipe is connected with a circulating water type multipurpose vacuum pump for washing gas for 3 times, 0.1MPa of carbon dioxide is filled, after the reaction is carried out for 24 hours under the magnetic stirring condition of normal temperature and 1000 revolutions per minute, heating and stirring are stopped, cooling is carried out to the room temperature, and unreacted carbon dioxide is slowly discharged.
In the step 3), the nuclear magnetism quantitative analysis method is adopted to obtain the catalytic conversion efficiency of 82 percent.
Example 5
The specific steps of this embodiment include:
in the step 1), the aqueous solution of the citraconic acid and the tetrabutylphosphonium hydroxide with the molar ratio of 1:3 is added into a reaction bottle to be sealed, and then the mixture of the tetrabutylphosphonium citraconic acid type ionic liquid and water is formed after mixing and stirring for 10 hours at 50 ℃.
And drying the mixture of the ionic liquid and water for 48 hours at 80 ℃ by using a vacuum drying oven to obtain the pure tetrabutyl phosphonium citrazine salt ionic liquid.
In the step 2), 10 millimoles of epoxy chloropropane and 2 millimoles of the citrazinic acid type ionic liquid and a magnet are added into a Schlenk glass three-way pipe, one end of the Shi Laike three-way pipe is connected with a circulating water type multipurpose vacuum pump to be washed with air for 3 times, 0.1MPa of carbon dioxide is filled, after the reaction is carried out for 24 hours under the magnetic stirring conditions of normal temperature and 1000 revolutions per minute, heating and stirring are stopped, cooling is carried out to the room temperature, and unreacted carbon dioxide is slowly emptied.
In the step 3), the nuclear magnetism quantitative analysis method is adopted to obtain the catalytic conversion efficiency of 96%.
Example 6
The specific steps of this embodiment include:
in the step 1), the aqueous solution of the citraconic acid and the tetrabutylphosphonium hydroxide with the molar ratio of 1:3 is added into a reaction bottle to be sealed, and then the mixture of the tetrabutylphosphonium citraconic acid type ionic liquid and water is formed after mixing and stirring for 10 hours at 50 ℃.
And drying the mixture of the ionic liquid and water for 48 hours at 80 ℃ by using a vacuum drying oven to obtain the pure tetrabutyl phosphonium citrazine salt ionic liquid.
In the step 2), 10 millimoles of epoxy bromopropane and 2 millimoles of the citrazinic acid type ionic liquid and a magnet are added into a Schlenk glass three-way pipe, one end of the Shi Laike three-way pipe is connected with a circulating water type multipurpose vacuum pump for washing gas for 3 times, 0.1MPa of carbon dioxide is filled, after the reaction is carried out for 24 hours under the magnetic stirring condition of normal temperature and 1000 revolutions per minute, heating and stirring are stopped, cooling is carried out to the room temperature, and unreacted carbon dioxide is slowly discharged.
In the step 3), the nuclear magnetism quantitative analysis method is adopted to obtain the catalytic conversion efficiency of 98%.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that various changes, modifications, additions and substitutions can be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (9)
1. A method for catalytically converting carbon dioxide using an ionic liquid, characterized by: using ionic liquid as a catalyst to catalyze the synthesis reaction of synthesizing carbonic ester by carbon dioxide and an epoxy compound; the ionic liquid is obtained by mixing and reacting hydroxide corresponding to cations and acid corresponding to anions;
the cationic structure of the ionic liquid is as follows:
the anionic structural formula of the ionic liquid is as follows:
2. the method for catalytic conversion of carbon dioxide using ionic liquids according to claim 1, wherein: the epoxy compounds contain different substituents; the structural formula of the epoxy compound containing different substituents is as follows:
3. the method for catalytic conversion of carbon dioxide using ionic liquids according to claim 1, wherein: the ionic liquid is obtained by mixing and reacting citrazinic acid with tetrabutyl phosphonium hydroxide and then drying at 80 ℃ for 48 hours, or the ionic liquid is obtained by mixing and reacting 2-hydroxy-4-picolinic acid with tetrabutyl phosphonium hydroxide and then drying at 80 ℃ for 48 hours.
4. The method for catalytic conversion of carbon dioxide using ionic liquids according to claim 1, wherein: the ionic liquid is prepared by stirring and mixing hydroxide corresponding to cations and acid corresponding to anions according to a molar ratio; in the stirring and mixing, the temperature is between 30 and 90 ℃, and the stirring and mixing time is 10 hours.
5. The method for catalytic conversion of carbon dioxide using ionic liquids according to claim 1, wherein: the molar ratio of ionic liquid to epoxide is 10 millimoles to 1 millimole to 10 millimoles to 2 millimoles.
6. The method for catalytic conversion of carbon dioxide using ionic liquids according to claim 1, wherein: the reaction of the epoxide and carbon dioxide catalytic conversion to carbonate is carried out under constant temperature magnetic stirring.
7. The method for catalytic conversion of carbon dioxide using ionic liquids according to claim 1, wherein: the reaction time of the ionic liquid for catalytic conversion of the epoxide and carbon dioxide to carbonate is 24 hours.
8. The method for catalytic conversion of carbon dioxide using ionic liquids according to claim 1, wherein: in the reaction of the ionic liquid for catalytically converting the epoxy compound and the carbon dioxide into the carbonic ester, the reaction substrate is any one of ethylene oxide, propylene oxide, epichlorohydrin, bromopropane, decane, 2-phenyl propylene oxide and cyclohexene oxide.
9. The method for catalytic conversion of carbon dioxide using ionic liquids according to claim 1, wherein: the reaction of the ionic liquid for catalytically converting the epoxy compound and the carbon dioxide into the carbonate is carried out at normal temperature and normal pressure.
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