CN107597172A - SBA 15 for formoxy- chemical conversion carboxylic acid loads Anderson types heteropolyacid catalyst, preparation method and application - Google Patents
SBA 15 for formoxy- chemical conversion carboxylic acid loads Anderson types heteropolyacid catalyst, preparation method and application Download PDFInfo
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- CN107597172A CN107597172A CN201710817764.3A CN201710817764A CN107597172A CN 107597172 A CN107597172 A CN 107597172A CN 201710817764 A CN201710817764 A CN 201710817764A CN 107597172 A CN107597172 A CN 107597172A
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- 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
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- 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
Abstract
The invention discloses a kind of SBA 15 for formoxy- chemical conversion carboxylic acid to load Anderson types heteropolyacid catalyst, preparation method and application.It prepares Fe Anderson polyacid with iron molybdate and ferric sulfate first；Then infusion process is used, by changing SBA 15 addition, prepares the Anderson type loaded by heteropoly acid catalyst of different loads amount, uses it for formoxy- chemical conversion carboxylic acid.The preparation technology and required equipment of the present invention is simple, and the advantage that reaction temperature substantially reduces, it is easy to accomplish large-scale production.The SBA 15 of acquisition, which loads Anderson type heteropolyacid catalysts, greatly shortens the catalysis oxidation time, and catalyst amount is very small, and is easily recycled, and yield also increases.
Description
Technical field
The present invention relates to catalysis technical field, is related to a kind of carried heteropoly acid catalyst, specifically a kind of SBA-
15 load [FeⅢMo6] Anderson types heteropolyacid catalyst, preparation method and application.
Background technology
Oxidation reaction is one of reaction most basic in nature, wherein, it is most common by formoxy- chemical conversion carboxylic acid.Although
Formoxy- can be melted into corresponding carboxylic acid by shirtsleeve operation in the lab, but the catalysis used in existing processes
Agent has specific surface area small, and toxicity is larger, and utilization rate is low, it is costly the deficiencies of.So low-conversion and the detrimental catalytic agent of aldehyde
Use be always the significant challenge faced in process of scientific research.Used mostly in today, these oxidation reactions
Evil oxidant, such as KMnO4, CrO3, KHSO5, KIO4.Molecular oxygen has many advantages relative to other oxidants, uses molecule
The economical in reaction high efficiency of oxygen and unique accessory substance are nontoxic water.However, by the use of molecular oxygen as terminal oxidized dose by aldehyde
Be catalytically oxidized to that carboxylic acid is still seldom, can direct activation molecular oxygen catalyst it is limited, and the use of noble metal increases reality
Test cost.In addition, using cheap and rich in substantial amounts of transition metal catalyst system, its catalyst system used can not be
It is commercially available, and can not be recycled.
Compared with ordinary organic solvents, naturally abundant water and its intrinsic more green characteristic make it for more environment friend
The development very attractive of good reaction.Such as have document report example of silver or copper catalysis aerobic oxidation in water,
Successfully by carboxylic acid of the various formoxy-s chemical conversion with almost 100% conversion ratio under gentle reaction condition.But this reacts
The middle organic ligand used is easy to oxidation from degrading, and thus limits its serviceability.Therefore can find a kind of Novel pollution-free and
The catalyst of high catalytic efficiency is extremely urgent.
Polyacid, as a kind of new multifunction catalyst, excellent performance can be used as in homogeneous and heterogeneous system
Soda acid, redox or bifunctional catalyst, there is the incomparable advantage of catalyst such as metal oxide, be widely used in
The fields such as catalysis, analysis, medicine, electrochemistry, photochemistry and petrochemistry.The structure type of heteropoly acid mainly has：1:12 series As
Type (structure with Keggin), 1:12 serial Type Bs (Silverton structures), 2:18 serial (Dawson structures) 1:(Waugh is tied 9 series
Structure and Keggin derived structures), 1:6 serial (Anderson structures) etc..Most common of which is structure with Keggin and Dawson
Structure, in recent years, the report on Anderson type heteropoly acids focus mostly in the optimization of structure and the modification of polyacid.So far,
The no document of research that Anderson types polyacid is applied to catalytic field is formally reported.Although more acid catalysts have many good qualities,
But specific surface area is smaller, the reaction time is longer.How further to improve catalyst makes its optimization, is worth us to do more
Deep research.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of SBA-15 for formoxy- chemical conversion carboxylic acid
Load [FeⅢMo6] Anderson types heteropolyacid catalyst, preparation method and applications.[the Fe of the present inventionⅢMo6] Anderson types
Heteropoly acid composite S BA-15 catalyst is used for the reaction that aldehyde compound is oxidized to carboxylic acid under the atmosphere of oxygen, with conventional method
Compare, the catalyst amount prepared by the present invention is few, substantially reduces the catalytic reaction time, improves reaction to a certain extent
Yield, and recoverable, it is economic and environment-friendly.
