CN113912493A - Method for synthesizing dimethyl carbonate by catalyzing fluorine-containing calcium zirconium aluminum solid base - Google Patents
Method for synthesizing dimethyl carbonate by catalyzing fluorine-containing calcium zirconium aluminum solid base Download PDFInfo
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Abstract
The invention relates to a method for synthesizing dimethyl carbonate by catalyzing fluorine-containing calcium zirconium aluminum solid base. The method comprises the following steps: adding propylene carbonate, methanol and fluorine-containing calcium zirconium aluminum solid alkali into a reactor, and reacting for 0.5-1 h at 50-80 ℃ under stirring to obtain dimethyl carbonate; the preparation method of the fluorine-containing calcium zirconium aluminum solid alkali comprises the following steps: roasting fluorine-containing calcium zirconium aluminum hydrotalcite as a precursor at 400-800 ℃ for 3-8 h to obtain the product; the general structural formula of the fluorine-containing calcium zirconium aluminum hydrotalcite is as follows: a. the+ xCa2+ yZr2+ zAl3+ (1‑x‑y‑z)(OH2)(F‑)2(CO3 2‑)(1‑x‑y‑z)/2·mH2And O. The invention has the advantages of easily obtained raw materials, low price and good catalyst stabilityHigh activity, easy separation and repeated use, and high yield.
Description
Technical Field
The invention relates to a solid base catalyst, a preparation method and application thereof, in particular to a method for synthesizing dimethyl carbonate by using fluorine-containing calcium zirconium aluminum solid base catalyst.
Background
Dimethyl carbonate (DMC) is a symmetric organic carbonate which is non-toxic and harmless to the environment, and is mainly applied to organic synthetic solvents, in particular to lithium battery electrolyte solvents. Compared with the traditional lithium battery electrolyte solvent, the dimethyl carbonate has the advantages of improving the storage capacity of the battery, improving the stability and safety of the battery, prolonging the service life of the battery, improving the cold resistance of the lithium battery and widening the application of the lithium battery in the low-temperature field.
In recent years, a large number of patents related to the production and application of dimethyl carbonate (DMC) are published at home and abroad, and the patents have relatively large-scale industrial production, and related patents are disclosed in J.F. Knifton et al [ J.mol.Catal,67(1991), 389-. The DMC production method mainly comprises an oxidative carbonylation method and an ester exchange method, and the ester exchange method is mainly adopted in China. The transesterification method comprises reacting ethylene oxide (or propylene oxide) with carbon dioxide to produce Ethylene Carbonate (EC) (or Propylene Carbonate (PC)), and then performing transesterification with methanol. Taking PC as a raw material, the reaction is as follows:
the transesterification reaction usually adopts a solid catalyst, and the reaction system for synthesizing DMC by transesterification is divided into a homogeneous catalysis reaction system and a heterogeneous catalysis reaction system according to whether the catalyst and the reactant are in the same phase state during the reaction. In the homogeneous reaction system, the catalysts used at the beginning are soluble alkali metal hydroxides, alkali metal carbonates, organic bases and the like. Such as NaOH, KOH, K2CO3And the like. Because the homogeneous catalyst is difficult to separate from the product, the purity of the product is reduced, the purification cost is increased,heterogeneous catalysts are therefore currently being studied relatively much. Heterogeneous reaction systems, mostly alkaline earth metal oxides, ionic resins, etc., such as Amberlyst39Wet ion exchange resin catalyst (Applied Catalysis B: Environmental:2012,125: 486-491); MgO-CeO2The double metal oxide catalyst (Catalysis Letters:2007,118:30-35) can effectively improve the yield of DMC, but the temperature required by the reaction is higher and is above 130 ℃, and the active components are easy to lose and cannot be reused. The Ca-based solid base has high activity and high stability, can be repeatedly used and can obviously reduce the reaction temperature, patent CN105879892B, and synthesized hydrotalcite-like Ca-Al-O-X (X ═ CO)3 2-、NO3-、F-、Cl-Or Br-) The DMC yield of the catalyst is 58.4 percent under the conditions of normal pressure, reaction temperature of 70 ℃ and reaction time of 2 hours. Although the catalyst can lower the reaction temperature, the DMC yield decreases by 8% after 5 times of repeated use.
