CN106582815A - Vanadium-based oxygen cluster compound catalyst, preparation method and application - Google Patents
Vanadium-based oxygen cluster compound catalyst, preparation method and application Download PDFInfo
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- CN106582815A CN106582815A CN201611182331.7A CN201611182331A CN106582815A CN 106582815 A CN106582815 A CN 106582815A CN 201611182331 A CN201611182331 A CN 201611182331A CN 106582815 A CN106582815 A CN 106582815A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The invention belongs the technical field of preparation of catalyst materials, and in particular relates to a preparation method and application of a (H3DBU)H3V10O28 compound catalyst. By use of the type of catalyst, in styrene epoxidation reaction, the conversion rate can reach 92%, and the selectivity can reach 94%. The preparation method of the type of catalyst has low-price and easily-available raw materials, and the preparation process is simple.
Description
Technical field
The invention belongs to catalyst material preparing technical field, is specifically related to one kind (H3DBU)H3V10O28(DBU is 1,
Carbon -7- the alkene of 8- diazabicylos 11) catalyst preparation method and its application in styrene oxidation.
Background technology
In the numerous material of multi-metal oxygen cluster, vanadium oxygen clusters are more because vanadium has to appraise at the current rate, thus urges with unique
Change characteristic.Therefore many vanadium oxygen clusters are always one of hot fields of catalytic chemistry man research.Many vanadium oxygen clusters are tied at different conditions
Structure is various, and valence state is changeable, and surface oxygen atoms are also easy to participate in coordination.Structure just because of many vanadium oxygen clusters is more special,
If changing reaction condition and reactant type, it is possible to derive that many structures are changeable, many vanadium oxygen clusters of different properties.Therefore
There is substantial amounts of document report.But for (H3DBU)H3V10O28Vanadium oxygen clusters yet there are no document report.
Additionally, styrene oxidation is a kind of important approach of synthesizing epoxy distyryl compound.Epoxy styrene chemical combination
Thing is the important oxygenatedchemicalss of a class, has important application at aspects such as chemical industry, biologies.Therefore epoxy styrene is catalyzed and synthesized
Compound is also chemist's focus of attention.Recently, Gulino A. et al. report (salen) Mn (III) catalyst and realize
Cinnamic epoxidation（Catal. Sci. Technol., 2015,5, 673-679）, but catalyst preparation is relatively complicated,
And the response time is longer.Thus design one simply synthesizes and the effective catalyst to epoxidation of styrene becomes crucial.
By retrieval, patent document related with the present patent application is not yet found.
The content of the invention
The present invention technical scheme be：(H3DBU)H3V10O28Composition catalyst, structural formula is：
Foregoing (H3DBU)H3V10O28The preparation method of compound catalyst, step is as follows：
Ammonium metavanadate, vanadyl acetylacetonate, water, DBU are sequentially added in 100 mL round-bottomed flasks, after 5 ~ 10h of strong agitation,
60 ~ 90 degrees Celsius of 2 ~ 4h of reaction, cooling is filtered, and slow evaporation under filtrate room temperature obtains bulk crystals after 6 ~ 8 days.
Foregoing preparation method, preferred scheme is, the ratio ammonium metavanadate of the amount of raw material in course of reaction：Second
Acyl acetone vanadyl：DBU is 1 ~ 5：2~4：1~3（Preferably, ammonium metavanadate：Vanadyl acetylacetonate：The ratio of the amount of DBU materials is 2：
3：2）.
Foregoing preparation method, preferred scheme is that the time is 5 ~ 10h during strong agitation in course of reaction（It is preferred that
, the strong agitation time is 8h）.
Foregoing preparation method, preferred scheme is that reaction temperature is 60 ~ 90 degrees Celsius in course of reaction（It is preferred that
, reaction temperature is 70 degrees Celsius）.
Present invention also offers (H3DBU)H3V10O28Application of the catalyst in styrene oxidation.Conversion ratio, selects
Property is obtained by gas chromatogram quantitative Analysis.
What the crystal structure information of this kind of catalyst was obtained by the following method：Obtained by conventional solution reaction synthesis
(H3DBU)H3V10O28The crystal of compound, specific description experimental technique is as follows：Add successively in the round-bottomed flask of a cleaning
Enter ammonium metavanadate（1~5 mmol）, vanadyl acetylacetonate（2~4 mmol）, DBU (1 ~ 3 mmol) and 40 ~ 80 mL water, stirring
5 ~ 10 h, the h of heated and stirred 2 ~ 4 at 60 ~ 90 DEG C, are cooled to room temperature, filter, filtrate slow evaporation at room temperature, after 4-5 days
Obtain red bar-shaped material.Yield about 52 ~ 74%.
