CN114643075A - Catalyst for synthesizing alkylene carbonate, preparation method and application thereof - Google Patents
Catalyst for synthesizing alkylene carbonate, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for synthesizing alkylene carbonate, a preparation method and application thereof. The catalyst has a composition of mMXy/nR[N‑P]Wherein, MXyIs an inorganic metal salt, R[N‑P]Is an organic compound containing N-P group, m is MXyN is R[N‑P]Is prepared from (A) and (B)The number of moles. The preparation method of the catalyst comprises the following steps: (1) dispersing metal salt in a first solvent, stirring and heating to obtain a mixed solution A; (2) dissolving an organic matter containing N-P groups in a second solvent to obtain a solution B; (3) mixing the mixed solution A and the solution B, and stirring for reaction; (4) and (4) filtering, washing and drying the reaction mixed liquid obtained in the step (3) to obtain the catalyst. The catalyst of the invention is used in the reaction of synthesizing alkylene carbonate from alkylene oxide and carbon dioxide, and has good activity and selectivity.
Description
Technical Field
The invention relates to a catalyst for synthesizing alkylene carbonate by using alkylene oxide and carbon dioxide, a preparation method and application thereof.
Background
Alkylene carbonates such as ethylene carbonate and propylene carbonate are an organic chemical raw material having a wide range of uses, and are widely used in industry as solvents and diluents. The ethylene carbonate can be used as a solvent in the aspects of spinning, printing, polymer synthesis and electrochemistry, and can also be used as a raw material of cosmetics and medicines and an intermediate of corresponding dihydric alcohol.
Alkylene carbonates are generally prepared industrially by reacting carbon dioxide with the corresponding alkylene oxide over a catalyst. Many catalysts have been found to have catalytic effects on this reaction, such as transition metal complexes, main group element complexes, quaternary ammonium salts, quaternary phosphonium salts and alkali metal salts, ionic liquids, supercritical carbon dioxide, and like catalytic systems.
CN1995032A discloses a method for preparing cyclic carbonate, wherein ionic liquid 1-methyl-3-butylimidazole bromide is used as catalyst, and the yield of Ethylene Carbonate (EC) obtained by reaction at 100 ℃ and 2.0MPa is 92.2%. CN101108843A discloses a method for synthesizing cyclic carbonate ester in aqueous system, wherein when bidentate ionic liquid 1, 2-dimethyl imidazole ethyl bromide and hydroxyl ionic liquid 1- (2-hydroxy-ethyl) -3-methyl imidazole bromine are used as catalysts to synthesize cyclic carbonate ester EC, the yield of EC is 93% and 99.5% respectively. CN1631886A discloses a method for synthesizing cyclic carbonate, in which ZnCl is used2As a catalyst, ionic liquid 1-methyl-3-butylimidazole bromide salt is used as a cocatalyst, the reaction is carried out for 1 hour at 100 ℃, and the selectivity of the product is 99 percent. The above methods all have a problem of low catalytic activity.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst for synthesizing alkylene carbonate and a preparation method and application thereof, aiming at solving the problem of low activity of a homogeneous catalyst in the prior art. The catalyst is used in the reaction of synthesizing alkylene carbonate with alkylene oxide and carbon dioxide as raw materials, and has the characteristics of low catalyst consumption, high activity and good selectivity.
In a first aspect of the present invention there is provided a catalyst for the synthesis of alkylene carbonate from alkylene oxide and carbon dioxide, the catalyst having the composition according to the schematic formula mMXy/nR[N-P]Wherein, MXyIs an inorganic metal salt, R[N-P]Is an organic compound containing N-P group, m is MXyN is R[N-P]The number of moles of (a).
In the technical scheme, MXyIs metal salt, wherein M is metal, X is anion corresponding to the metal salt, and y is the value when the metal salt reaches valence state equilibrium.
In the above technical solution, preferably, in the catalyst, the metal (M) is at least one of copper, zinc, lithium, magnesium, cobalt, and nickel, and preferably at least one of copper, zinc, cobalt, and nickel. The metal salt (MX)y) Is selected from one or more of sulfate, nitrate or halide.
In the above technical solution, preferably, in the catalyst, the molar ratio of the inorganic metal salt to the N — P bond-containing organic compound, that is, m: n ranges from 1: 0.5 to 10.0, preferably 1: 0.8-8.0.