In summary, the reaction temperature required by the existing heterogeneous solid base catalyst is higher, the higher temperature can increase the occurrence of side reactions, and the high polymer of the polyhydric alcohol is easily formed. Based on this, it has become eager to design and adjust the catalyst structure and prepare a novel Ca-based solid base catalyst capable of reacting at low temperature and normal pressure.
Disclosure of Invention
The invention aims to provide a method for synthesizing dimethyl carbonate by using a solid alkali catalyst containing fluorine, calcium, zirconium and aluminum, aiming at the defects of the prior art. According to the method, a plurality of fluorides are added in the preparation, different compounds can be formed by using different fluoride salts, calcium fluoride can be formed by adding potassium fluoride, F-CaO can be formed by adding sodium fluoride, and the activity of the catalyst can be improved by the substances; addition of ammonium fluoride can form AlF6 3-The material can improve the stability and catalytic activity of the catalyst. The invention has the advantages of easily obtained and cheap raw materials, good catalyst stability, high activity, easy separation, repeated use and high product yield.
The technical scheme of the invention is as follows:
a method for synthesizing dimethyl carbonate by using fluorine-containing calcium zirconium aluminum solid base as a catalyst comprises the following steps:
adding propylene carbonate, methanol and fluorine-containing calcium zirconium aluminum solid alkali into a reactor, and reacting for 0.5-1 h at 50-80 ℃ under stirring to obtain dimethyl carbonate;
wherein the raw materials have the molar ratio of propylene carbonate: methanol 1: 5-15; the mass ratio of the fluorine-containing calcium zirconium aluminum solid alkali is as follows: the raw materials are 0.5-2.5: 100.
the stirring revolution is 800 +/-50 r/min;
the preparation method of the fluorine-containing calcium zirconium aluminum solid alkali comprises the following steps: roasting fluorine-containing calcium zirconium aluminum hydrotalcite as a precursor at 400-800 ℃ for 3-8 h to obtain the product; the general structural formula of the fluorine-containing calcium zirconium aluminum hydrotalcite is as follows:
A+ xCa2+ yZr2+ zAl3+ (1-x-y-z)(OH2)(F-)2(CO3 2-)(1-x-y-z)/2·mH2o; wherein A is+Is K+Or Na+；0.2≤x+y+z≤0.8，0.02≤x≤0.2，0.1≤y≤0.3，0.05≤z≤0.3，6≤m≤12。
The preparation method of the fluorine-containing calcium zirconium aluminum hydrotalcite comprises the following steps:
(1) according to Ca in the composition of calcium zirconium aluminum hydrotalcite2+、Zr2+And Al3+The ratio of the amount of the substances is that calcium salt, zirconium salt and aluminum salt are prepared into mixed salt solution according to the molar ratio,
wherein, in the mixed salt solution, the concentration range of the metal salt is as follows: [ Ca ]2+]＝0.2～1.6mol/L、[Zr2+]＝0.05～0.6mol/L、[Al3+]＝0.2～1.2mol/L、[A+]＝0.2～0.8mol/L；
(2) Adding fluoride into water to obtain a fluoride solution;
wherein, the fluoride is two or three of potassium fluoride, sodium fluoride and ammonium fluoride; the mole number of the fluoride is 0.5-30% of the total mole number of the metal salt in the mixed salt solution in the step (1); the volume of the fluoride solution is 45-55% of that of the mixed salt solution;
(3) dissolving sodium carbonate and sodium hydroxide in water to obtain a mixed alkali solution;
wherein, the mol ratio is sodium carbonate: sodium hydroxide ═ 0.5: 0.5 to 2; the concentration of sodium carbonate in the mixed alkali is 2.0-5 mlo/L;
(4) under stirring, simultaneously dropwise adding the mixed salt solution and the fluoride solution into the mixed solvent of the reactor at the same flow rate, and simultaneously dropwise adding a mixed alkali solution, wherein the pH of the mixed solution in the reaction is kept at 9-11; after the dropwise adding is completed within 0.5-3 hours, continuously stirring for 1-1.5 hours, standing and crystallizing for 5-24 hours at the temperature of 30-90 ℃, carrying out suction filtration on the precipitate, washing to be neutral, and drying and grinding the obtained solid to obtain the fluorine-containing calcium-zirconium-aluminum hydrotalcite.
