CN109317207A - It is a kind of to be efficiently recycled olefin epoxidation catalysts and its preparation method and application - Google Patents
It is a kind of to be efficiently recycled olefin epoxidation catalysts and its preparation method and application Download PDFInfo
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- CN109317207A CN109317207A CN201811297804.7A CN201811297804A CN109317207A CN 109317207 A CN109317207 A CN 109317207A CN 201811297804 A CN201811297804 A CN 201811297804A CN 109317207 A CN109317207 A CN 109317207A
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- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- 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
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- 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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- B01J2231/72—Epoxidation
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Abstract
The invention discloses one kind using rich nitrogen covalent organic framework material C IN-1 as carrier, the preparation method of the new and effective recyclable epoxidation reaction of olefines catalyst of immobilized polyoxometallate.Catalyst prepared by the present invention can be used for the epoxidation reaction of a variety of alkene when using oxygen as oxygen source, have very high conversion and selectivity, and the recyclable recycling of catalyst.The advantage of the invention is that having the characteristics that preparation method is simple, the reaction time is short, high catalytic efficiency, selectivity height, environmental protection and energy saving, at low cost, have broad application prospects in catalytic field.
Description
Technical field
The invention belongs to catalysis materials and technical field, and in particular to a kind of covalent organic framework material using rich nitrogen is solid
Carry the preparation method and application that polyoxometallate prepares new olefin epoxidation catalysts.
Background technique
Epoxide is the extremely wide important organic synthesis intermediate and industrial chemicals of a kind of purposes, is widely used in fine
The fields such as chemical industry, surfactant, perfume industry, pharmaceuticals industry.The epoxidation reaction of alkene is the important of synthesizing epoxy compound
Approach, oxidant mainly have inorganic oxidizer and organic peroxide two major classes, and wherein oxygen is with its economic and environment-friendly characteristic
It gets more and more people's extensive concerning.With the increase of epoxide demand, catalyst operation persons be dedicated to studying it is cheap,
Efficient olefin epoxidation catalysts easily prepared, being recycled.
Covalent organic framework material (COF) is constituted as emerging one of thermocatalytic material, structure by covalently key connection
Element is all lightweight element, has that structure is predictable, channel design is clear, hole is adjustable, large specific surface area, thermal stability and change
Learn the high feature of stability.The material has a wide range of applications in terms of gas storage, photoelectricity, but the material is in catalytic field
In application there are still wide exploration spaces.The COF material structure being keyed by imines is more stable and in water and common
Organic solvent in do not decompose, be very suitable to the environment of heterogeneous catalytic reaction.Polyoxometallate is as a kind of inexpensive, ring
The selective oxidation of olefins catalysts of guarantor are it has been reported that currently, be carrier loaded with imines covalent organic framework material
The work that polyoxometallate prepares epoxidation reaction of olefines catalyst under Oxygen Condition yet there are no disclosure.So by multi-metal oxygen
Hydrochlorate is immobilized to preparing epoxidation reaction of olefines catalyst on covalent organic framework material with very big application value and development
Prospect.
Therefore, how using polyoxometallate and covalent organic framework material to provide a kind of method simple, at low cost, together
When can be recycled, reactivity and the excellent olefin epoxidation catalysts and preparation method thereof of selectivity are this field skills
The problem of art personnel's urgent need to resolve.
Summary of the invention
In view of this, can be recycled the purpose of the present invention is to provide one kind, for being catalyzed a variety of olefin epoxides
Change the preparation method of the polyoxometallate functionalization covalent organic framework material of reaction and is catalyzed epoxy reactive condition, tool
Preparation is as follows.
(1) preparation of support C IN-1: 1,4- diformyl piperazine, melamine and the dimethyl sulfoxide of proper proportion are added
Enter in reaction kettle crystallization 1-3 days under certain temperature, crude product through excessive dehydrated alcohol, anhydrous propanone, anhydrous tetrahydro furan and
It is filtered after methylene chloride washing, vacuum drying obtains the CIN-1 of imines key connection.