In the above technical scheme, R[N-P]The N-P group-containing organic compound is at least one selected from the group consisting of bis (triphenylphosphine) ammonium chloride, morpholinophosphoryl dichloride, chlorodimorpholinylphosphine, tris (4-morpholino) phosphine oxide, morpholinophosphonic acid diphenyl ester, N, N-2(2 phenylphosphoryl) -2-pyridylamine, and N, N-2 (phenylphosphino) -propylamine, and preferably at least one selected from the group consisting of bis (triphenylphosphine) ammonium chloride, morpholinophosphoryl dichloride, and chlorodimorpholinylphosphine.
The second aspect of the present invention provides a method for preparing the above catalyst, comprising the following steps:
(1) dispersing metal salt in a first solvent, stirring and heating to obtain a mixed solution A;
(2) dissolving an organic matter containing N-P groups in a second solvent to obtain a solution B;
(3) mixing the mixed solution A and the solution B, and stirring for reaction;
(4) and (4) filtering, washing and drying the reaction mixed liquid obtained in the step (3) to obtain the catalyst.
In the above technical solution, preferably, the first solvent and the second solvent are each independently selected from one or more of toluene, methanol, ethanol, N-propanol, N-butanol, isobutanol, tert-butanol, toluene, dichloromethane, chloroform, an amide (such as N, N-dimethylformamide), and an ether (such as tetrahydrofuran). The first solvent and the second solvent may be the same or different.
In the above technical solution, the metal is at least one of copper, zinc, lithium, magnesium, cobalt, and nickel, and the metal salt is at least one selected from sulfate, nitrate, and halide.
In the above technical solution, the conditions of stirring and heating in step (1) are as follows: the temperature is 0-150 ℃.
In the above technical scheme, the reaction conditions in step (3) are as follows: the reaction temperature is 0-150 ℃, and the reaction time is 1-10 h.
In the above technical scheme, the filtering, washing and drying in step (4) can adopt a conventional method, and the washing can adopt ethanol washing. The main purpose of said drying is to remove the organic solvent, preferably by vacuum drying.
In a third aspect of the present invention, there is provided a process for the synthesis of alkylene carbonate from alkylene oxide and carbon dioxide, wherein the above-mentioned catalyst provided in the first or second aspect of the present invention is used.
In the technical scheme, alkylene oxide and carbon dioxide are used as raw materials, and the raw materials are contacted with the catalyst under the reaction condition to react to generate the alkylene carbonate.
In the above technical scheme, the alkylene oxide is one or more of ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin.
In the above technical scheme, the reaction temperature is preferably 60-180 ℃, and preferably 70-150 ℃.
In the above technical scheme, the reaction pressure is preferably 0.1-10.0MPa, preferably 1.0-8.0 MPa.
In the above technical solution, preferably, the mass ratio of the catalyst to the alkylene oxide is 0.001-0.1: 1, preferably 0.001 to 0.05: 1.
in the technical scheme, the reaction time is preferably 0.5-48h, and preferably 1-36 h.
The catalyst of the invention has the following technical effects:
1. the catalyst of the invention adopts a compound containing N-P bonds, enhances the ring-opening capability of alkylene oxide, is matched with inorganic metal salt, has good activity and selectivity when being used as a catalyst for synthesizing alkylene carbonate by alkylene oxide and carbon dioxide (especially ethylene carbonate synthesized by the addition reaction of ethylene oxide and carbon dioxide), and improves the conversion rate of alkylene oxide and the selectivity of alkylene carbonate.
2. The catalyst is used in the reaction of synthesizing ethylene carbonate by the addition reaction of ethylene oxide and carbon dioxide, the conversion rate of ethylene oxide can reach more than 99.5%, the selectivity of ethylene carbonate can reach more than 99.6%, and remarkable technical effect is achieved.
Detailed Description
The invention is further illustrated by the following examples. It is to be noted that the following examples are provided for the purpose of further illustrating the present invention and are not to be construed as limiting the scope of the present invention.
[ example 1 ]
Dispersing 1.36g of zinc chloride in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 4.78g of chlorodimorpholinyl phosphine, reacting at 40 ℃ for 5h, cooling the reaction to room temperature, vacuumizing to volatilize the solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst S1.
