CN112206796A - Phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst and method for synthesizing lactide - Google Patents
Phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst and method for synthesizing lactide Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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Abstract
The invention relates to a method for synthesizing lactide, in particular to a phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst and a method for efficiently catalyzing lactic acid to generate lactide. Dripping phosphoric acid aqueous solution on the surface of the molybdenum vanadium niobium catalyst for wetting, drying and roasting to obtain the catalyst, wherein the catalyst contains Mo in all componentsxV0.95‑ xNb0.05OxPyWherein x is 0.30-0.63, and y is 0.01-0.05. The catalyst of the invention is a heterogeneous catalyst, has high activity, easy separation of the product and the catalyst, recyclability of the catalyst, low reaction temperature, simple process operation and higher selectivity to lactide.
Description
Technical Field
The invention relates to a method for synthesizing lactide, in particular to a phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst and a method for efficiently catalyzing lactic acid to generate lactide.
Background
Lactide is a cyclic dimer of lactic acid and an important intermediate for synthesizing polylactic acid, the relative molecular mass of the polylactic acid prepared by lactide can reach one hundred thousand to one million, and the lactide is the best degradable high polymer material for replacing white plastics. Therefore, the structure and the existing form of the lactide are different, and the variety and the structure of the polylactic acid and the final physical and chemical properties are directly influenced.
At present, the synthesis method of lactide mainly comprises two major methods, namely a biological method and a chemical method, wherein the latter method generally takes lactic acid as a raw material and obtains lactide through dehydration-depolymerization processes. The reaction equation is shown below (Polymer Degradation and Stability,1998,59, 145):
because the synthesis of lactide is sequentially subjected to two processes of lactic acid dehydration esterification and lactic acid oligomer depolymerization, most of the used catalysts are solid acid catalysts rich in Lewis acid centers, wherein the metal salt catalysts (such as stannous octoate, stannous chloride and the like) are Chinese patent application numbers 201510076939, 201210289443 and 201210288955. In addition, catalysts containing other metal elements such as Al, Zn, Ti, Ca, and Fe are also included, and many of them are mainly halides and oxides. Research shows that (plastic chemical industry, 2004, 32, 8-10), stannous octoate, zinc oxide, zinc chloride, stannous chloride and the like have good catalytic effects, wherein the stannous octoate has the best effect. However, the sn (ii) type catalyst has certain physiological toxicity, so that the application of polylactic acid produced by using the sn (ii) type catalyst in the medical field is limited. In addition, when a metal salt catalyst is used, the conversion rate of lactic acid is slow and the reaction time is long. Therefore, it is required to develop a catalyst which is non-toxic, easy to prepare, high in activity and capable of producing a high-performance polylactic acid product, instead of the original sn (ii) -based catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst and a method for efficiently catalyzing lactic acid to generate lactide.
In order to achieve the purpose, the invention adopts the technical scheme that:
a phosphoric acid modified Mo-V-Nb composite metal oxide catalyst is prepared through dropping the aqueous solution of phosphoric acid on the surface of Mo-V-Nb catalyst, wetting, and bakingDrying and roasting to obtain the catalyst, namely the catalyst contains Mo in all componentsxV0.95-xNb0.05OxPyWherein x is 0.30-0.63, and y is 0.01-0.05.
The molybdenum vanadium niobium catalyst wetted by the phosphoric acid aqueous solution is dried at 80-100 ℃ overnight, and the dried powder is roasted at 400-600 ℃ for 4 hours in the air atmosphere to obtain the catalyst; wherein the concentration of the phosphoric acid aqueous solution is 30-50 wt%.
Dissolving oxalic acid and ammonium metavanadate in deionized water to prepare a solution 1, dissolving ammonium molybdate in deionized water to prepare a solution 2, dissolving ammonium niobate oxalate hydrate in deionized water to prepare a solution 3, pouring the solution 2 into the solution 1 while stirring, dropwise adding the solution 3 into a mixed solution of the solution 1 and the solution 2, heating to 60-90 ℃ after mixing, stirring, steaming the solution, drying at 110-120 ℃ overnight, and roasting the dried powder at 400-600 ℃ for 4 hours in an air atmosphere to prepare the catalyst, wherein the content of each component of the catalyst is MoxV0.95-xNb0.05Ox. Wherein x is 0.30-0.63.