Technical scheme is specifically described as follows.
The present invention provides a kind of SBA-15 load Anderson type heteropolyacid catalysts for formoxy- chemical conversion carboxylic acid, and this is urged
Agent is using SBA-15 as carrier, supported on carriers [FeⅢMo6] Anderson type polyacid.Preferably, the diameter control of SBA-15 carriers
System is in 7-10nm.[FeⅢMo6] Anderson type polyacid load capacity be 1~2%.
The present invention also provides a kind of above-mentioned SBA-15 load Anderson type heteropoly acids that carboxylic acid is turned to for formoxy- and urged
The preparation method of agent, comprises the following steps：
(1) will be soluble in water by ammonium molybdate, after being heated to boiling, ferrum sulfuricum oxydatum solutum, while hot stirring, mistake are added thereto
Filter；Then filtrate is stood, waits crystal to separate out, filter drying；Recrystallize again, filter drying and obtain [FeⅢMo6]Anderson
Type polyacid；
(2) by [FeⅢMo6] Anderson type polyacid is configured to the aqueous solution of various concentrations, add in aqueous identical
The SBA-15 hot submersions stirring of amount, filters, dries afterwards, obtains the SBA-15 loads [Fe of different loads amountⅢMo6]
Anderson type polyacid solids.
In the present invention, in step (2), [FeⅢMo6] Anderson types polyacid and SBA-15 mass ratio is 1:10~3:
10。
In the present invention, in step (2), hot submersion temperature is 65~75 DEG C.
The present invention further provides a kind of above-mentioned SBA-15 loads Anderson types for being used for formoxy- chemical conversion carboxylic acid are miscellaneous more
Application of the acid catalyst in terms of formoxy- turns to carboxylic acid.Its reaction expression is as follows：
Wherein：R fatty aldehydes, aromatic aldehyde or heteroaryl aldehyde.Preferably, aldehyde compound is aromatic aldehyde or fatty aldehyde.
The method of above-mentioned application comprises the following steps that：
By aldehyde compound and SBA-15 load Anderson type heteropolyacid catalysts be added in reaction tube, addition go from
Sub- water is passed through oxygen, 6~24h is reacted at a temperature of 65~75 DEG C, react after terminating, isolated respective acids as solvent；
Wherein：Because carrier relative molecular mass is indefinite, so being [Fe with the actually active composition of catalystⅢMo6] Anderson types
The mole of polyacid is amount of calculation；Quantity through Fe ions in the remaining more acid solutions of ICP detections, we can calculate actual more
Sour load capacity is 1%~2%.Thus we calculate：SBA-15 load Anderson type heteropolyacid catalysts inventory be
0.01mol%~0.1mol% of aldehyde compound.Preferably, aldehyde compound is aromatic aldehyde or fatty aldehyde.
Compared to the prior art, the beneficial effects of the present invention are：
1st, the present invention can recycle in catalyst, and it adds organic by after the completion of reaction into phase system
Solvent (ether, ethanol, methanol etc.) so that SBA-15 load Anderson types heteropolyacid catalysts separate out, and are returned after processing
Receive, the reusable reaction that carboxylic acid is turned in formoxy- of catalyst of recovery.
2nd, when catalyst of the present invention turns to the catalytic oxidation of acid for formoxy-, can be carried out directly in aqueous systems anti-
Should, it is green.
3rd, the present invention uses infusion process, by changing the addition of heteropoly acid, prepares the Anderson of different loads amount
Type loaded by heteropoly acid catalyst.The Anderson type heteropoly acid composite S BA-15 catalyst obtained by the method for the present invention is short
Can completes reaction in time, is compared with the heteropolyacid catalyst not loaded, and yield is high and catalyst amount is extremely low, bears
Carrying capacity is only 1%~2%, is one of preferable catalyst during formoxy- is melted into carboxylic acid.The present invention preparation technology and
Required equipment is simple, and the advantage that reaction temperature substantially reduces, it is easy to accomplish the features such as large-scale production.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the SBA-15 load Anderson type heteropolyacid catalysts of the gained of embodiment 1.