(2) PCoMo11Preparation: PMA is dissolved in ultrapure water, and under 50 °C of constant temperatures, unsaturated carbonate hydrogen is added dropwise
Sodium solution, adjustment pH value are 4 ~ 5, and the CoSO of equimolar quality is then added into the solution4·7H21h is sufficiently stirred in O.It will be molten
Liquid is evaporated to half thick, has stood overnight colourless needles Na2SO4·10H2O is precipitated, and collects filtrate, is precipitated to bulk crystals, ties again
It is brilliant to obtain PCoMo11。
(3) PCoMo is synthesized using infusion process11@CIN-1.CIN-1 is dispersed in the mixed solution of ethyl alcohol and deionized water
In, the PCoMo of equimolar quality is added11, 80 °C of 12 h of reflux.Separating mixture after reaction, solid product ethyl alcohol
It is washed with deionized water.80 °C of very dry 12 h obtain PCoMo11@CIN-1。
Invention olefin epoxida tion catalyst application, its step are as follows:
(4) catalyst, solvent, alkene and isobutylaldehyde are added into the two neck bottles for being equipped with reflux condensing tube and magnetic stirring apparatus, instead
Should during be passed through the molecular oxygen of certain flow, 20 ~ 80 °C of reaction temperature.After reacting a period of time, one is taken out from reaction flask
Quantitative reaction mixture, membrane filtration.It is detected using chromatography.
Preferably, in the preparation method of above-mentioned olefin epoxidation catalysts, crystallization temperature is 160 ~ 180 in step (1)
°C, it can guarantee that the yield of resulting materials is higher within this temperature range, purity is preferable.
Preferably, in the preparation method of above-mentioned olefin epoxidation catalysts, phosphomolybdic acid and CoSO in step (2)4·7H2O
Molar ratio be 1:1.
Preferably, in the preparation method of above-mentioned olefin epoxidation catalysts, in step (2) under 50 DEG C of constant temperatures by
It is added dropwise to saturated sodium bicarbonate solution, adjustment pH value to 4 ~ 5；It is precipitated the study found that pH is crossed lower than sodium sulphate impurity.
Preferably, in the preparation method of above-mentioned olefin epoxidation catalysts, time of repose is at least 12h in step (2),
To prevent the polyoxometallate of preparation from aoxidizing in air, collected in time after crystallization.
Preferably, in the preparation method of above-mentioned olefin epoxidation catalysts, PCoMo in step (3)11With the quality of COF
Than for (1 ~ 3): 1, appropriate load capacity is conducive to improve the efficiency of catalyst, while can be reduced unnecessary waste.
Preferably, in the preparation method of above-mentioned olefin epoxidation catalysts, heating reflux reaction is 80 ° in step (3)
C 12 h of reflux, can make active material be substantially adhered to the inside and surface of carrier under this condition.
The present invention also provides a kind of application of olefin epoxidation catalysts, the catalyst is used for catalyzing expoxidation of olefines
The step of reaction, is as follows:
(1) catalyst, solvent, styrene and isobutylaldehyde are added into the two neck bottles for being equipped with reflux condensing tube and magnetic stirring apparatus,
The molecular oxygen of certain flow is passed through in reaction process.
(2) after reacting a period of time, a certain amount of reaction mixture is taken out from reaction flask, by using after membrane filtration
Gas-chromatography is detected.
Preferably, in the application of above-mentioned olefin epoxidation catalysts, n(styrene): n(isobutylaldehyde)=1:(1 ~ 5), oxygen
Air-flow is set as 5 ~ 30 mL/min, and reaction temperature is 40 ~ 80 °C, due to isobutylaldehyde physico-chemical property, oxygen flow and temperature pair
Alkene epoxidation is affected, so above-mentioned condition can be only achieved ideal effect within the specified scope.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides one kind with rich nitrogen imines
Class covalent organic framework material be the immobilized polyoxometallate of carrier, preparation in oxygen EPOXIDATION OF ALKENES CATALYZED BY it is novel
Catalyst PCoMo11@CIN-1, nitrogen content is abundant in the CIN-1 skeleton of imines key connection, and active material load is relatively firm, urges
Change effect and stability is good, can be recycled；In addition the preparation method of catalyst of the present invention is simple, and raw material is cheap and easy to get, at
This is low, and higher reactivity and selectivity are all had in a variety of epoxidation reaction of olefines, and reaction condition is mild, reaction
Time is short, reaction temperature is low, using oxygen as oxygen source energy conservation and environmental protection.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing is PCoMo of the present invention11The scanning electron microscope (SEM) photograph of@CIN-1.