The concentration of the solution 1 is 20-40 wt%, wherein the mass ratio of oxalic acid to ammonium metavanadate is (2-3): 1; the concentration of ammonium molybdate in the solution 2 is 20-40 wt%; the concentration of ammonium niobate oxalate in the solution 3 is 5-12 wt%; solution 1, solution 2 and solution 3 were mixed at a ratio of 0.8-1.2: 1-1.5: mixing at a ratio of 1.
The 3 solutions were heated to 50 ℃ separately after being placed and stirred until each solution was completely dissolved.
An application of a phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst in catalyzing lactic acid to synthesize lactide.
The efficient synthesis method of lactide adopts the phosphoric acid modified molybdenum vanadium niobium composite metal oxide as a catalyst, and the reaction is carried out for 0.5 to 3 hours at the temperature of 160-200 ℃ under the conditions of oxidizing atmosphere and negative pressure, so as to catalyze the dehydration-depolymerization of lactic acid serving as a raw material to generate the lactide; wherein the catalyst accounts for 5-50% of the raw material.
The oxidizing atmosphere is one or a mixture of air, oxygen and nitrogen.
The negative pressure is 0.05-0.09 MPa.
The concentration of the reactant lactic acid is 0.1g/mL pure lactic acid.
Compared with the prior art, the invention has the following advantages:
lactic acid is used as a reaction raw material, phosphoric acid modified molybdenum vanadium niobium composite metal oxide is used as a catalyst, and lactide products are obtained through dehydration-depolymerization reaction of the lactic acid. The catalyst is a heterogeneous catalyst, the introduction of phosphoric acid promotes the molybdenum vanadium niobium surface to form a phosphomolybdic heteropoly acid structure, the number of surface protonic acid centers is increased, the acid strength of the catalyst is improved, and the activity and the selectivity of the catalyst are further improved. In addition, the product and the catalyst are easy to separate, the catalyst can be recycled, the cost is reduced, the reaction temperature is low, the process operation is simple, the selectivity to the lactide is high, and the environment is hardly polluted.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following specific examples.
Example 1
Firstly, dissolving 7.2g of oxalic acid and 3.63g of ammonium metavanadate in 25mL of deionized water to prepare a solution 1, dissolving 10.77g of ammonium paramolybdate in 25mL of deionized water to prepare a solution 2, dissolving 2.42g of ammonium niobate oxalate hydrate in 25mL of deionized water to prepare a solution 3, heating all 3 solutions to 30 ℃, stirring until the solutions are completely dissolved, then pouring the solution 2 into the solution 1 while stirring, dropwise adding the solution 3 into a mixed solution of the solution 1 and the solution 2, mixing the 3 solutions, heating the mixed solution to 90 ℃, stirring and evaporating the solution to dryness, then transferring the mixed solution into a drying oven for drying overnight at 120 ℃, finally, roasting the dried powder at 600 ℃ for 6 hours in an air atmosphere to prepare a catalyst, wherein the air flow rate during roasting is 100mL/min, and the temperature rising rate is controlled to 10 ℃/min.
Step two, taking 5.0g of lactic acid, diluting the lactic acid to 50mL by using deionized water, adding 0.5g of the catalyst, heating the lactic acid to 160 ℃ in an oil bath, introducing air with the air flow of 100mL/min, and reacting for 6 hours.
The reaction product was analyzed by HPLC, and the results showed that the conversion of lactic acid was 87% and the selectivity to lactide was 52%.
