CN109748894A - A method of producing 2,5- furans dicarbaldehyde - Google Patents
A method of producing 2,5- furans dicarbaldehyde Download PDFInfo
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- CN109748894A CN109748894A CN201711088585.7A CN201711088585A CN109748894A CN 109748894 A CN109748894 A CN 109748894A CN 201711088585 A CN201711088585 A CN 201711088585A CN 109748894 A CN109748894 A CN 109748894A
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Abstract
The invention discloses a kind of methods for producing 2,5- furans dicarbaldehyde.Using TiO2Carried metal nano particle efficiently produces 2,5-furandaldehyde using solar energy as the light source and heat source of reaction as photochemical catalyst.The present invention generates thermocatalytic effect using the metal nanoparticle on photochemical catalyst, in the case where not consuming other input energy sources, significantly promotes the rate of 5 hydroxymethyl furfural selective oxidation, is a kind of method that green produces 2,5-furandaldehyde.
Description
Technical field
The present invention relates to solar energy and its applications, in particular to a kind of to utilize sunlight selective oxidation 5 hydroxymethyl furfural
Produce the technology of 2,5- furans dicarbaldehyde.
Background technique
In fossil fuel increasingly depleted today, energy shortages and environmental pollution have become the generation for threatening sustainable development
Criticality problem.Realize the sustainable development of human society, it is necessary to put forth effort to develop using lignocellulose-like biomass as representative
Renewable resource produces clean energy resource and chemicals, reduces the dependence to fossil energy.Currently, research work both domestic and external is
Potentiality through the substitution petroleum refining of preliminary proof biorefinery, and establish more specific target product and conversion pathway.
Wherein, 5 hydroxymethyl furfural (5-Hydroxymethylfurfural, abbreviation HMF) is waste 2,5-furandaldehyde
(2,5-Furandicarbaldehyde, abbreviation DFF) is most representative and development potentiality one of path.As one kind
Multi-functional monomer, DFF have broad application prospects in fields such as pesticide, medicine and materials synthesis.
The process that catalysis oxidation HMF produces DFF at present mostly uses greatly thermocatalytic mode to carry out.From environment and economic angle
Degree considers, is before having development using a kind of clean reproducible energy (luminous energy and oxygen) selective oxidation HMF preparation DFF
The method of scape, the in recent years favor by many researchers.2013, Yurdakal et al. reported a kind of crystallization journey for the first time
Not high rutile titania phase titanic oxide is spent, HMF can be oxidized to DFF, but selectivity only 22% under ultraviolet light.In the recent period,
Krivtsov selects g-C3N4 to be modified from by the way of as photochemical catalyst, and using hot soarfing, to reduce the NH2 not being condensed
Site and the specific surface area for increasing g-C3N4.The catalyst selectively reaches 45% under ultraviolet light, is promoted under normal sunshine
To 50%.
Mainly in the laboratory research stage, efficiency is lower for the development of photocatalysis technology；And traditional thermocatalytic relies primarily on electricity
Energy heat supply, energy consumption are huge.Therefore, it by being combined photocatalysis with heat catalysis using solar focusing effect, both utilized
Ultraviolet and visible light wave range in sunlight realizes light excitation, also realizes thermal excitation using infrared band.Therefore, solar energy is utilized
This cheap reproducible energy carries out photo-thermal catalysis oxidation and produces DFF, can realize the green syt of DFF in a mild condition,
Commercial Prospect is wide.
Summary of the invention
The present invention provides a kind of method for producing 2,5-furandaldehyde, solves in existing photocatalysis to selectively oxidation technology
The problems such as reaction efficiency is low.
The technical scheme is that
Luminous energy and thermal energy are provided using focusing sunlight as catalytic oxidation process, photochemical catalyst is made on the one hand to can absorb ultraviolet light
With visible photo-induced light-catalyzed reaction, the fuel factor on the other hand generated again using focusing sunlight induces heat catalysis,
Significantly promote reaction rate.
The photochemical catalyst is made of the semiconductor material (carrier material) and metal nanoparticle of photocatalytic activity, is used
Photodeposition preparation.Wherein carrier material is nano-TiO2(rutile titania phase), nano-TiO2(Rutile Type), nano-TiO2(Degussa
P25).The metal nanoparticle of load is Au, Ag, Pt, Pd, Ru, Ir, Rh.