The calcium salt in the step (1) is calcium chloride or calcium nitrate, the zirconium salt is zirconium nitrate, zirconium oxychloride or zirconium isopropoxide, and the aluminum salt is aluminum chloride or aluminum nitrate.
The stirring speed is 1100-1300 r/min;
the mixed solvent is water and ethanol; the volume ratio of the two is 2: 3; the volume of the mixed solvent is 0.1-0.5 times of the volume of the mixed salt solution.
The invention has the beneficial effects that:
the fluorine-containing calcium zirconium aluminum solid base catalyst is prepared by roasting fluorine-containing calcium zirconium aluminum hydrotalcite; as the anion fluorine and the metal calcium and zirconium are introduced into the framework, the surface alkaline center alkali strength of the fluorine-containing calcium-zirconium-aluminum hydrotalcite is higher than that of the calcium-aluminum hydrotalcite; in addition, the atomic radius of the fluorine ions is small, and the oxygen ions and the carbonate ions enable the layered compounds to be more compact, the specific surface area to be increased, a large number of strong base active centers to be exposed, and the reaction of propylene carbonate and methanol to be promoted to rapidly occur.
In the prior art, the manganese-aluminum composite oxide prepared by taking manganese-aluminum hydrotalcite as a precursor is used as a catalyst for ester exchange reaction, the PC conversion rate is 58.7 percent, and the DMC yield is 80 percent; compared with the catalyst, the catalyst has the advantages that the PC conversion rate is between 60 and 85 percent and the DMC yield is between 85 and 90 percent under the same conditions. Therefore, the method has the advantages of high catalyst activity and high product yield. In addition, the invention is easy for industrial synthesis, low in cost, reusable and easy for product separation.
Detailed Description
The following provides a more detailed description of the present invention. The features and advantages of the present invention will be apparent to those skilled in the art from the detailed description of the invention.
Example 1
Preparation of the catalyst: preparing 0.3mol of calcium chloride, 0.1mol of zirconium oxychloride, 0.1mol of aluminum chloride and 500ml of deionized water into a solution A; preparing 0.1mol of potassium fluoride, 0.01mol of ammonium fluoride and 250ml of deionized water into a solution B; preparing 1mol of sodium hydroxide, 0.5mol of sodium carbonate and 500ml of deionized water into a solution C; keeping the constant temperature at 40 ℃, adding the solution A and the solution B into 100ml (water and ethanol in a volume ratio of 2: 3) of solution under the condition of continuous stirring, simultaneously dropwise adding the solution C, keeping the pH of the mixed solution at 9-11 by adjusting the dropping speed of the solution C, completing dropwise adding within 0.5-1 h, continuously stirring for 70 minutes, and standing and crystallizing for 15h at 60 ℃; then filtering, washing to be neutral, drying at 105 ℃ for 12h, crushing to obtain fluorine-containing calcium zirconium aluminum hydrotalcite-like compound, and roasting the obtained hydrotalcite-like compound at 500 ℃ for 6h to obtain the fluorine-containing calcium zirconium aluminum solid base catalyst. By XPS elemental analysis, the product was obtained with the formula: k+ 0.15Ca2+ 0.3Zr2+ 0.3Al3+ 0.25(OH2)(F-)2(CO3 2-)0.125·6H2O。
Synthesizing dimethyl carbonate by using different fluorine-containing calcium zirconium aluminum solid base catalyst adding amounts:
(1) 0.1mol of propylene carbonate, 0.5mol of methanol and 0.3g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 1 are added into a reactor, and the mixture reacts for 1h at 50 ℃ and at the rotating speed of 800r/min, is cooled, centrifuged and detected by liquid chromatography, and the product yield is 42.37%.
(2) 0.1mol of propylene carbonate, 0.8mol of methanol and 0.5g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 1 are added into a reactor, and the mixture reacts for 1h at the temperature of 60 ℃ and the rotating speed of 800r/min, is cooled, is centrifuged and is detected by liquid chromatography, and the yield of the product is 58.62 percent.