Example 2
Firstly, dissolving 7.2g of oxalic acid and 3.63g of ammonium metavanadate in 25mL of deionized water to prepare a solution 1, dissolving 10.77g of ammonium paramolybdate in 25mL of deionized water to prepare a solution 2, dissolving 2.42g of ammonium niobate oxalate hydrate in 25mL of deionized water to prepare a solution 3, heating all 3 solutions to 30 ℃, stirring until the solutions are completely dissolved, then pouring the solution 2 into the solution 1 while stirring, dropwise adding the solution 3 into a mixed solution of the solution 1 and the solution 2, mixing the 3 solutions, heating the mixed solution to 90 ℃, stirring and evaporating the solution to dryness, then transferring the mixed solution into a drying oven for drying overnight at 120 ℃, finally, roasting the dried powder at 450 ℃ for 6 hours in an air atmosphere to prepare a catalyst, wherein the air flow rate during roasting is 100mL/min, and the temperature rising rate is controlled to 10 ℃/min.
Step two, taking 5.0g of lactic acid, diluting the lactic acid to 50mL by using deionized water, adding 0.5g of the catalyst, heating the lactic acid to 160 ℃ in an oil bath, introducing oxygen at the oxygen flow of 100mL/min, and reacting for 6 hours.
The reaction product was analyzed by HPLC, and the results showed that the conversion of lactic acid was 92% and the selectivity of lactide was 60%.
Example 3
Firstly, dissolving 7.2g of oxalic acid and 3.63g of ammonium metavanadate in 25mL of deionized water to prepare a solution 1, dissolving 10.77g of ammonium paramolybdate in 25mL of deionized water to prepare a solution 2, dissolving 2.42g of ammonium niobate oxalate hydrate in 25mL of deionized water to prepare a solution 3, heating all 3 solutions to 30 ℃, stirring until the solutions are completely dissolved, then pouring the solution 2 into the solution 1 while stirring, dropwise adding the solution 3 into a mixed solution of the solution 1 and the solution 2, mixing the 3 solutions, heating the mixed solution to 90 ℃, stirring and evaporating the solution to dryness, then transferring the mixed solution into a drying oven for drying overnight at 120 ℃, finally, roasting the dried powder at 450 ℃ for 6 hours in an air atmosphere to prepare a catalyst, wherein the air flow rate during roasting is 100mL/min, and the temperature rising rate is controlled to 10 ℃/min.
Step two, taking 13mL of phosphoric acid aqueous solution with the concentration of 30 wt.%, and uniformly dropwise adding the phosphoric acid aqueous solution to the surface of the molybdenum-vanadium-niobium catalyst prepared in the step one, wherein the surface of the molybdenum-vanadium-niobium catalyst is 10 g. And after the molybdenum-vanadium-niobium catalyst is completely wetted, transferring the molybdenum-vanadium-niobium catalyst into an oven to be dried at 80 ℃ overnight, and finally roasting the dried powder for 4 hours at 450 ℃ in an air atmosphere to obtain the catalyst, wherein the airflow rate during roasting is 100mL/min, and the heating rate is controlled to be 5 ℃/min.
And step three, taking 5.0g of lactic acid, diluting the lactic acid to 50mL by using deionized water, adding 0.5g of the catalyst, heating the lactic acid to 160 ℃ in an oil bath, introducing oxygen at the oxygen flow of 100mL/min, and reacting for 6 hours.
The reaction product was analyzed by HPLC, and the results showed that the conversion of lactic acid was 96% and the selectivity to lactide was 74%.
Example 4
Firstly, dissolving 7.2g of oxalic acid and 3.63g of ammonium metavanadate in 25mL of deionized water to prepare a solution 1, dissolving 10.77g of ammonium paramolybdate in 25mL of deionized water to prepare a solution 2, dissolving 2.42g of ammonium niobate oxalate hydrate in 25mL of deionized water to prepare a solution 3, heating all 3 solutions to 30 ℃, stirring until the solutions are completely dissolved, then pouring the solution 2 into the solution 1 while stirring, dropwise adding the solution 3 into a mixed solution of the solution 1 and the solution 2, mixing the 3 solutions, heating the mixed solution to 90 ℃, stirring and evaporating the solution to dryness, then transferring the mixed solution into a drying oven for drying overnight at 120 ℃, finally, roasting the dried powder at 450 ℃ for 6 hours in an air atmosphere to prepare a catalyst, wherein the air flow rate during roasting is 100mL/min, and the temperature rising rate is controlled to 10 ℃/min.