Product is characterized by single crystal X diffraction, elementary analysiss, obtains the accurate information with regard to crystal structure.Specifically
As a result it is as follows：
The molecular formula of crystal is (H3DBU)H3V10O28.Its cationic is matched somebody with somebody for the carbon -7- alkene of protonation 1,8- diazabicylos 11
Cation（H3DBU）, anion is H3V10O28 3-。
This invention has mainly synthesized the vanadium oxygen cluster compound catalyst of an organic inorganic hybridization, has been applied
In epoxidation of styrene reaction.This invention relate to (H3DBU)H3V10O28The preparation method of compound catalyst.It is this kind of to urge
Agent can realize that epoxidation of styrene reacts, and up to 92%, selectivity is up to 94% to high conversion rate.The preparation method of such catalyst
Course of reaction is simple.
Description of the drawings
Fig. 1 is compound (H3DBU)H3V10O28Crystal structure（For clear, V10O28On hydrogen atom save）.
Specific embodiment
With reference to embodiment, the invention will be further described, but protection domain is not limited by this.
It is raw materials used in embodiment all to buy from market.
Instantiation 1：
Ammonium metavanadate is sequentially added in the round-bottomed flask of a cleaning（1mmol）, vanadyl acetylacetonate（2mmol）, DBU
(1.5 mmol) and 80 mL water, stir 5h, and heated and stirred 2h at 90 DEG C is cooled to room temperature, filter, and filtrate is at room temperature
Slow evaporation, obtains red bar-shaped material after 6 ~ 8 days.Yield about 54%.
Instantiation 2：Ammonium metavanadate is sequentially added in the round-bottomed flask of a cleaning（1mmol）, vanadyl acetylacetonate
（3mmol）, DBU (1.5 mmol) and 80 mL water stir 5h, and heated and stirred 4h at 90 DEG C is cooled to room temperature, filters,
Filtrate slow evaporation at room temperature, obtains red bar-shaped material after 6 ~ 8 days.Yield about 65%.
Instantiation 3：Ammonium metavanadate is sequentially added in the round-bottomed flask of a cleaning（3mmol）, vanadyl acetylacetonate
（4mmol）, DBU (3 mmol) and 60 mL water stir 7h, and heated and stirred 2h at 90 DEG C is cooled to room temperature, filters, filter
Liquid slow evaporation at room temperature, obtains red bar-shaped material after 6 ~ 8 days.Yield about 67%.
Instantiation 4：Ammonium metavanadate is sequentially added in the round-bottomed flask of a cleaning（2mmol）, vanadyl acetylacetonate
（3mmol）, DBU (2 mmol) and 60 mL water stir 8h, and heated and stirred 2h at 70 DEG C is cooled to room temperature, filters, filter
Liquid slow evaporation at room temperature, obtains red bar-shaped material after 6 ~ 8 days.Yield about 74%.
Instantiation 5：Ammonium metavanadate is sequentially added in the round-bottomed flask of a cleaning（2mmol）, vanadyl acetylacetonate
（3mmol）, DBU (2 mmol) and 80 mL water stir 9h, and heated and stirred 4h at 80 DEG C is cooled to room temperature, filters, filter
Liquid slow evaporation at room temperature, obtains red bar-shaped material after 6 ~ 8 days.Yield about 70%.
Instantiation 6：Ammonium metavanadate is sequentially added in the round-bottomed flask of a cleaning（1mmol）, vanadyl acetylacetonate
（3mmol）, DBU (1 mmol) and 60 mL water stir 7h, and heated and stirred 2h at 80 DEG C is cooled to room temperature, filters, filter
Liquid slow evaporation at room temperature, obtains red bar-shaped material after 6 ~ 8 days.Yield about 66%.
Instantiation 7：Ammonium metavanadate is sequentially added in the round-bottomed flask of a cleaning（1mmol）, vanadyl acetylacetonate
（2mmol）, DBU (1.5 mmol) and 60 mL water stir 6h, and heated and stirred 4h at 70 DEG C is cooled to room temperature, filters,
Filtrate slow evaporation at room temperature, obtains red bar-shaped material after 6 ~ 8 days.Yield about 59%.