Fig. 2 is the infrared ray diffraction spectrogram of the SBA-15 load Anderson type heteropolyacid catalysts of gained.
Fig. 3 is the proton nmr spectra of the catalysis gained benzoic acid of embodiment 11H NMR(CDCl3)。
Fig. 4 is the proton nmr spectra of the catalysis gained parafluorobenzoic acid of embodiment 21H NMR(CDCl3)。
Fig. 5 is the proton nmr spectra of the catalysis gained butyric acid of embodiment 31H NMR(CDCl3)。
Fig. 6 is the schematic diagram for preparing catalyst of the present invention.
Embodiment
The present invention is expanded on further below by specific embodiment and with reference to accompanying drawing, but is not intended to limit the present invention.
Fig. 6 is the schematic diagram for preparing catalyst of the present invention.
Embodiment 1
It is a kind of to load reaction of the Anderson types heteropolyacid catalyst efficient oxidation aldehyde into carboxylic acid with SBA-15
0.0318g (0.3mmol) benzaldehyde is added in clean reaction bulb, it is solvent to add 1ml deionized waters, most
0.0036g SBA-15 load Anderson type heteropolyacid catalysts are added afterwards, react 24h, and after reaction terminates, GC- is surveyed in sampling
MS, learn that reaction substrate conversion ratio is more than 99%.5ml ethanol is taken to add reaction system, centrifugation makes catalyst sedimentation, added
3ml ethanol separating catalyst again, filtering, obtains catalyst, is dried in vacuo.Fig. 3 is the core of the catalysis gained benzoic acid of embodiment 1
Magnetic resonance hydrogen is composed1H NMR(CDCl3)。
Embodiment 2
It is a kind of to load reaction of the Anderson types heteropolyacid catalyst efficient oxidation aldehyde into carboxylic acid with SBA-15
0.0372g (0.3mmol) 4-Fluorobenzaldehyde is added in clean reaction bulb, it is molten to add 1ml deionized waters
Agent, 0.0036g SBA-15 load Anderson type heteropolyacid catalysts are eventually adding, react 24h, after reaction terminates, sampling is surveyed
GC-MS, learn that reaction substrate conversion ratio is more than 99%.5ml ethanol is taken to add reaction system, centrifugation makes catalyst sedimentation, then adds
Enter 3ml ethanol separating catalyst again, filter, obtain catalyst, be dried in vacuo.Fig. 4 is the catalysis gained of embodiment 2 to fluorobenzene first
The proton nmr spectra of acid1H NMR(CDCl3)。
Embodiment 3
It is a kind of to load reaction of the Anderson types heteropolyacid catalyst efficient oxidation aldehyde into carboxylic acid with SBA-15
0.0256g (0.3mmol) butyraldehyde is added in clean reaction bulb, it is solvent to add 1ml deionized waters, finally
0.0036g SBA-15 load Anderson type heteropolyacid catalysts are added, react 24h, after reaction terminates, GC-MS is surveyed in sampling,
Learn reaction substrate conversion ratio 90%.5ml ethanol is taken to add reaction system, centrifugation makes catalyst sedimentation, adds 3ml ethanol again
Secondary separating catalyst, filtering, obtains catalyst, is dried in vacuo.Gained catalyst is used for embodiment 4 after reclaiming.Fig. 5 is to implement
The proton nmr spectra of the catalysis gained butyric acid of example 31H NMR(CDCl3)。
Embodiment 4
It is a kind of to load reaction of the Anderson types heteropolyacid catalyst efficient oxidation aldehyde into carboxylic acid with SBA-15
0.0267g (0.3mmol) butyraldehyde is added in clean reaction bulb, it is solvent to add 1ml deionized waters, finally
The SBA-15 load Anderson type heteropolyacid catalysts reclaimed are added in 0.0035g embodiments 3, react 24h, reaction terminates
Afterwards, GC-MS is surveyed in sampling, learns reaction substrate conversion ratio 89%.It is little with changing compared with the yield of example 3, illustrate this experiment
Catalytic effect is reused after catalyst recovery used still to stablize.