Step two, taking 13mL of phosphoric acid aqueous solution with the concentration of 30 wt.%, and uniformly dropwise adding the phosphoric acid aqueous solution to the surface of the molybdenum-vanadium-niobium catalyst prepared in the step one, wherein the surface of the molybdenum-vanadium-niobium catalyst is 10 g. And after the molybdenum-vanadium-niobium catalyst is completely wetted, transferring the molybdenum-vanadium-niobium catalyst into an oven to be dried at 80 ℃ overnight, and finally roasting the dried powder for 4 hours at 450 ℃ in an air atmosphere to obtain the catalyst, wherein the airflow rate during roasting is 100mL/min, and the heating rate is controlled to be 5 ℃/min.
And step three, taking 5.0g of lactic acid, diluting the lactic acid to 50mL by using deionized water, adding 0.5g of the catalyst, heating the lactic acid to 180 ℃ in an oil bath, introducing oxygen at the oxygen flow of 100mL/min, and reacting for 6 hours.
The reaction product was analyzed by HPLC, and the results showed that the conversion of lactic acid was 96% and the selectivity of lactide was 88%.
Example 5
Firstly, dissolving 7.2g of oxalic acid and 3.63g of ammonium metavanadate in 25mL of deionized water to prepare a solution 1, dissolving 10.77g of ammonium paramolybdate in 25mL of deionized water to prepare a solution 2, dissolving 2.42g of ammonium niobate oxalate hydrate in 25mL of deionized water to prepare a solution 3, heating all 3 solutions to 30 ℃, stirring until the solutions are completely dissolved, then pouring the solution 2 into the solution 1 while stirring, dropwise adding the solution 3 into a mixed solution of the solution 1 and the solution 2, mixing the 3 solutions, heating the mixed solution to 90 ℃, stirring and evaporating the solution to dryness, then transferring the mixed solution into a drying oven for drying overnight at 120 ℃, finally, roasting the dried powder at 450 ℃ for 6 hours in an air atmosphere to prepare a catalyst, wherein the air flow rate during roasting is 100mL/min, and the temperature rising rate is controlled to 10 ℃/min.
Step two, taking 13mL of phosphoric acid aqueous solution with the concentration of 50 wt.%, and uniformly dropwise adding the phosphoric acid aqueous solution to the surface of 10g of the molybdenum-vanadium-niobium catalyst prepared in the step one. And after the molybdenum-vanadium-niobium catalyst is completely wetted, transferring the molybdenum-vanadium-niobium catalyst into an oven to be dried at 80 ℃ overnight, and finally roasting the dried powder for 4 hours at 450 ℃ in an air atmosphere to obtain the catalyst, wherein the airflow rate during roasting is 100mL/min, and the heating rate is controlled to be 5 ℃/min.
And step three, taking 5.0g of lactic acid, diluting the lactic acid to 50mL by using deionized water, adding 0.5g of the catalyst, heating the lactic acid to 200 ℃ in an oil bath, introducing oxygen at the oxygen flow of 100mL/min, and reacting for 6 hours.
The reaction product was analyzed by HPLC, and the results showed that the conversion of lactic acid was 98% and the selectivity of lactide was 96%.
From the above examples, it can be seen that, in the process of synthesizing lactide from lactic acid catalyzed by the molybdenum-vanadium-niobium catalyst, the conversion of lactic acid can be effectively catalyzed, but the yield of lactide is low due to the relatively weak surface acid strength; however, the molybdenum vanadium niobium catalyst is subjected to phosphorylation modification according to the method of the invention, so that the surface acid strength of the catalyst, particularly the number of protonic acid centers, is increased, the molybdenum vanadium niobium catalyst after the phosphorylation modification maintains the high conversion rate of lactic acid, and simultaneously the selectivity of the target product lactide is remarkably improved, and further the yield of lactide is improved.