Fig. 2 attached drawing is PCoMo of the present invention11The infrared spectrogram of@CIN-1.
Fig. 3 attached drawing is PCoMo of the present invention11The evaluation of@CIN-1 catalytic performance.
Fig. 4 attached drawing is PCoMo of the present invention11@CIN-1 circulation experiment by taking styrene as an example is examined or check.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
PCoMo11The preparation of@CIN-1 catalyst includes the following steps:
(1) it prepares support C IN-1: 1.69 g Isosorbide-5-Nitraes-diformyl piperazine, 1.00 g melamines and 12 being added in a kettle
ML dimethyl sulfoxide, 170 °C of 72 h of crystallization, is cooled to room temperature opening reaction kettle.It is filtered to obtain solid CIN-1 with cloth funnel,
Crude product filters after the washing of excessive dehydrated alcohol, anhydrous propanone, anhydrous tetrahydro furan and methylene chloride, and 80 °C of vacuum are dry
Dry 12 h, obtains white powder CIN-1；
(2) it weighs PMA to be dissolved in deionized water, under 50 °C of constant temperatures, saturated sodium bicarbonate solution is added dropwise, adjust
PH value is 4.5, and the CoSO of equimolar quality is then added into the solution4·7H2O, solution, which gradually becomes dark-brown, to be continued to stir
1 h.Solution is evaporated to half thick, has stood overnight colourless needles Na2SO4·10H2O is precipitated, and collects filtrate, analyses to bulk crystals
Out, recrystallization can once obtain PCoMo11；
(3) PCoMo is synthesized using infusion process11@CIN-1: by the mixed solution that CIN-1 is dispersed in water and ethyl alcohol volume ratio is 1:2
In, a certain amount of PCoMo is added11, 80 °C of 12 h of reflux.It crosses after reaction and uses filtered on buchner funnel mixture, it is solid to obtain grey
Body powder ethyl alcohol and milli-Q water.80 °C of very dry 8 h obtain PCoMo11@CIN-1。
Embodiment 2
PCoM11@CIN-1 is catalyzed cyclo-octene epoxidation reaction, is added 20 to being equipped in reflux condensing tube and two neck bottle of magnetic agitation
mg PCoM11@CIN-1 catalyst, 10 mL acetonitriles, 0.28 mL cyclo-octene and 0.72 mL isobutylaldehyde, are passed through 10 mL/min flows
Molecular oxygen, 60 °C of 3 h of reaction take out a certain amount of reaction mixture, membrane filtration from reaction flask.It is examined using chromatography
It surveys.3 h conversion ratios are 98%, 99% or more selectivity.
Embodiment 3
PCoM11The styrene catalyzed epoxidation reaction of@CIN-1 is added 20 to being equipped in reflux condensing tube and two neck bottle of magnetic agitation
mg PCoM11@CIN-1 catalyst, 10 mL acetonitriles, 0.22 mL styrene and 0.72 mL isobutylaldehyde, are passed through 10 mL/min flows
Molecular oxygen, when 60 °C of 1 h of reaction, a certain amount of reaction mixture, membrane filtration are taken out from reaction flask.It is examined using chromatography
It surveys.1 h high conversion rate is up to 99%, selectivity 85%.
Embodiment 4
PCoM11@CIN-1 is catalyzed epoxidation of cyclohexene reaction, is added 20 to being equipped in reflux condensing tube and two neck bottle of magnetic agitation
mg PCoM11@CIN-1 catalyst, 10 mL acetonitriles, 0.20 mL cyclohexene, 0.20 mL chlorobenzene and 0.72 mL isobutylaldehyde, are passed through
The molecular oxygen of 10 mL/min flows when 60 °C of 6 h of reaction, takes out a certain amount of reaction mixture, filter membrane mistake from reaction flask
Filter.It is detected using chromatography.6 h conversion ratios are 54%, selectivity 85%.