Instantiation 8：Ammonium metavanadate is sequentially added in the round-bottomed flask of a cleaning（4mmol）, vanadyl acetylacetonate
（4mmol）, DBU (3 mmol) and 80 mL water stir 9h, and heated and stirred 2h at 80 DEG C is cooled to room temperature, filters, filter
Liquid slow evaporation at room temperature, obtains red bar-shaped material after 6 ~ 8 days.Yield about 64%.
Gained vanadium system of the invention oxygen cluster compound catalyst, molecular formula is：(H3DBU)H3V10O28。
Fig. 1 is compound (H3DBU)H3V10O28Crystal structure.Table 1 below is the crystallographic data of the compound.
Table 1
Test example：(H3DBU)H3V10O28Application of the compound catalyst in Catalytic Oxidation of Styrene：Take styrene
2mmol, acetonitrile 10mL, 70% tert-butyl hydroperoxide 3mmol, and the gained catalyst 13mg of embodiment 1 is added, heated and stirred is simultaneously
Temperature is maintained at 40 ~ 60 degrees Celsius, after 10 ~ 16h of reaction, through gas chromatographic analysiss, cinnamic conversion ratio is selected up to 92%
Property is up to 94%.
Claims (6)
1.(H3DBU)H3V10O28Compound catalyst, is characterized in that, structural formula is：
。
2. (H according to claim 13DBU)H3V10O28The preparation method of compound catalyst, is characterized in that, to 100
Ammonium metavanadate, vanadyl acetylacetonate, water, DBU are sequentially added in mL round-bottomed flasks, it is Celsius 60 ~ 90 after 5 ~ 10h of strong agitation
Degree 2 ~ 4h of reaction, cooling is filtered, and slow evaporation under filtrate room temperature obtains bulk crystals after 4 ~ 5 days.
3. preparation method according to claim 2, is characterized in that, the ratio metavanadic acid of the amount of raw material in course of reaction
Ammonium：Vanadyl acetylacetonate：DBU is 1 ~ 5：2~4：1~3（Preferably, ammonium metavanadate：Vanadyl acetylacetonate：The ratio of the amount of DBU materials
For 2：3：2）.
4. preparation method according to claim 2, is characterized in that, the time is 5 ~ 10h during strong agitation in course of reaction（It is excellent
Choosing, the strong agitation time is 8h）.
5. preparation method according to claim 2, is characterized in that, reaction temperature is 60 ~ 90 degrees Celsius in course of reaction（It is excellent
Choosing, reaction temperature is 70 degrees Celsius）.
6. (H according to claim 13DBU)H3V10O28Compound catalyst is in styrene catalyzed epoxidation reaction
Using.
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| CN106582815B CN106582815B (en) | 2019-04-19 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107093731A (en) * | 2017-05-10 | 2017-08-25 | 南阳师范学院 | Many vanadium oxygen cluster compounds and its preparation method and application, and the lithium ion battery comprising it |
| CN107417741A (en) * | 2017-08-09 | 2017-12-01 | 龙岩学院 | Diethylenetriamine vanadium (III) tungsten (VI) vanadium (IV) oxygen cluster compound and its synthetic method |
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2016
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Patent Citations (4)
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Non-Patent Citations (3)
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| LUDMILA ZUEKOVA ET AL.: ""Synthesis and Properties of Dipropylammonium and 1,3-Propanediammonium Polyvanadates"", 《MONATSHEFTE FUR CHEMIE》 * |
| VIOLAINE COUE ET AL.: ""Synthesis and characterization of two new photochromic organic-inorganic hybrid materials based on isopolyoxomolybdate: (HDBU)3(NH4)[β-Mo8O26]•H2O and (HDBU)4[δ-Mo8O26]"", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107093731A (en) * | 2017-05-10 | 2017-08-25 | 南阳师范学院 | Many vanadium oxygen cluster compounds and its preparation method and application, and the lithium ion battery comprising it |
| CN107093731B (en) * | 2017-05-10 | 2020-01-10 | 南阳师范学院 | Polyvanadyl compound, preparation method and application thereof, and lithium ion battery containing same |
| CN107417741A (en) * | 2017-08-09 | 2017-12-01 | 龙岩学院 | Diethylenetriamine vanadium (III) tungsten (VI) vanadium (IV) oxygen cluster compound and its synthetic method |
| CN107417741B (en) * | 2017-08-09 | 2019-10-22 | 龙岩学院 | Diethylenetriamine vanadium (III)-tungsten (VI)-vanadium (IV)-oxygen cluster compound and its synthetic method |
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