CN106582815B - Vanadium system oxygen cluster compound catalyst, preparation method and application - Google Patents

Vanadium system oxygen cluster compound catalyst, preparation method and application Download PDF

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Publication number
CN106582815B
CN106582815B CN201611182331.7A CN201611182331A CN106582815B CN 106582815 B CN106582815 B CN 106582815B CN 201611182331 A CN201611182331 A CN 201611182331A CN 106582815 B CN106582815 B CN 106582815B
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preparation
dbu
catalyst
compound catalyst
room temperature
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CN106582815A (en
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崔传生
于丽娜
邵明发
孙仁君
蔡建兴
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Liaocheng University
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Liaocheng University
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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Abstract

The invention belongs to catalyst material preparation technical fields, are specifically related to one kind (H3DBU)H3V10O28The preparation method and application of compound catalyst.This kind of catalyst can realize epoxidation of styrene reaction, and conversion ratio is selective up to 94% up to 92%.The preparation method reaction raw materials of such catalyst are cheap and easy to get, and preparation process is simple.

Description

Vanadium system oxygen cluster compound catalyst, preparation method and application
Technical field
The invention belongs to catalyst material preparation technical fields, are specifically related to one kind (H3DBU)H3V10O28(DBU 1, 11 carbon -7- alkene of 8- diazabicylo) catalyst preparation method and its application in styrene oxidation.
Background technique
In the numerous substance of multi-metal oxygen cluster, vanadium oxygen cluster is more since vanadium has to appraise at the current rate, thus has unique urge Change characteristic.Therefore more vanadium oxygen clusters are always one of the hot fields of catalytic chemistry man research.More vanadium oxygen clusters are tied at different conditions Structure multiplicity, valence state is changeable, and surface oxygen atoms are also easy to participate in coordination.Structure just because of more vanadium oxygen clusters is more special, If changing reaction condition and reactant type, so that it may derive that many structures are changeable, more vanadium oxygen clusters of different properties.Therefore There is a large amount of document report.But for (H3DBU)H3V10O28Vanadium oxygen cluster yet there are no document report.
In addition, styrene oxidation is a kind of important approach of synthesizing epoxy distyryl compound.Epoxy styrene chemical combination Object is a kind of important oxygenatedchemicals, chemical industry, in terms of there is important application.Therefore epoxy styrene is catalyzed and synthesized Compound is also chemist's focus of attention.Recently, Gulino A. et al. reports (salen) Mn (III) catalyst and realizes The epoxidation (Catal. Sci. Technol., 2015,5,673-679) of styrene, but catalyst preparation is relatively complicated, And the reaction time is longer.Thus design one simply synthesizes and becomes key to the effective catalyst of epoxidation of styrene.
By retrieval, patent document related with the present patent application is not yet found.
Summary of the invention
Technical solution of the invention is: (H3DBU)H3V10O28Composition catalyst, structural formula are as follows:
Mentioned-above (H3DBU)H3V10O28The preparation method of compound catalyst, steps are as follows:
Ammonium metavanadate, vanadyl acetylacetonate, water, DBU are sequentially added into 100 mL round-bottomed flasks, strongly 5 ~ 10h of stirring Afterwards, cooling in 60 ~ 90 degrees Celsius of 2 ~ 4h of reaction, filtering, filtrate slow evaporation at room temperature obtained bulk crystals after 6 ~ 8 days.
Mentioned-above preparation method, Preferable scheme is that, the ratio between amount of raw material ammonium metavanadate in reaction process: second Acyl acetone vanadyl: DBU is that 1 ~ 5:2 ~ 4:1 ~ 3(is preferred, ammonium metavanadate: vanadyl acetylacetonate: the ratio between amount of DBU substance is 2: 3:2).
Mentioned-above preparation method, Preferable scheme is that, the time is that 5 ~ 10h(is preferred when stirring strongly in reaction process , strong mixing time is 8h).
Mentioned-above preparation method, Preferable scheme is that, in reaction process reaction temperature be 60 ~ 90 degrees Celsius (preferably , reaction temperature is 70 degrees Celsius).
The present invention also provides (H3DBU)H3V10O28Application of the catalyst in styrene oxidation.Conversion ratio, selection Property be quantitatively calculated by gas-chromatography.