(3) 0.1mol of propylene carbonate, 1.2mol of methanol and 0.7g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 1 are added into a reactor, and the mixture reacts for 1h at 80 ℃ and at the rotating speed of 800r/min, is cooled, centrifuged and detected by liquid chromatography, and the product yield is 62.76%.
(4) Centrifuging the catalyst used in the step (3), alternately washing with distilled water and absolute ethyl alcohol, drying, repeatedly using the catalyst for 10 times according to the reaction conditions of the step (3), wherein the product yield of the tenth time is 61.26 percent
Example 2
Preparation of the catalyst: preparing 0.45mol of calcium nitrate, 0.2mol of zirconium nitrate, 0.35mol of aluminum nitrate and 500ml of deionized water into a solution A; preparing 0.155mol of sodium fluoride, 0.015mol of ammonium fluoride and 250ml of deionized water into a solution B; preparing 2mol of sodium hydroxide, 0.5mol of sodium carbonate and 500ml of deionized water into a solution C; keeping the constant temperature at 50 ℃, adding the solution A and the solution B into 100ml (water and ethanol in a volume ratio of 2: 3) of solution under the condition of continuous stirring, simultaneously dropwise adding the solution C, keeping the pH of the mixed solution at 9-11 by adjusting the dropping speed of the solution C, completing dropwise adding within 0.5-1 h, continuously stirring for 100 minutes, and standing and crystallizing for 15h at 80 ℃; then filtering, washing to be neutral, drying for 12h at 105 ℃, crushing to obtain fluorine-containing calcium zirconium aluminum hydrotalcite-like compound, and roasting the obtained hydrotalcite-like compound for 6h at 600 ℃ to obtain the fluorine-containing calcium zirconium aluminum solid base catalyst. The product was obtained by XPS elemental analysis and was of formula Na+ 0.12Ca2+ 0.28Zr2+ 0.25Al3+ 0.35(OH2)(F-)2(CO3 2-)0.175·8H2O。
(1) 0.1mol of propylene carbonate, 0.8mol of methanol and 0.5g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 2 are added into a reactor, and the mixture reacts for 1h at the temperature of 60 ℃ and the rotating speed of 800r/min, is cooled, is centrifuged and is detected by liquid chromatography, and the yield of the product is 61.34%.
(2) 0.1mol of propylene carbonate, 1.2mol of methanol and 0.7g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 2 are added into a reactor, and the mixture reacts for 1h at 80 ℃ and at the rotating speed of 800r/min, is cooled, centrifuged and detected by liquid chromatography, and the product yield is 74.35%.
(3) Centrifuging the catalyst used in the step (2), alternately washing with distilled water and absolute ethyl alcohol, drying, repeatedly using the catalyst for 10 times according to the reaction conditions of the step (2), wherein the product yield of the tenth time is 73.69 percent
Example 3
Preparation of the catalyst: preparing 0.45mol of calcium chloride, 0.25mol of zirconium isopropoxide, 0.35mol of aluminum chloride and 500ml of deionized water into a solution A; preparing 0.16mol of potassium fluoride, 0.02mol of ammonium fluoride and 250ml of deionized water into a solution B; preparing 3mol of sodium hydroxide, 0.5mol of sodium carbonate and 500ml of deionized water into a solution C; keeping the constant temperature at 50 ℃, adding the solution A and the solution B into 100ml (water and ethanol in a volume ratio of 2: 3) of solution under the condition of continuous stirring, simultaneously dropwise adding the solution C, keeping the pH of the mixed solution at 9-11 by adjusting the dropping speed of the solution C, completing dropwise adding within 0.5-1 h, continuously stirring for 90 minutes, and standing and crystallizing for 15h at 90 ℃; then filtering, washing to be neutral, drying for 12h at 105 ℃, crushing to obtain fluorine-containing calcium zirconium aluminum hydrotalcite-like compound, and roasting the obtained hydrotalcite-like compound for 6h at 600 ℃ to obtain the fluorine-containing calcium zirconium aluminum solid base catalyst. By XPS elemental analysis, the product was obtained with the formula: k+ 0.18Ca2+ 0.3Zr2+ 0.28Al3+ 0.24(OH2)(F-)2(CO3 2-)0.12·8H2O。
(1) 0.1mol of propylene carbonate, 0.8mol of methanol and 0.5g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 3 are added into a reactor, and the mixture reacts for 1h at the temperature of 60 ℃ and the rotating speed of 800r/min, is cooled, is centrifuged and is detected by liquid chromatography, and the product yield is 63.24%.