[ example 2 ]
Dispersing 2.25g of zinc bromide in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 18.8g of bis (triphenylphosphine) ammonium chloride, reacting at 35 ℃ for 8h, cooling the reaction to room temperature, vacuumizing to volatilize a solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst S2.
[ example 3 ] A method for producing a polycarbonate
Dispersing 2.25g of zinc bromide in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 5.7g of morpholinophosphoryl dichloride, reacting at 40 ℃ for 5 hours, cooling the reaction to room temperature, vacuumizing to volatilize the solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst S3.
[ example 4 ]
Dispersing 2.19g of nickel bromide in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 18.8g of bis (triphenylphosphine) ammonium chloride, reacting at 40 ℃ for 5h, cooling the reaction to room temperature, vacuumizing to volatilize a solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst S4.
[ example 5 ]
Dispersing 1.62g of zinc sulfate in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 18.8g of bis (triphenylphosphine) ammonium chloride, reacting at 40 ℃ for 5 hours, cooling the reaction to room temperature, vacuumizing to volatilize a solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst S5.
[ example 6 ]
Dispersing 1.3g of cobalt chloride in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 9.6g of chlorodimorpholinyl phosphine, reacting at 40 ℃ for 5h, cooling the reaction to room temperature, vacuumizing to volatilize the solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst S6.
[ example 7 ] A method for producing a polycarbonate
Dispersing 2.23g of copper bromide in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of N, N-dimethylformamide solution containing 4.78g of chlorodimorpholinyl phosphine, reacting at 90 ℃ for 5h, cooling the reaction to room temperature, vacuumizing to volatilize a solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst S7.
[ example 8 ]
Dispersing 1.36g of zinc chloride in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 14.4g of chlorodimorpholinyl phosphine, reacting at 50 ℃ for 10h, cooling the reaction to room temperature, vacuumizing to volatilize the solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst S8.
Comparative example 1
Dispersing 1.36g of zinc chloride in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 1.64g of 1-methylimidazole, reacting at 40 ℃ for 5h, cooling the reaction to room temperature, vacuumizing to volatilize a solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst C1.
Comparative example 2
Dispersing 2.25g of zinc bromide in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 8.46g of triphenylphosphine, reacting at 40 ℃ for 5h, cooling the reaction to room temperature, vacuumizing to volatilize the solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain the catalyst C2.
[ COMPARATIVE EXAMPLE 3 ]
Dispersing 2.25g of zinc bromide in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 3.7 tri-n-butylamine, reacting at 40 ℃ for 5h, cooling the reaction to room temperature, vacuumizing to volatilize a solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain a catalyst C3.
Comparative example 4
Dispersing 2.25g of zinc bromide in 50mL of tetrahydrofuran solution, stirring and heating to reflux, adding 50mL of tetrahydrofuran solution containing 4.21g of triphenylphosphine and 0.82g of 1-methylimidazole, reacting at 40 ℃ for 5h, cooling the reaction to room temperature, vacuumizing to volatilize a solvent to obtain a solid sample, washing with excessive ethanol, and drying overnight to obtain a catalyst C4.
[ example 9 ] A method for producing a polycarbonate
The catalyst samples prepared in the above examples and comparative examples were used for the reaction of ethylene oxide and carbon dioxide, respectively, under the following conditions: under the protection of inert gas, 50.0 g of ethylene oxide and 0.2 g of catalyst are added into a 300 ml autoclave, and 3.0MPa of CO is charged2Heating to 120 deg.C, and charging CO2Maintaining the reaction pressure at 3.0MPa, taking a liquid sample after reacting for 2 hours, and analyzing on a chromatogram to obtain the conversion rate C of the ethylene oxideEOAnd ethylene carbonate selectivity SECThe results are shown in Table 1.