All above-mentioned primary embodiments, it is not this new product of implementation and/or new method to other forms
Limit.Those skilled in the art will utilize this important information, the above modification, to realize similar implementation status.But
All modifications or transformation based on new product of the present invention belong to the right that the present invention retains.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (9)
1. a kind of SBA-15 load Anderson type heteropolyacid catalysts for formoxy- chemical conversion carboxylic acid, it is characterised in that this is urged
Agent is using SBA-15 as carrier, supported on carriers [FeⅢMo6] Anderson type polyacid.
2. SBA-15 according to claim 1 loads Anderson type heteropolyacid catalysts, it is characterised in that SBA-15 is carried
The particle diameter of body is between 7-10nm.
3. SBA-15 according to claim 1 loads Anderson type heteropolyacid catalysts, it is characterised in that [FeⅢMo6]
The load capacity of Anderson type polyacid is 1~2%.
A kind of 4. SBA-15 load Anderson type heteropoly acid catalysis according to claim 1 that carboxylic acid is turned to for formoxy-
The preparation method of agent, it is characterised in that comprise the following steps：
(1) it is ammonium molybdate is soluble in water, after being heated to boiling, ferrum sulfuricum oxydatum solutum is added thereto, stirring, is filtered while hot；Then
Filtrate is stood, waits crystal to separate out, filters drying；Recrystallize again, filter drying and obtain [FeⅢMo6] Anderson type polyacid；
(2) by [FeⅢMo6] Anderson type polyacid is configured to the aqueous solution of various concentrations, add in aqueous same amount of
SBA-15 hot submersions stir, and filter, dry afterwards, obtain the SBA-15 loads [Fe of different loads amountⅢMo6] Anderson types
Polyacid solid.
5. preparation method according to claim 4, it is characterised in that in step (2), [FeⅢMo6] Anderson type polyacid
Mass ratio with SBA-15 is 1:10~3:10.
6. preparation method according to claim 4, it is characterised in that in step (2), hot submersion temperature is 65~75
℃。
A kind of 7. SBA-15 load Anderson type heteropoly acid catalysis according to claim 1 for formoxy- chemical conversion carboxylic acid
Application of the agent in terms of formoxy- turns to carboxylic acid.
8. application according to claim 7, it is characterised in that application process comprises the following steps that：
Aldehyde compound and SBA-15 load Anderson type heteropolyacid catalysts are added in reaction tube, add deionized water
As solvent, oxygen is passed through, 6~24h is reacted at a temperature of 65~75 DEG C, after reaction terminates, isolated respective acids；Its
In：The inventory of SBA-15 load Anderson type heteropolyacid catalysts is 0.01mol%~0.1mol% of aldehyde compound.
9. application according to claim 7, it is characterised in that aldehyde compound is fatty aldehyde, aromatic aldehyde or heteroaryl aldehyde.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424373A (en) * | 2018-04-12 | 2018-08-21 | 上海应用技术大学 | A kind of method that primary amine oxidative coupling prepares imine compound |
| CN111072722A (en) * | 2019-12-27 | 2020-04-28 | 湖北工业大学 | Anderson polyacid and application thereof as CVB3 virus inhibitor |
| CN111150736A (en) * | 2019-12-27 | 2020-05-15 | 湖北工业大学 | Application of mono-iodo benzoic acid modified Anderson polyacid as coxsackie virus inhibitor |
-
2017
- 2017-09-12 CN CN201710817764.3A patent/CN107597172A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| HAN YU, ET AL.: "An efficient iron(III)-catalyzed aerobic oxidation of aldehydes in water for the green preparation of carboxylic acids", 《ANGEW. CHEM. INT. ED.》 * |
| 徐蕾 等，主编: "《负载型多酸光催化材料及应用》", 31 March 2015, 东北师范大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424373A (en) * | 2018-04-12 | 2018-08-21 | 上海应用技术大学 | A kind of method that primary amine oxidative coupling prepares imine compound |
| CN111072722A (en) * | 2019-12-27 | 2020-04-28 | 湖北工业大学 | Anderson polyacid and application thereof as CVB3 virus inhibitor |
| CN111150736A (en) * | 2019-12-27 | 2020-05-15 | 湖北工业大学 | Application of mono-iodo benzoic acid modified Anderson polyacid as coxsackie virus inhibitor |
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Application publication date: 20180119 |