Embodiment 5
PCoM11@CIN-1 catalyzed 1-octylene epoxidation reaction is added 20 to being equipped in reflux condensing tube and two neck bottle of magnetic agitation
mg PCoM11@CIN-1 catalyst, 10 mL acetonitriles, 0.32 mL 1- octene and 0.72 mL isobutylaldehyde are passed through 10 mL/min stream
The molecular oxygen of amount when 60 °C of 6 h of reaction, takes out a certain amount of reaction mixture, membrane filtration from reaction flask.6 h conversion ratios
It is 92%, 99% or more selectivity.
Embodiment 6
PCoM11@CIN-1 is catalyzed cyclododecene epoxidation reaction, is added to being equipped in reflux condensing tube and two neck bottle of magnetic agitation
20mg PCoM11@CIN-1 catalyst, 10 mL acetonitriles, 0.38 mL cyclododecene, 0.72 mL isobutylaldehyde, are passed through 10 mL/min
The molecular oxygen of flow when 60 °C of 6 h of reaction, takes out a certain amount of reaction mixture, membrane filtration from reaction flask.6 h conversion
Rate is 92%, 99% or more selectivity.
Embodiment 7
With PCoM11For the styrene catalyzed epoxidation reaction of@CIN-1, catalytic reaction condition is constant, and recycling is urged after reacting primary
Agent, isolated solid catalyst are repeatedly washed with solvent, 80 °C of vacuum drying, the spare circular response of sealed storage.As above
State step PCoM11For five activity of@CIN-1 catalyst circulation there is no losing, conversion ratio is still up to 99%, selectivity 85% with
On.
In addition, electron-microscope scanning and infrared analysis detection are carried out to catalyst obtained above respectively, referring to attached drawing 1-4, figure
1 is PCoMo of the present invention11The scanning electron microscope (SEM) photograph of@CIN-1, as can be seen from the figure PCoMo11@CIN-1 is round fine granularity
, and particle size is smaller, surface area is conducive to greatly the immobilized of active material；Fig. 2 is PCoMo of the present invention11The infrared light of@CIN-1
Spectrogram, as can be seen from the figure the characteristic absorption peak of imido grpup key (C=N) is in 1598cm-1Left and right, PCoMo after load11Feature
Absorption peak is in PCoMo11It corresponding can be found in@CIN-1 infrared spectrogram, and opposite position all has occurred in characteristic absorption peak
It moves, illustrates PCoMo11It successfully loads on CIN-1, PCoMo11There are chemical interactions between support C IN-1；Fig. 3 is
PCoMo11The evaluation of@CIN-1 catalytic performance, catalysis 3 h conversion ratio of cyclo-octene epoxidation reaction are 96%, and selectivity is 99%.It urges
Changing epoxidation of styrene to react 1 h conversion ratio is 99%, and selectivity is 85%.It is catalyzed epoxidation of cyclohexene and reacts 6 h conversion ratios
It is 54%, selectivity is 85%.6 h conversion ratio of catalyzed 1-octylene epoxidation reaction is 92%, and selectivity is 99%.It is catalyzed ring 12
1 h conversion ratio of alkene epoxidation reaction is 90%, and selectivity is 99%；Fig. 4 is by taking styrene catalyzed epoxidation reaction as an example
PCoMo11The styrene catalyzed epoxidation circulation experiment of@CIN-1, PCoM11Five activity of@CIN-1 catalyst circulation do not damage
It loses, conversion ratio is still up to 99%, 85% or more selectivity.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (9)
1. a kind of olefin epoxidation catalysts that can be recycled, which is characterized in that the catalyst is PCoMo11@CIN-1, with
The covalent organic framework material of the imines key connection of rich nitrogen is carrier, the polyoxometallate phosphomolybdic acid PCoMo that immobilized cobalt replaces11
It is prepared.