TABLE 1
| Test number | Catalyst type | Catalyst dosage per gram | Reaction pressure/MPa | CEO/％ | SEC/％ |
| 1 | S1 | 0.2 | 3.0 | 99.8 | 99.8 |
| 2 | S2 | 0.2 | 3.0 | 99.5 | 99.9 |
| 3 | S3 | 0.2 | 3.0 | 99.6 | 99.7 |
| 4 | S4 | 0.2 | 3.0 | 99.5 | 99.7 |
| 5 | S5 | 0.2 | 3.0 | 99.7 | 99.6 |
| 6 | S6 | 0.2 | 3.0 | 99.6 | 99.7 |
| 7 | S7 | 0.2 | 3.0 | 99.6 | 99.6 |
| 8 | S8 | 0.2 | 3.0 | 99.5 | 99.8 |
| 9 | C1 | 0.2 | 3.0 | 78.7 | 99.7 |
| 10 | C2 | 0.2 | 3.0 | 82.3 | 99.8 |
| 11 | C3 | 0.2 | 3.0 | 45.5 | 95.7 |
| 12 | C4 | 0.2 | 3.0 | 77.8 | 99.6 |
[ example 10 ]
The catalyst S1 prepared above was used for the reaction of propylene oxide and carbon dioxide under the following conditions: under the protection of inert gas, 50.0 g of propylene oxide and 0.2 g of catalyst are added into a 300 ml autoclave, and 3.0MPa CO is charged2Heating to 120 deg.C, and charging CO2And maintaining the reaction pressure at 3.0MPa, taking a liquid sample after reacting for 2 hours, and analyzing on a chromatogram to obtain the propylene oxide conversion rate of 99.7 percent and the propylene carbonate selectivity of 99.8 percent.
[ example 11 ]
The catalytic reaction of ethylene oxide and carbon dioxide was carried out in the same manner as in example 9 while varying the amount of the catalyst used, and the temperature and pressure of the reaction, and the reaction results were shown in Table 2.
TABLE 2 Effect of reaction conditions on catalyst Performance
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A catalyst for the synthesis of alkylene carbonate from alkylene oxide and carbon dioxide, wherein the catalyst has the composition of formula mMXy/nR[N-P]Wherein, MXyIs an inorganic metal salt, R[N-P]Is an organic compound containing N-P group, m is MXyN is R[N-P]The number of moles of (a).
2. The catalyst of claim 1, wherein: in the catalyst, the metal is at least one of copper, zinc, lithium, magnesium, cobalt and nickel, preferably at least one of copper, zinc, cobalt and nickel; the metal salt is selected from one or more of sulfate, nitrate or halide.
3. The catalyst of claim 1, wherein: in the catalyst, R[N-P]At least one selected from the group consisting of bis (triphenylphosphine) ammonium chloride, morpholinophosphoryl dichloride, chlorodimorpholinyl phosphine, tris (4-morpholino) phosphine oxide, morpholino phosphonic acid diphenyl ester, N, N-2(2 phenylphosphoryl) -2-pyridylamine, and N, N-2 (phenylphosphino) -propylamine, and preferably at least one selected from the group consisting of bis (triphenylphosphine) ammonium chloride, morpholinophosphoryl dichloride, chlorodimorpholinyl phosphine.
4. The catalyst of claim 1, wherein: in the catalyst, m: n ranges from 1: 0.5 to 10.0, preferably 1: 0.8-8.0.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, comprising the steps of:
(1) dispersing metal salt in a first solvent, stirring and heating to obtain a mixed solution A;
(2) dissolving an organic matter containing N-P groups in a second solvent to obtain a solution B;
(3) mixing the mixed solution A and the solution B, and stirring for reaction;
(4) and (4) filtering, washing and drying the reaction mixed liquid obtained in the step (3) to obtain the catalyst.
6. The method of claim 5, wherein: the first solvent and the second solvent are respectively and independently selected from one or more of toluene, methanol, ethanol, n-propanol, n-butanol, isobutanol, tert-butanol, toluene, dichloromethane, chloroform, amide and ether.
7. The method of claim 5, wherein: the reaction conditions in the step (3) are as follows: the reaction temperature is 0-150 ℃, and the reaction time is 1-10 h.
8. A method for synthesizing alkylene carbonate by alkylene oxide and carbon dioxide is characterized in that: a catalyst obtained by the use of the catalyst according to any one of claims 1 to 4 or the production method according to any one of claims 5 to 7.
9. The method of claim 8, wherein: the alkylene oxide is one or more of ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin.
10. The method of claim 8, wherein: the reaction temperature is 60-180 ℃; and/or the reaction pressure is 0.1-10.0 MPa; and/or the reaction time is 0.5-48 h; and/or the mass ratio of the catalyst to the alkylene oxide is 0.001-0.1: 1.
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| CN114643075B (en) | 2023-08-29 |
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