(2) 0.1mol of propylene carbonate, 1.2mol of methanol and 0.7g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 3 are added into a reactor, and the mixture reacts for 1h at the temperature of 120 ℃ and the rotating speed of 800r/min, is cooled, is centrifuged and is detected by liquid chromatography, and the product yield is 79.36%.
(3) Centrifuging the catalyst used in the step (2), alternately washing with distilled water and absolute ethyl alcohol, drying, repeatedly using the catalyst for 10 times according to the reaction conditions of the step (2), wherein the product yield of the tenth time is 78.98 percent
Example 4
Preparation of the catalyst: preparing 0.65mol of calcium chloride, 0.2mol of zirconium isopropoxide, 0.35mol of aluminum chloride and 500ml of deionized water into a solution A; preparing 0.165mol of potassium fluoride, 0.08mol of ammonium fluoride and 250ml of deionized water into a solution B; preparing 3mol of sodium hydroxide, 0.5mol of sodium carbonate and 500ml of deionized water into a solution C; keeping the constant temperature at 50 ℃, adding the solution A and the solution B into 100ml (water and ethanol in a volume ratio of 2: 3) of solution under the condition of continuous stirring, simultaneously dropwise adding the solution C, keeping the pH of the mixed solution at 9-11 by adjusting the dropping speed of the solution C, completing dropwise adding within 0.5-1 h, continuously stirring for 90 minutes, and standing and crystallizing for 20h at 90 ℃; then filtering, washing to be neutral, drying for 12h at 105 ℃, crushing to obtain fluorine-containing calcium zirconium aluminum hydrotalcite-like compound, and roasting the obtained hydrotalcite-like compound for 6h at 800 ℃ to obtain the fluorine-containing calcium zirconium aluminum solid base catalyst. By XPS elemental analysis, the product was obtained with the formula: k+ 0.16Ca2+ 0.3Zr2+ 0.22Al3+ 0.32(OH2)(F-)2(CO3 2-)0.16·9H2O
(1) 0.1mol of propylene carbonate, 0.8mol of methanol and 0.5g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 4 are added into a reactor, and the mixture reacts for 1h at the temperature of 60 ℃ and the rotating speed of 800r/min, is cooled, is centrifuged and is detected by liquid chromatography, and the yield of the product is 74.23%.
(2) 0.1mol of propylene carbonate, 1.2mol of methanol and 0.7g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 4 are added into a reactor, and the mixture reacts for 1h at 80 ℃ and at the rotating speed of 800r/min, is cooled, centrifuged and detected by liquid chromatography, and the product yield is 85.78%.
(3) Centrifuging the catalyst used in the step (2), alternately washing with distilled water and absolute ethyl alcohol, drying, repeatedly using the catalyst for 10 times according to the reaction conditions of the step (2), wherein the product yield of the tenth time is 84.69 percent
Example 5
Preparation of the catalyst: preparing 0.75mol of calcium chloride, 0.2mol of zirconium oxychloride, 0.45mol of aluminum chloride and 500ml of deionized water into a solution A; preparing 0.23mol of potassium fluoride, 0.06mol of ammonium fluoride and 250ml of deionized water into a solution B; preparing 2.5mol of sodium hydroxide, 0.5mol of sodium carbonate and 500ml of deionized water into a solution C; keeping the constant temperature at 60 ℃, adding the solution A and the solution B into 100ml (water and ethanol in a volume ratio of 2: 3) of solution under the condition of continuous stirring, simultaneously dropwise adding the solution C, keeping the pH of the mixed solution at 9-11 by adjusting the dropping speed of the solution C, completing dropwise adding within 0.5-1 h, continuously stirring for 80 minutes, and standing and crystallizing for 20h at 90 ℃; then filtering, washing to be neutral, drying for 12h at 105 ℃, crushing to obtain fluorine-containing calcium zirconium aluminum hydrotalcite-like compound, and roasting the obtained hydrotalcite-like compound for 6h at 800 ℃ to obtain the fluorine-containing calcium zirconium aluminum solid base catalyst. By XPS elemental analysis, the product was obtained with the formula: k+ 0.18Ca2+ 0.3Zr2+ 0.26Al3+ 0.26(OH2)(F-)2(CO3 2-)0.13·10H2O
(1) 0.1mol of propylene carbonate, 0.8mol of methanol and 0.5g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 5 are added into a reactor, and the mixture reacts for 1h at the temperature of 60 ℃ and the rotating speed of 800r/min, is cooled, is centrifuged and is detected by liquid chromatography, and the product yield is 80.49%.