The photo-thermal catalytic selectivity produces the reaction of DFF, using heavy wall pressure bottle, by the photochemical catalyst of synthesis with react
Substrate HMF is added in solvent (using benzotrifluoride, toluene, acetonitrile, water), after being filled with pure oxygen, is reacted and is held with soft plug seal
Device.Reaction vessel is ultrasonically treated, comes into full contact with catalyst with reaction substrate.Entire reaction is erected at magnetic heating stirrer
On, and temperature control is carried out to it using circulation.
The beneficial effects of the present invention are embodied in: for the disadvantage that single photocatalytic process reaction rate is slow, utilize sunlight
Light field and thermal field in energy realize that light, hot concerted catalysis, the conversion ratio of HMF promote 6 times or more.
Specific embodiment
Embodiment 1
By TiO2Sample dispersion then adds suitable chlorine into the heat resistant glass cup equipped with 40 mL methanol (10%) solution respectively
Auric acid metal front liquid.It is filled with argon gas in mixed liquor, processing then is sealed to the container.Finally under stirring,
Sealing container is irradiated 2 hours using the high-pressure sodium lamp of 300 W, mixed liquor color changes aubergine (Au forerunner by white
Liquid) after, show that the Au precursor liquid in mixed liquor has been reduced into Au nano particle.Then, sediment is filtered out, and in deionized water
It is cleaned three times in dehydrated alcohol, is placed in 80oC drying in oven 12 hours, finally in Muffle furnace by the catalyst of synthesis with
350oC is calcined 5 hours.Obtain Au2/TiO2Photochemical catalyst.
The P160006 heavy wall pressure bottle (15mL) produced using Beijing Xin Weier glass apparatus Co., Ltd is closed 10 mg
At Au2/TiO2The benzyl alcohol of photochemical catalyst and 0.1 mmol are added in the benzotrifluoride solvent of 1.5 mL, are filled with purity and are
99.99% 5 min of oxygen, and with polytetrafluorethylescrewed screwed lid sealed reaction vessel.Reactor, which is ultrasonically treated 3 minutes, to be made to urge
Agent comes into full contact with reaction substrate.The reactor handled well is placed on blender, (too using simulation using convergence sunlight
Sunlight, light intensity are 15 times of AM1.5) irradiation reactor 4 hours.Entire reaction is erected in magnetic heating stirrer, and is utilized
Circulation carries out temperature control to it.Analysis the result shows that, when reaction temperature is limited to 30oWhen C, the conversion ratio of HMF is
The selectivity of 31.4%, DFF are 84.3%；When reaction temperature is limited to 60oWhen C, the conversion ratio of HMF is the selection of 73.1%, DFF
Property is 82.7%.
Embodiment 2
By TiO2Sample dispersion then adds suitable chlorine into the heat resistant glass cup equipped with 40 mL methanol (10%) solution respectively
Platinic acid metal front liquid.It is filled with argon gas in mixed liquor, processing then is sealed to the container.Finally under stirring,
Sealing container is irradiated 2 hours using the high-pressure sodium lamp of 300 W, mixed liquor color changes light grey (Pt forerunner by white
Liquid) after, show that the Pt precursor liquid in mixed liquor has been reduced into Pt nano particle.Then, sediment is filtered out, and in deionized water
It is cleaned three times in dehydrated alcohol, is placed in 80oC drying in oven 12 hours, finally in Muffle furnace by the catalyst of synthesis with
350oC is calcined 5 hours.Obtain Pt2/TiO2Photochemical catalyst.
The P160006 heavy wall pressure bottle (15mL) produced using Beijing Xin Weier glass apparatus Co., Ltd is closed 10 mg
At Pt2/TiO2The benzyl alcohol of photochemical catalyst and 0.1 mmol are added in the benzotrifluoride solvent of 1.5 mL, are filled with purity and are
99.99% 5 min of oxygen, and with polytetrafluorethylescrewed screwed lid sealed reaction vessel.Reactor, which is ultrasonically treated 3 minutes, to be made to urge
Agent comes into full contact with reaction substrate.The reactor handled well is placed on blender, (too using simulation using convergence sunlight
Sunlight, light intensity are 15 times of AM1.5) irradiation reactor 4 hours.Analysis the result shows that, when reaction temperature is limited to 60oWhen C,
The selectivity that the conversion ratio of HMF is 80.9%, DFF is 87.2%.