Claims (10)
1. A phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst is characterized in that: dripping phosphoric acid aqueous solution on the surface of the molybdenum vanadium niobium catalyst for wetting, drying and roasting to obtain the catalyst, wherein the catalyst contains Mo in all componentsxV0.95- xNb0.05OxPyWherein x is 0.30-0.63, and y is 0.01-0.05.
2. The phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst of claim 1, wherein: the molybdenum vanadium niobium catalyst wetted by the phosphoric acid aqueous solution is dried at 80-100 ℃ overnight, and the dried powder is roasted at 400-600 ℃ for 4 hours in the air atmosphere to obtain the catalyst; wherein the concentration of the phosphoric acid aqueous solution is 30-50 wt%.
3. The phosphoric acid-modified molybdenum vanadium niobium composite metal oxide catalyst according to claim 1 or 2, characterized in that: dissolving oxalic acid and ammonium metavanadate in deionized water to prepare a solution 1, dissolving ammonium molybdate in deionized water to prepare a solution 2, dissolving ammonium niobate oxalate hydrate in deionized water to prepare a solution 3, pouring the solution 2 into the solution 1 while stirring, dropwise adding the solution 3 into a mixed solution of the solution 1 and the solution 2, heating to 60-90 ℃ after mixing, stirring to evaporate the solution, drying at 110-120 ℃ overnight, and roasting the dried powder at 400-600 ℃ for 4 hours in an air atmosphere to prepare the catalyst, wherein the content of each component of the catalyst is MoxV0.95-xNb0.05Ox. Wherein x is 0.30-0.63.
4. The phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst of claim 3, wherein: the concentration of the solution 1 is 20-40 wt%, wherein the mass ratio of oxalic acid to ammonium metavanadate is (2-3): 1; the concentration of ammonium molybdate in the solution 2 is 20-40 wt%; the concentration of ammonium niobate oxalate in the solution 3 is 5-12 wt%; solution 1, solution 2 and solution 3 were mixed at a ratio of 0.8-1.2: 1-1.5: mixing at a ratio of 1.
5. The phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst of claim 3, wherein: the 3 solutions were heated to 50 ℃ separately after being placed and stirred until each solution was completely dissolved.
6. The use of the phosphoric acid-modified molybdenum vanadium niobium composite metal oxide catalyst of claim 1, wherein: the catalyst is applied to catalyzing lactic acid to synthesize lactide.
7. A method for efficiently synthesizing lactide is characterized by comprising the following steps: the phosphoric acid modified molybdenum vanadium niobium composite metal oxide of claim 1 is adopted as a catalyst to react for 0.5 to 3 hours at the temperature of 160-200 ℃ under the conditions of oxidizing atmosphere and negative pressure, and the lactic acid serving as a catalytic raw material is dehydrated and depolymerized to generate lactide; wherein the catalyst accounts for 5-50% of the raw material.
8. The process for the efficient synthesis of lactide according to claim 7, characterized in that: the oxidizing atmosphere is one or a mixture of air, oxygen and nitrogen.
9. The process for the efficient synthesis of lactide according to claim 7, characterized in that: the negative pressure is 0.05-0.09 MPa.
10. The process for the efficient synthesis of lactide according to claim 7, characterized in that: the concentration of the reactant lactic acid is 0.1g/mL pure lactic acid.
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| CN114588919A (en) * | 2022-03-07 | 2022-06-07 | 常州大学 | High-efficiency water-phase stable porous ceramic solid acid catalyst for hydrolysis of glycosidic bond and application thereof |
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| US20150239863A1 (en) * | 2012-08-20 | 2015-08-27 | Korea Research Institute Of Chemical Technology | Method for producing lactide directly from lactic acid and a catalyst used therein |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114588919A (en) * | 2022-03-07 | 2022-06-07 | 常州大学 | High-efficiency water-phase stable porous ceramic solid acid catalyst for hydrolysis of glycosidic bond and application thereof |
| CN114588919B (en) * | 2022-03-07 | 2023-11-14 | 常州大学 | Efficient water-phase stable porous ceramic solid acid catalyst for hydrolysis of glycosidic bond and application thereof |
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