2. a kind of preparation method of olefin epoxidation catalysts described in claim 1, which comprises the following steps:
(1) covalent organic framework material C IN-1 is prepared: by 1,4- diformyl piperazine, melamine and the diformazan of proper proportion
Sulfoxide is added in reaction kettle crystallization 1-3 days under certain temperature, and crude product is through excessive dehydrated alcohol, anhydrous propanone, anhydrous tetrahydro
It is filtered after furans and methylene chloride washing, vacuum drying obtains the CIN-1 of imines key connection；
(2) polyoxometallate PCoMo is prepared11: phosphomolybdic acid is dissolved in deionized water, and saturated carbon is added dropwise under constant temperature conditions
Sour hydrogen sodium solution adjusts pH value, CoSO is then added4·7H2O is sufficiently stirred；Solution is evaporated to half thick shape, is stood to precipitation
After colourless needles substance, filtrate is collected, PCoMo is recrystallized to obtain11；
(3) infusion process synthesizes PCoMo11@CIN-1: it is by ultrasonic wave that CIN-1 is evenly dispersed in a solvent, then it is added
PCoMo11Hot back flow reaction is carried out, separation product, washing, vacuum drying obtain PCoMo after reaction11@CIN-1。
3. the preparation method of olefin epoxidation catalysts according to claim 2, which is characterized in that appropriate in step (1)
The mass ratio of the material of the 1,4- diformyl piperazine of ratio, melamine and dimethyl sulfoxide is 15:10:2.
4. the preparation method of olefin epoxidation catalysts according to claim 2, which is characterized in that anti-in step (1)
The temperature for answering crystallization in kettle is 160 ~ 180 DEG C.
5. the preparation method of olefin epoxidation catalysts according to claim 2, which is characterized in that 50 in step (2)
Saturated sodium bicarbonate solution, adjustment pH value to 4 ~ 5 are added dropwise under DEG C constant temperature.
6. the preparation method of olefin epoxidation catalysts according to claim 2, which is characterized in that in step (3)
PCoMo11Mass ratio with CIN-1 is (1 ~ 3): 1.
7. the preparation method of olefin epoxidation catalysts according to claim 2, which is characterized in that reaction in step (3)
After with the decompression of cloth funnel filter separation product, solid product ethyl alcohol and deionized water wash 3 ~ 5 times, very at 80 °C
Sky is dry.
8. a kind of application of the described in any item olefin epoxidation catalysts of claim 1-7, which is characterized in that the catalyst
The step of for EPOXIDATION OF ALKENES CATALYZED BY, is as follows:
(1) catalyst, solvent, alkene and isobutylaldehyde are added into the two neck bottles for being equipped with reflux condensing tube and magnetic stirring apparatus, instead
It should be passed through the molecular oxygen of certain flow in the process；
(2) after reacting a period of time, a certain amount of reaction mixture is taken out from reaction flask, by using gas phase after membrane filtration
Chromatography is detected.
9. the application of olefin epoxidation catalysts according to claim 8, which is characterized in that mole of alkene and isobutylaldehyde
Than for 1:(1 ~ 5), solvent for use is acetonitrile or methylene chloride or toluene or n,N-Dimethylformamide, oxygen flow is set as 5 ~
30 mL/min, reaction temperature are 40 ~ 80 DEG C.
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| CN109999917A (en) * | 2019-05-21 | 2019-07-12 | 南昌航空大学 | A kind of the covalent organic framework base composite photocatalyst and preparation method of Organic Pollutants In Water of degrading |
| CN109999917B (en) * | 2019-05-21 | 2021-05-25 | 南昌航空大学 | Covalent organic framework-based composite photocatalyst for degrading organic pollutants in water and preparation method thereof |
| CN111905822A (en) * | 2020-08-10 | 2020-11-10 | 吉林化工学院 | Preparation method of polyoxometallate/covalent organic framework material and application of polyoxometallate/covalent organic framework material in styrene air epoxidation reaction |
| CN111974455A (en) * | 2020-08-17 | 2020-11-24 | 吉林化工学院 | Catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11@PC |
| CN112138698A (en) * | 2020-09-16 | 2020-12-29 | 吉林化工学院 | Preparation method of nitrogen-doped carbon nano material and application of nitrogen-doped carbon nano material in nitrobenzene hydrogenation reaction |
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