Comparative example 1
The P160006 heavy wall pressure bottle (15 mL) produced using Beijing Xin Weier glass apparatus Co., Ltd, by 10 mg TiO2
The benzyl alcohol of photochemical catalyst and 0.1 mmol are added in the benzotrifluoride solvent of 1.5 mL, are filled with the oxygen that purity is 99.99%
5 min, and with polytetrafluorethylescrewed screwed lid sealed reaction vessel.By reactor ultrasonic treatment make within 3 minutes catalyst with react bottom
Object comes into full contact with.The reactor handled well is placed on blender, (uses simulated solar irradiation, light intensity is using convergence sunlight
15 times of AM1.5) irradiation reactor 4 hours.Entire reaction is erected in magnetic heating stirrer, and utilizes circulation pair
It carries out temperature control.Analysis the result shows that, when reaction temperature is limited to 30oWhen C, the conversion ratio of HMF is the choosing of 12.8%, DFF
Selecting property is 40.3%；When reaction temperature is limited to 60oWhen C, the selectivity that the conversion ratio of HMF is 16.3%, DFF is 37.1%.
Claims (5)
1. a kind of method for producing 2,5-furandaldehyde, which is characterized in that utilizing convergence sunlight is catalysis oxidation 5- hydroxyl first
Base furfural process provides luminous energy and thermal energy.
2. a kind of method for producing 2,5-furandaldehyde according to claim 1, which is characterized in that the photochemical catalyst
By with photocatalytic activity semiconductor material and metal nanoparticle form.
3. a kind of method for producing 2,5-furandaldehyde according to claim 2, which is characterized in that the photocatalytic activity
Semiconductor material is nano-TiO2(rutile titania phase), nano-TiO2(Degussa P25).
4. a kind of method for producing 2,5-furandaldehyde according to claim 2, which is characterized in that the metal of the load
Nano particle is Au, Ag, Pt, Pd, Ru, Ir, Rh.
5. a kind of method for producing 2,5-furandaldehyde according to claim 1, which is characterized in that reaction temperature 30 oC
~80oC, wherein preferable temperature is 60 oC。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087371A (en) * | 2019-12-17 | 2020-05-01 | 北京理工大学 | Photocatalytic synthesis method of 2, 5-furan dicarbaldehyde |
| CN111269202A (en) * | 2020-02-26 | 2020-06-12 | 南京林业大学 | Preparation method of 2, 5-furan diformaldehyde under illumination condition |
| CN113198469A (en) * | 2021-05-07 | 2021-08-03 | 云南大学 | Copper-titanium heterojunction photocatalyst and preparation method and application thereof |
| CN113387911A (en) * | 2021-06-11 | 2021-09-14 | 中国科学技术大学 | Method for preparing 2, 5-furan dicarboxaldehyde by photo-catalytic dehydrogenation of 5-hydroxymethyl furfural |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087371A (en) * | 2019-12-17 | 2020-05-01 | 北京理工大学 | Photocatalytic synthesis method of 2, 5-furan dicarbaldehyde |
| CN111269202A (en) * | 2020-02-26 | 2020-06-12 | 南京林业大学 | Preparation method of 2, 5-furan diformaldehyde under illumination condition |
| CN111269202B (en) * | 2020-02-26 | 2022-04-15 | 南京林业大学 | Preparation method of 2, 5-furan diformaldehyde under illumination condition |
| CN113198469A (en) * | 2021-05-07 | 2021-08-03 | 云南大学 | Copper-titanium heterojunction photocatalyst and preparation method and application thereof |
| CN113387911A (en) * | 2021-06-11 | 2021-09-14 | 中国科学技术大学 | Method for preparing 2, 5-furan dicarboxaldehyde by photo-catalytic dehydrogenation of 5-hydroxymethyl furfural |
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Application publication date: 20190514 |