(2) 0.1mol of propylene carbonate, 1.2mol of methanol and 0.7g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 5 are added into a reactor, and the mixture reacts for 1h at 80 ℃ and at the rotating speed of 800r/min, is cooled, centrifuged and detected by liquid chromatography, and the product yield is 87.96%.
(3) And (3) centrifuging the catalyst used in the step (2), washing the catalyst with distilled water and absolute ethyl alcohol alternately, drying the catalyst, and repeatedly using the catalyst for 10 times according to the reaction conditions of the step (2), wherein the product yield of the tenth time is 86.94%.
Example 6
Preparation of the catalyst: 0.78mol of calcium nitrate and 0.26mPreparing solution A from ol zirconium nitrate, 0.35mol of aluminum nitrate and 500ml of deionized water; preparing 0.21mol of potassium fluoride, 0.08mol of ammonium fluoride and 250ml of deionized water into a solution B; preparing 2.5mol of sodium hydroxide, 0.5mol of sodium carbonate and 500ml of deionized water into a solution C; keeping the constant temperature at 70 ℃, adding the solution A and the solution B into 100ml (water and ethanol in a volume ratio of 2: 3) of solution under the condition of continuous stirring, simultaneously dropwise adding the solution C, keeping the pH of the mixed solution at 9-11 by adjusting the dropping speed of the solution C, completing dropwise adding within 0.5-1 h, continuously stirring for 90 minutes, and standing and crystallizing for 20h at 100 ℃; then filtering, washing to be neutral, drying for 12h at 105 ℃, crushing to obtain fluorine-containing calcium zirconium aluminum hydrotalcite-like compound, and roasting the obtained hydrotalcite-like compound for 6h at 800 ℃ to obtain the fluorine-containing calcium zirconium aluminum solid base catalyst. By XPS elemental analysis, the product was obtained with the formula: k+ 0.19Ca2+ 0.3Zr2+ 0.24Al3+ 0.27(OH2)(F-)2(CO3 2-)0.135·8H2O
(1) 0.1mol of propylene carbonate, 0.8mol of methanol and 0.5g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 6 are added into a reactor, and the mixture reacts for 1h at the temperature of 60 ℃ and the rotating speed of 800r/min, is cooled, is centrifuged and is detected by liquid chromatography, and the product yield is 72.12 percent.
(2) 0.1mol of propylene carbonate, 1.2mol of methanol and 0.7g of fluorine-containing calcium zirconium aluminum solid base catalyst prepared in the embodiment 6 are added into a reactor, and the mixture reacts for 1h at 80 ℃ and at the rotating speed of 800r/min, is cooled, centrifuged and detected by liquid chromatography, and the product yield is 89.96%.
(3) And (3) centrifuging the catalyst used in the step (2), washing the catalyst with distilled water and absolute ethyl alcohol alternately, drying the catalyst, and repeatedly using the catalyst for 10 times according to the reaction conditions of the step (2), wherein the yield of the product for the tenth time is 89.25%.
The above embodiments are merely exemplary and not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The invention is not the best known technology.
Claims (7)
1. A method for synthesizing dimethyl carbonate by using fluorine-containing calcium zirconium aluminum solid base catalysis is characterized by comprising the following steps:
adding propylene carbonate, methanol and fluorine-containing calcium zirconium aluminum solid alkali into a reactor, and reacting for 0.5-1 h at 50-80 ℃ under stirring to obtain dimethyl carbonate;
wherein the raw materials have the molar ratio of propylene carbonate: methanol 1: 5-15; the mass ratio of the fluorine-containing calcium zirconium aluminum solid alkali is as follows: the raw materials are 0.5-2.5: 100, respectively;
the fluorine-containing calcium zirconium aluminum solid alkali is obtained by roasting fluorine-containing calcium zirconium aluminum hydrotalcite as a precursor at 400-800 ℃ for 3-8 h.
