CN112206796A - A kind of phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst and method for synthesizing lactide - Google Patents
A kind of phosphoric acid modified molybdenum vanadium niobium composite metal oxide catalyst and method for synthesizing lactide Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 42
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- -1 phosphoric acid modified molybdenum vanadium niobium Chemical class 0.000 title claims description 12
- SXZJFAXGFNHJEM-UHFFFAOYSA-N [V].[Nb].[Mo] Chemical class [V].[Nb].[Mo] SXZJFAXGFNHJEM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000010955 niobium Substances 0.000 claims abstract description 7
- 238000009736 wetting Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 94
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 80
- 235000014655 lactic acid Nutrition 0.000 claims description 40
- 239000004310 lactic acid Substances 0.000 claims description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000003570 air Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 229920000747 poly(lactic acid) Polymers 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000026731 phosphorylation Effects 0.000 description 2
- 238000006366 phosphorylation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- 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
- 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
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明是丙交酯的合成方法，具体的说是一种磷酸改性的钼钒铌复合金属氧化物催化剂及其高效催化乳酸生成丙交酯的方法。将磷酸水溶液滴加至钼钒铌催化剂表面润湿，烘干、焙烧后得催化剂，即催化剂各组分含量为MoxV0.95‑ xNb0.05OxPy，其中x＝0.30‑0.63，y＝0.01‑0.05。本发明催化剂是非均相催化剂，催化剂活性高，产物与催化剂容易分离，催化剂可回收再利用，反应温度低，工艺操作简单，对丙交酯有较高的选择性。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 lactide to generate lactide. The phosphoric acid aqueous solution is added dropwise to the surface of the molybdenum vanadium niobium catalyst for wetting, drying and roasting to obtain a catalyst, that is, the content of each component of the catalyst is Mo x V 0.95- x Nb 0.05 O x P y , wherein x=0.30-0.63, y =0.01‑0.05. The catalyst of the invention is a heterogeneous catalyst with high catalyst activity, easy separation of product and catalyst, recyclable catalyst, low reaction temperature, simple process operation and high 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 | Efficient water-phase stable porous ceramic solid acid catalyst for glycosidic bond hydrolysis and its application |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114588919A (en) * | 2022-03-07 | 2022-06-07 | 常州大学 | Efficient water-phase stable porous ceramic solid acid catalyst for glycosidic bond hydrolysis and its application |
| 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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