What the crystal structure information of this kind of catalyst obtained by the following method: synthesizing to obtain by conventional solution reaction (H3DBU)H3V10O28The crystal of compound, specific description experimental method are as follows: successively adding in a clean round-bottomed flask Enter ammonium metavanadate (1 ~ 5 mmol), vanadyl acetylacetonate (2 ~ 4 mmol), DBU (1 ~ 3 mmol) and 40 ~ 80 mL water, stirs 5 ~ 10 h, 2 ~ 4 h of heating stirring, is cooled to room temperature at 60 ~ 90 DEG C, filtering, filtrate slow evaporation at room temperature, after 4-5 days Obtain red rodlike substance.Yield about 52 ~ 74%.
Product is characterized by single crystal X diffraction, elemental analysis, obtains the accurate information about crystal structure.Specifically As a result as follows:
The molecular formula of crystal is (H3DBU)H3V10O28.Wherein cation is protonation 11 carbon -7- of 1,8- diazabicylo Alkene complex cation (H3DBU), anion H3V10O28 3-。
This invention has mainly synthesized the vanadium oxygen cluster compound catalyst an of organic inorganic hybridization, has been applied In epoxidation of styrene reaction.This invention relates to (H3DBU)H3V10O28The preparation method of compound catalyst.It is this kind of to urge Epoxidation of styrene reaction may be implemented in agent, and for high conversion rate up to 92%, selectivity is up to 94%.The preparation method of such catalyst Reaction process is simple.
Detailed description of the invention
Fig. 1 is compound (H3DBU)H3V10O28Crystal structure (for clarity, V10O28On hydrogen atom save).
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the scope of protection is not limited by this.
It is raw materials used in embodiment all to be bought from market.
Specific example 1:
Ammonium metavanadate (1mmol), vanadyl acetylacetonate (2mmol), DBU are sequentially added in a clean round-bottomed flask (1.5 mmol) and 80 mL water stir 5h, and heating stirring 2h, is cooled to room temperature at 90 DEG C, and filtering, filtrate is at room temperature Slow evaporation obtains red rodlike substance after 6 ~ 8 days.Yield about 54%.
Specific example 2: ammonium metavanadate (1mmol), vanadyl acetylacetonate are sequentially added in a clean round-bottomed flask (3mmol), DBU (1.5 mmol) and 80 mL water stir 5h, and heating stirring 4h, is cooled to room temperature at 90 DEG C, filtering, Filtrate slow evaporation at room temperature obtains red rodlike substance after 6 ~ 8 days.Yield about 65%.
Specific example 3: ammonium metavanadate (3mmol), vanadyl acetylacetonate are sequentially added in a clean round-bottomed flask (4mmol), DBU (3 mmol) and 60 mL water stir 7h, and heating stirring 2h, is cooled to room temperature at 90 DEG C, filter, filter Liquid slow evaporation at room temperature obtains red rodlike substance after 6 ~ 8 days.Yield about 67%.
Specific example 4: ammonium metavanadate (2mmol), vanadyl acetylacetonate are sequentially added in a clean round-bottomed flask (3mmol), DBU (2 mmol) and 60 mL water stir 8h, and heating stirring 2h, is cooled to room temperature at 70 DEG C, filter, filter Liquid slow evaporation at room temperature obtains red rodlike substance after 6 ~ 8 days.Yield about 74%.
Specific example 5: ammonium metavanadate (2mmol), vanadyl acetylacetonate are sequentially added in a clean round-bottomed flask (3mmol), DBU (2 mmol) and 80 mL water stir 9h, and heating stirring 4h, is cooled to room temperature at 80 DEG C, filter, filter Liquid slow evaporation at room temperature obtains red rodlike substance after 6 ~ 8 days.Yield about 70%.
Specific example 6: ammonium metavanadate (1mmol), vanadyl acetylacetonate are sequentially added in a clean round-bottomed flask (3mmol), DBU (1 mmol) and 60 mL water stir 7h, and heating stirring 2h, is cooled to room temperature at 80 DEG C, filter, filter Liquid slow evaporation at room temperature obtains red rodlike substance after 6 ~ 8 days.Yield about 66%.
Specific example 7: ammonium metavanadate (1mmol), vanadyl acetylacetonate are sequentially added in a clean round-bottomed flask (2mmol), DBU (1.5 mmol) and 60 mL water stir 6h, and heating stirring 4h, is cooled to room temperature at 70 DEG C, filtering, Filtrate slow evaporation at room temperature obtains red rodlike substance after 6 ~ 8 days.Yield about 59%.
Specific example 8: ammonium metavanadate (4mmol), vanadyl acetylacetonate are sequentially added in a clean round-bottomed flask (4mmol), DBU (3 mmol) and 80 mL water stir 9h, and heating stirring 2h, is cooled to room temperature at 80 DEG C, filter, filter Liquid slow evaporation at room temperature obtains red rodlike substance after 6 ~ 8 days.Yield about 64%.
Gained vanadium system of the invention oxygen cluster compound catalyst, molecular formula are as follows: (H3DBU)H3V10O28。
Fig. 1 is compound (H3DBU)H3V10O28Crystal structure.The following table 1 is the crystallographic data of the compound.
Table 1
Test example: (H3DBU)H3V10O28Application of the compound catalyst in Catalytic Oxidation of Styrene: styrene is taken 2mmol, acetonitrile 10mL, 70% tert-butyl hydroperoxide 3mmol, and 1 gained catalyst 13mg of embodiment is added, heating stirring is simultaneously Maintain temperature at 40 ~ 60 degrees Celsius, after reacting 10 ~ 16h, by gas chromatographic analysis, the conversion ratio of styrene is selected up to 92% Property is up to 94%.