2. The method for synthesizing dimethyl carbonate by solid base catalysis of fluorine-containing calcium zirconium aluminum according to claim 1, wherein the structural general formula of the fluorine-containing calcium zirconium aluminum hydrotalcite is as follows:
A+ xCa2+ yZr2+ zAl3+ (1-x-y-z)(OH2)(F-)2(CO3 2-)(1-x-y-z)/2·mH2O；A+is K+Or Na+；0.2≤x+y+z≤0.8，0.02≤x≤0.2，0.1≤y≤0.3，0.05≤z≤0.3，6≤m≤12。
3. The method for synthesizing dimethyl carbonate by solid base catalysis of fluorine calcium zirconium aluminum as claimed in claim 1, wherein the stirring rotation number is 800 ± 50 r/min.
4. The method for synthesizing dimethyl carbonate by solid base catalysis of fluorine calcium zirconium aluminum containing as claimed in claim 1, wherein the preparation method of the fluorine calcium zirconium aluminum containing hydrotalcite comprises the following steps:
(1) according to Ca in the composition of calcium zirconium aluminum hydrotalcite2+、Zr2+And Al3+The ratio of the amount of the substances is that calcium salt and zirconium are mixedPreparing a mixed salt solution from salt and aluminum salt according to a molar ratio;
wherein, in the mixed salt solution, the concentration range of the metal salt is as follows: [ Ca ]2+]＝0.2～1.6mol/L、[Zr2+]＝0.05～0.6mol/L、[Al3+]＝0.2～1.2mol/L、[A+]＝0.2～0.8mol/L；
(2) Adding fluoride into water to obtain a fluoride solution;
wherein, the fluoride is two or three of potassium fluoride, sodium fluoride and ammonium fluoride; the mole number of the fluoride is 0.5-30% of the total mole number of the metal salt in the mixed salt solution in the step (1); the volume of the fluoride solution is 45-55% of that of the mixed salt solution;
(3) dissolving sodium carbonate and sodium hydroxide in water to obtain a mixed alkali solution;
wherein, the mol ratio is sodium carbonate: sodium hydroxide ═ 0.5: 0.5 to 2; the concentration of sodium carbonate in the mixed alkali is 2.0-5 mlo/L;
(4) under stirring, simultaneously dropwise adding the mixed salt solution and the fluoride solution into the mixed solvent of the reactor at the same flow rate, and simultaneously dropwise adding a mixed alkali solution, wherein the pH of the mixed solution in the reaction is kept at 9-11; after the dropwise adding is completed within 0.5-3 hours, continuously stirring for 1-1.5 hours, standing and crystallizing for 5-24 hours at the temperature of 30-90 ℃, carrying out suction filtration on the precipitate, washing to be neutral, and drying and grinding the obtained solid to obtain the fluorine-containing calcium-zirconium-aluminum hydrotalcite.
5. The method for synthesizing dimethyl carbonate by solid base catalysis of fluorine calcium-containing zirconium aluminum according to claim 4, wherein the calcium salt in step (1) is calcium chloride or calcium nitrate, the zirconium salt is zirconium nitrate, zirconium oxychloride or zirconium isopropoxide, and the aluminum salt is aluminum chloride or aluminum nitrate.
6. The method for synthesizing dimethyl carbonate by solid base catalysis of fluorine calcium zirconium aluminum according to claim 4, wherein the stirring speed in the step (4) is 1100-1300 r/min.
7. The method for synthesizing dimethyl carbonate by solid base catalysis of fluorine calcium zirconium aluminum as claimed in claim 4, characterized in that the mixed solvent is water and ethanol; the volume ratio of the two is 2: 3; the volume of the mixed solvent is 0.1-0.5 times of the volume of the mixed salt solution.
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| CN101249452A (en) * | 2008-03-19 | 2008-08-27 | 北京化工大学 | Load type solid body base catalyst of synthesizing dimethyl carbonate and method of preparing the same |
| CN105879892A (en) * | 2016-05-27 | 2016-08-24 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthesizing dimethyl carbonate through transesterification method and preparation method and application |
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