Claims (5)

1.(HDBU) 3H3V10O28The preparation method of compound catalyst, characterized in that structural formula are as follows:
；
Ammonium metavanadate, vanadyl acetylacetonate, water, DBU, raw material in reaction process are sequentially added into 100 mL round-bottomed flasks The ratio between amount ammonium metavanadate: vanadyl acetylacetonate: DBU is 1 ~ 5:2 ~ 4:1 ~ 3, after 5 ~ 10h of stirring strongly, at 60 ~ 90 degrees Celsius 2 ~ 4h is reacted, cooling, filtering, filtrate slow evaporation at room temperature obtained bulk crystals after 4 ~ 5 days.
2. preparation method according to claim 1, characterized in that the ratio between amount of raw material metavanadic acid in reaction process Ammonium: vanadyl acetylacetonate: DBU 2:3:2.
3. preparation method according to claim 1, characterized in that the time is 8h when stirring strongly in reaction process.
4. preparation method according to claim 1, characterized in that reaction temperature is 70 degrees Celsius in reaction process.
(HDBU) 5. of preparation method preparation according to claim 13H3V10O28Compound catalyst is styrene catalyzed Application in epoxidation reaction.
CN201611182331.7A 2016-12-20 2016-12-20 Vanadium system oxygen cluster compound catalyst, preparation method and application Expired - Fee Related CN106582815B (en)

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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
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

Citations (4)

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CN1260786A (en) * 1997-05-29 2000-07-19 耶路撒冷希伯来语大学依苏姆研究开发公司 Process for epoxidation of alkenes
CN101456586A (en) * 2008-12-22 2009-06-17 浙江工业大学 Li2Na4V10O28 and preparation method and use thereof
CN103589450A (en) * 2012-08-14 2014-02-19 中国科学院大连化学物理研究所 Ultra-deep oxidative desulfurization method of diesel oil
CN105597824A (en) * 2015-12-22 2016-05-25 聊城大学 Imidazole functionalized molybdenum oxygen cluster catalyst as well as preparation method and application thereof

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CN103589450A (en) * 2012-08-14 2014-02-19 中国科学院大连化学物理研究所 Ultra-deep oxidative desulfurization method of diesel oil
CN105597824A (en) * 2015-12-22 2016-05-25 聊城大学 Imidazole functionalized molybdenum oxygen cluster catalyst as well as preparation method and application thereof

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Title
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"无机-有机杂化多钒氧簇合成及烯烃环氧化特性";牛彦红等;《中国化学会第六届全国多酸化学学术研讨会论文摘要集》;20150918;第143页
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》.2006,第179卷(第12期),第3615-3627页.

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